Patent Publication Number: US-2023136736-A1

Title: Binary phosphorus nitride protective solid electrolyte intermediary structures for electrode assemblies

Description:
INCORPORATION BY REFERENCE 
     An Application Data Sheet is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed Application Data Sheet is incorporated by reference herein in its entirety and for all purposes. 
    
    
     STATEMENT OF GOVERNMENT SUPPORT 
     This invention was made with Government support under Award No.: DEAR0000772 awarded by the Advanced Research Projects Agency - Energy (ARPA-E), U.S. Department of Energy. The Government has certain rights in this invention. 
    
    
     BACKGROUND 
     Solid state battery technology may be advanced by the incorporation of an electrochemically operable moisture-resistant inorganic film on the surface of a solid electrolyte layer, such as films deposited by sputtering methods. The quality of the film depends on the quality of the sputtering target material, and, in particular, high purity and excellent mechanical integrity is especially important for producing smooth pinhole free films. Sputtering targets that have not been properly fabricated suffer from undesirable features including low density, poor cohesive strength, and friability, which generally leads to subsequent deposition of non-uniform films. The films may also be contaminated by impurities which are present in the target material as a result of its difficult manufacture. Non-uniformity of the target material is generally reproduced in the sputtered film as morphological irregularities and defects, and this is highly undesirable, and in some instances prohibitive, for a smooth dense pinhole film. 
     SUMMARY 
     In one aspect the present disclosure provides a high-quality nitrogen rich thin film having a chemical makeup that - in its as-deposited state - is composed of constituent elements lithium (Li), phosphorus (P) and nitrogen (N). In various embodiments the nitrogen rich Li-P-N film, in its as-deposited state, is amorphous. In various embodiments the nitrogen rich Li-P-N film is substantially devoid of oxygen as a constituent element, and in such instances the film is sometimes referred to herein as oxygen-free. In various embodiments the film is moisture resistant in its as-deposited state. In various embodiments the nitrogen rich Li-P-N film is a single-phase material. In other embodiments the film is multi-phase, composed of two or more phases. For example, multi-phase and amorphous. In accordance with the present disclosure the nitrogen rich Li-P-N film is formed on a substrate surface or a particle surface. For example, in various embodiments, the as-deposited film is formed on the surface of a Li ion conducting solid electrolyte layer serving as substrate. In other embodiments, the film may cover surfaces of a cathode or anode electroactive material layer or powder particle. 
     In a related aspect, the present disclosure provides a surface coated Li ion conducting solid electrolyte layer having a major surface covered by a nitrogen rich Li-P-N film of the present disclosure. In various embodiments the as-deposited film is moisture-resistant, and thereon serves as a protective film on an otherwise moisture-sensitive Li ion conducting solid electrolyte layer that, if not for the presence of the protective film, would adversely react with moisture and/or carbon dioxide in the ambient air or ambient environment of a dry room or glovebox (e.g., Argon filled). In various embodiments the nitrogen rich Li-P-N film (e.g., moisture resistant) serves as an interlayer film for making a solid-state lithium negative electrode. For example, the interlayer stabilizing or, otherwise, enhancing the interface between the solid electrolyte layer on which it is deposited and an anode active material (e.g., lithium metal). In various embodiments the interlayer film is a conversion type interlayer. As described in more detail herein below, in various embodiments, lithium metal, which is deposited onto the as-deposited conversion type interlayer film, reactively converts the interlayer film composition and properties. 
     In another aspect the present disclosure provides a mechanically robust and preferably moisture-resistant physical vapor deposition target (e.g., sputtering target) composed of lithium, phosphorus, and nitrogen as constituent elements of the target material. In various embodiments the target is oxygen-free. In various embodiments the sputtering target is moisture resistant. In various embodiments the target is a precisely shaped ceramic body composed of a nitrogen rich Li-P-N material. In various embodiments, for example, the sputtering target is composed of a moisture-resistant nitrogen rich Li-P-N material. In various embodiments the sputtering target is shaped into a disc-like ceramic body. In other embodiments it is a cylindrically shaped ceramic body. And yet in other embodiments the target material component may be formed as an array of rectangular or circular or oval shaped ceramic tiles composed of moisture resistant nitrogen rich Li-P-N material. 
     In another aspect the present disclosure provides methods of making the afore described Li-P-N based PVD targets (e.g., an Li-P-N sputtering target), and in related aspects to methods of making a nitrogen rich Li-P-N thin film (e.g., on the surface of a solid electrolyte substrate). 
     In yet another aspect, the present disclosure provides a composite solid electrolyte PVD target. In various embodiments the composite solid electrolyte PVD target has a layered architecture composed of a primary target material layer composed of phosphorus and/or nitrogen as constituent elements of the target (e.g., P 3 N 5 ) and a secondary target material disposed between the primary target material and a backing plate of the sputtering target. In various embodiments the primary target material is phosphorus nitride (e.g., composed of a primary (e.g.,P 3 N 5 )ceramic body as the target material) and a second ceramic body, serving as the secondary target material, disposed between the primary (e.g., P 3 N 5 )target material body (e.g., in the form of a sputtering target, such as disc shaped) and the backing plate (e.g., a copper backing plate as is known in the sputtering arts). In various embodiments the second ceramic body is similar in shape and size to the ceramic body of the primary (e.g., P 3 N 5 )target body (e.g., disc shaped). In various embodiments the second ceramic body is a dense layer, typically disc shaped, of lithium phosphate (e.g., Li 3 PO 4  or LiPO 3 ). In various embodiments the first ceramic body, serving as the primary target material layer, is formed as a disc, with a ceramic body density in the range of 40% to 90% dense (e.g., about 40%, or about 50%, or about 60% or about 70%, or about 805 or about 90% dense). In such instances, during sputtering the secondary target material layer (e.g., Li 3 PO 4 ) undergoes sputtering simultaneous with that of the primary target (e.g., the P 3 N 5  target material), and in so doing offers protection against unwanted sputtering from the copper backing plate. 
     In some specific embodiments, a suitable composite solid electrolyte PVD target is composed of a mixture of a first component material of P 3 N 5  or a lithiated phosphorus nitride and a second component material such as LiPO 3 , which serves as a sintering or densifying aid for forming a dense composite target. In various embodiments, the mole ratio of P 3 N 5  to LiPO 3  can be between 50% to 95% P 3 N 5  or 60% to 95%, or 70% to 95%, or 80% to 95%, or 90% to 95%. In various embodiments the mixed composite target has a weight percent of P 3 N 5  that is between 50% to 95% P 3 N 5 , or 60% to 95%, or 70% to 95%, or 80% to 95%, or 90% to 95%. 
     In yet still another aspect the present disclosure relates to improvements of the Li / solid electrolyte interface electrical properties (e.g., sulfide glass solid electrolyte or other solid electrolyte such as Li ion conducting garnets or Li ion conducting phosphates such as lithium titanium phosphates). In various embodiments, improved performance may be achieved by deposition (e.g., physical vapor deposition (PVD)) of a composite film containing phosphorus nitride (e.g., P 3 N 5 ) onto the solid electrolyte surface (e.g., glass surface). In one embodiment, physical vapor deposition of P 3 N 5  and LiPON onto the glass electrolyte surface followed by thermal deposition of Li metal that reacts with the composite film forms a stable interface with low resistance. Suitable physical vapor deposition techniques may include RF sputtering, E-beam, and pulse laser deposition. 
     In various embodiments, a P 3 N 5  compacted powder or solid fragments may be used to make a mosaic target. 
     In another aspect the present disclosure provides a solid electrolyte (e.g., a sheet of Li-conducting solid electrolyte) having a surface that is covered by an as-deposited nitrogen rich Li-P-N surface film of the present disclosure. In a related aspect the present disclosure also provides methods of making a solid electrolyte (e.g., a sheet of Li-conducting solid electrolyte) having a surface that is covered by an as-deposited nitrogen rich Li-P-N surface film of the present disclosure. 
     In another aspect the present disclosure provides a solid-state lithium metal anode and methods of making the same, wherein a nitrogen rich Li-P-N thin film is incorporated in the solid-state anode as conversion type interlayer, as described in more detail herein below. In various embodiments the method includes applying a layer of lithium metal onto the moisture resistant Li-P-N film protected surface of the solid electrolyte. 
     In another aspect the present disclosure provides battery cells and methods of making battery cells using one or more of the afore-described material components and methods of the present disclosure. 
     In another aspect, protection of solid electrolyte surfaces against reaction with moisture during solid electrolyte storage, transportation, and cell assembly in a dry room atmosphere can provide important benefits. Accordingly, in various embodiments the present disclosure describes binary phosphorus nitride thin films (e.g., nanofilms) and methods of making/coating thin binary phosphorus nitride films and protecting/encapsulating one or both major surfaces (or all surfaces) of a Li ion conducting sulfide glass layer (e.g., a sulfide glass solid electrolyte sheet) with a thin coating of a binary phosphorus nitride film (e.g., a P x N y  film, with x and y &gt;0). The disclosure also describes methods for making lithium electrode structures that involve lithiation of the binary phosphorus nitride thin film by applying Li metal directly onto the P x N y  film (e.g., by thermal evaporation of Li metal). In various embodiments the lithiated layer (e.g., Li z P x N y  film, with x, y, and z &gt; 0) is formed by depositing Li metal in an amount that is sufficient to yield a sandwich structure wherein the Li z P x N y  film serves as a solid electrolyte interphase between the sulfide glass sheet and the deposited Li metal layer. Sulfide glass solid electrolyte layers and sheets suitable for use herein and are described in U.S. Pat. 10,164,289, which is incorporated by reference herein for this disclosure. 
     In various embodiments the binary phosphorus nitride thin film of the present disclosure is deposited onto the surface of a sulfide glass sheet as an amorphous P x N y  thin film. It is contemplated that the P x N y  thin film may be converted to a crystalline layer (e.g., by heat treating) and this followed by Li metal deposition and subsequent lithiation. For instance, a P 3  N 5  layer so formed and lithiated (e.g., to Li 7 PN 4  or Li 7 PN 4  or to a mixed phase layer of Li 3  N and Li 3 P). However, the disclosure also contemplates directly lithiating the as-formed amorphous P x N y  thin film. In various embodiments the stoichiometry of the binary phosphorus nitride thin film can be x of about 3 (e.g., 3) and y of about 5 (e.g., 5), and the film a triphosphorus pentanitride (e.g., P 3  N 5 ). Other stoichiometries are also contemplated, including a binary phosphorus nitride thin film having x and y of about 1, and the film a mononitride of phosphorus (e.g., PN). 
     In one aspect the present disclosure provides an intermediary sulfide glass solid electrolyte product that is composed of a sulfide glass solid electrolyte layer (e.g., in the form of a sheet) having a first surface that is protected by a thin precursor conversion coating (such as a nanofilm) that is not lithium-ion conductive and generally devoid of lithium ions. In various embodiments the thin conversion coating (or precursor conversion film) of the intermediary product is a non-metal and in particular embodiments the protective thin film is substantially devoid of metal elements. Preferably, the thin non-metal protective film is substantially non-reactive with ambient humidity in which it is stored or handled. For instance, the intermediary solid electrolyte product may be handled in a dry room environment. In accordance with the present disclosure, in various embodiment the thin film coating on the surface of the sulfide glass solid electrolyte sheet is a phosphorous nitride material. In a particular embodiment the thin film phosphorous nitride coating has a composition of P3N5. Thickness of a suitable thin phosphorous nitride coating can be in the range of 5 nm to 1 um, for example in the range of 5 nm to 100 nm, such as about 5 nm to 10 nm, or 10 nm to 20 nm, or 20 nm to 30 nm, or 30 nm to 40 nm, or 40 nm to 50 nm, or 50 nm to 60 nm, or 60 nm to 70 nm or 70 nm to 80 nm, or 80 nm to 90 nm or 90 nm to 100 nm. Thickness less than 5 nm are also contemplated (e.g., 1 nm to 5 nm), including in the context of multiple coating and lithiation steps, as described hereinbelow. 
     In one aspect the present disclosure provides a method of making the intermediary sulfide glass solid electrolyte product by providing a sheet of lithium-ion conductive sulfide glass and depositing by physical or chemical vapor deposition the phosphorous nitride layer. In particular embodiments the phosphorus nitride layer may be deposited by sputtering or pulsed laser deposition. A thin phosphorus nitride layer may be coated onto one or more glass surfaces to provide such protection. Accordingly, in yet another aspect of the present disclosure there is provided a precursor source for making the phosphorous nitride that is in the form of a substantially dense (e.g., sintered) PVD target (e.g., a sputtering target). In various embodiments powder processing may be used, and a dense sputtering target may be made by sintering phosphorous nitride particles (e.g., sintering P3N5 powders), for instance, by hotisostatically pressing phosphorous nitride particles into a solid article using a hot isostatic press (HIP). In other embodiments, cold isostatic pressing (CIP) may be used to make the target. Pressure may be applied using a gas, typically inert (e.g., argon). For instance, in some suitable implementations of embodiments a powder of a P3N5 or a compact thereof may be sealed inside a container (e.g., a metal enclosure) and then processed at the requisite temperature and pressure to produce the dense target material. Cold isostatic pressing (CIP) is also contemplated herein. In various embodiments the PVD target is a solid of a first composition (e.g., a P3N5) and the thin phosphorus nitride layer is also a solid of the same composition as the target (e.g., P3N5). In yet another embodiment, a deposition target (e.g., a sputtering target) of phosphorus nitride (e.g., P3N5) may be fabricated by melting a starting material of phosphorus nitride (e.g., P3N5), and cooling the melt to a solid block, preferably the as-melted block having the desired shape and size for use as a target (e.g., sputtering target). In a particular embodiment, the P3N5 material may be melted inside a vacuum or controlled atmosphere furnace (e.g., under a partial pressure of nitrogen gas). In various embodiments, the P3N5 may be melted in a mold to form a target of desired shape and size (e.g., a disc), such as an Inconel™ mold or other mold material suitable for processing the material at its melt temperature. 
     In various embodiments the thin phosphorus nitride layer may be deposited as a phosphorus rich layer using a sputtering or pulse laser deposition target that includes elemental P (e.g., black phosphorus), which may be used as a binder therein to improve processability of the P3N5 target. For instance, a suitable sputter target may be composed of at least 50 vol% of P3N5 (e.g., about 95% P3N5 and 5% elemental phosphorus, or about 90% P3N5 and 10% elemental phosphorus, or about 80% P3N5 and 20% elemental phosphorus, or about 70% P3N5 and 30% elemental phosphorus, or about 60% P3N5 and 40% elemental phosphorus, or about 50% P3N5 and 50% elemental phosphorus). In other embodiments it is contemplated that the combination target of P3N5 and elemental phosphorus has less than 50 vol% of P3N5. It is also contemplated that elemental phosphorus may be deposited as a layer on the sulfide glass from a target of elemental phosphorus (e.g., black phosphorus). In various embodiments the target of P3N5 may be made by incorporating lithium phosphide, for example, as a binder material (e.g., Li3P). For instance, a suitable sputter target may be composed of at least 50 vol% ofP3N5 (e.g., about 95% P3N5 and 5% Li3P, or about 90% P3N5 and 10% Li3P, or about 80% P3N5 and 20% Li3P, or about 70% P3N5 and 30% Li3P, or about 60% P3N5 and 40% Li3P, or about 50% P3N5 and 50% Li3P. In yet other embodiments it is contemplated that both elemental P (e.g., black phosphorus) and Li3P may be used as binders for a P3N5 target. For instance, a suitable sputter target may be composed of at least 50 vol% of P3N5 (e.g., about 95% P3N5 and 5% (Li3P + P), or about 90% P3N5 and 10% (Li3P + P), or about 80% P3N5 and 20% (Li3P + P), or about 70% P3N5 and 30% (Li3P+P), or about 60% P3N5 and 40% (Li3P + P), or about 50% P3N5 and 50% (Li3P + P). 
     In yet another embodiment, a target of P3N5 may be made by incorporating lithium nitride as a binder material (e.g., Li3N). In various embodiments the target is made by mixing lithium nitride, which melts at about 813° C., with P3N5 and heated above 813° C. (e.g., heated to 850° C.) which leads to molten Li3N wetting and binding to P3N5 particles to form a solid target mixture. While this disclosure is not limited by any particular theory of operation, in various embodiments it is contemplated that the lithium nitride reacts with the phosphorus nitride particles to form a lithiated phosphorus nitride compound (e.g., 4 Li3N + P3N5 ® Li4PN3). In various embodiments the target is made by heating the mixture to a temperature that melts the lithium nitride component but does not melt the phosphorus nitride component (i.e., the processing temperature is above the melt temperature of Li3N and below the melt temperature of P3N5). In other embodiments, it is contemplated that the lithium nitride and the phosphorus nitride components are heated to a temperature that melts both components. For instance, a suitable sputter target may be composed of at least 50 vol% of P3N5 (e.g., about 95% P3N5 and 5% Li3N, or about 90% P3N5 and 10% Li3N, or about 80% P3N5 and 20% Li3N, or about 70% P3N5 and 30% Li3N, or about 60% P3N5 and 40% Li3N, or about 50% P3N5 and 50% Li3N). 
     In another aspect the present disclosure provides a method of making a lithium metal electrode assembly from the intermediary sulfide glass solid electrolyte product by applying (e.g., depositing) active lithium (e.g., lithium metal) onto the thin phosphorous nitride film to transform it (e.g., the P3N5 film) by reacting it with the deposited lithium metal to effectuate a lithiated phosphorous nitride layer that may be dense and fully reacted by the as-deposited lithium metal to a ternary lithium phosphorous-nitride compound. In various embodiments the transformation is caused to fully take place directly as a result of the lithium metal deposition step (i.e., the layer is a fully lithiated phosphorous nitride layer). In other embodiments, the structure so formed may be treated (e.g., heat treated) to react the phosphorous nitride layer to its full extent (e.g., fully lithiated). For instance, a P3N5 film reacted to a layer of a ternary lithium phosphorous-nitride compound, such as Li4PN3, Li7PN4, LiPN2, Li12P3N9 or Li10P4N10, or a mixed phase layer of Li3N and Li3P, or some combination of Li3N and/or Li3P and a LizPxNy compound, wherein x, y and z &gt; 1. 
     Accordingly, in yet other aspects the present disclosure provides a lithium electrode assembly composed of a sulfide glass solid electrolyte layer having a first surface that is covered in intimate contact by a lithiated phosphorous nitride layer. In accordance with various embodiments of the present disclosure the lithiated phosphorous nitride layer is fully lithiated. However, the disclosure also contemplates a partially lithiated layer. 
     In other aspects the present disclosure provides battery cells composed of the afore described lithium metal electrode assembly and methods of making such battery cells, which involves providing the instant lithium metal electrode assembly and an opposing electrode (e.g., a positive electrode) adjacently opposing the lithium metal electrode assembly. Phosphorus nitride layers described herein and processes for making lithium metal electrode assemblies and phosphorus nitride layer protected solid electrolytes may be applied to other solid electrolyte layers, including oxide-based lithium ion conducting solid electrolyte layers such as those which are generally referred to as garnet or garnet-like. 
     In various embodiments thin metal layers may be coated onto the glass surfaces to provide such protection, and removed prior to cell assembly (e.g., by ion etching the metal layer to remove it). In other embodiments a thin metal layer coating may be converted to a thin electrochemically functional and protective compound layer rather than removed prior to cell assembly. In accordance with the present disclosure, the converted protective compound layer may be composed of the metal element of the thin protective metal layer and a non-metal selected from the group consisting of a nonmetal chalcogen, nonmetal halogen, and nonmetal pnictogen. In various embodiments the nonmetal may be one of oxygen, sulfur, nitrogen, iodine and bromine. The converted protective compound layer is electrochemically functional in that it allows for through transport of lithium ions. Sulfide glasses are known to be highly sensitive to moisture. In a hybrid cell configuration, where the glass is facing liquid electrolyte (catholyte), a benefit of the thin protective compound layer is higher allowable electrolyte moisture content and consequently a reduction in the requirement for dryness of cell components, in particular that of the porous cathode (i.e., positive electrode). 
     In various embodiments the protected sulfide glass solid electrolyte of the present disclosure is composed of a lithium ion conducting sulfide glass sheet having first and second opposing principal side surfaces that are each protected by a converted compound layer. In certain embodiments all surfaces of the glass sheet are covered in a thin protective metal layer that is subsequently converted, on all surfaces, to a protective compound layer, preferably continuous. In various embodiments the protective layers on the first and second major surfaces of the glass sheet have a different chemical and material makeup. The converted compound layers are composed of a metal element, Me, and a non-metal element, X. In various embodiments the converted protective compound so formed is a metal oxide, metal sulfide, metal nitride, metal phosphide or metal halogenide. For instance, in particular embodiments the as-converted compound layer may have the general formula MenXk, where Me is the metal of the thin metal coating (and not lithium) and X is oxygen, sulfur, nitrogen, phosphorous or a halogen, with n and k selected for stoichiometry. A beneficial property of thin protective compound layers with these compositions is the ability to transfer Li ions across during cell charge and discharge. Another property for the case of a fully solid-state cell is protection of the sulfide glass solid electrolyte from oxidation in direct contact with high-voltage cathodes including traditional cathodes used in Li-ion batteries, such as nickel manganese cobalt (NMC) cathodes. 
     In some implementations, conversion to a thin protective compound layer is performed just after deposition of the thin metal layer onto the glass, or in a specific case, later, after the anode is assembled in a dry room atmosphere (e.g., after deposition of a thin seed layer of lithium metal). Accordingly, the thin metal layer, in such instances, may be used for glass protection from reaction with moisture during assembly of the anode (i.e., negative electrode). 
     In various implementations, thin converted protective compound layers are metal oxides that may be formed by converting thin metal layers using the following methods: direct oxidation in oxygen-containing atmosphere (at a variety of temperatures and oxygen partial pressures), treatment in oxygen plasma, and treatment with atomic oxygen (in particular, produced by dissociation of ozone). 
     In various implementations, thin converted protective compound layers are metal sulfide layers that may be formed by converting thin metal layers by direct reaction with sulfur from the gas phase (e.g., sublimed sulfur) or reaction with elemental sulfur dissolved in a liquid carrier (in particular, in amines). The excess of sulfur can be removed by rinsing in amines. 
     In various implementations, thin converted protective compound layers are metal nitride layers that may be formed from thin metal layers by treatment in an atmosphere containing nitrogen or by treatment in nitrogen plasma. 
     In various implementations, a thin converted protective compound layer is a metal halogenide (e.g., iodide, bromide) layer that may be formed from thin metal layers by treatment with halogens (e.g., iodine /bromine) from the gas phase or from liquid solutions of halogens (e.g., iodine / bromine) complexes. 
     In some implementations, these compounds are formed from thin metal layers of Al, Sn, In, Si, Cu, Fe, Mo, W, Ta, and Ti. 
     In a specific implementation, the thin metal layer is Al, which can be deposited onto both sides of a sulfide glass solid electrolyte sheet/ribbon simultaneously. 
     In specific implementations, the entire thin metal layer is fully converted into a thin layer of oxide, sulfide, nitride or halogenide. In specific implementations, the thin metal layer is deposited onto both sides of a sulfide glass solid electrolyte sheet and the thin metal layer on just one side of the sheet is fully converted into a thin layer of oxide, sulfide, nitride or halogenide. 
     In various embodiments the first and/or second protective coating is continuous and lacks through-porosity. 
     In various embodiments, the thin protective metal layer, prior to its conversion to a compound layer, has a thickness of less than 10 nm or about 10 nm, or from 10 nm to 100 nm, from 10 nm to 20 nm, greater than 100 nm. 
     The thickness of the converted protective compound layer is generally in the range of 10 to 100 nm. For example, the compound layer thickness about 10 nm, about 20 nm, about 30 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, or about 100 nm. It is contemplated that in some embodiments the compound layer thickness may be greater than 100 nm(e.g., between 100 to 200 nm or between 200 to 500 nm, orbetween 500 to 1000 nm). 
     In various implementations, a thin converted protective compound layer is a metal oxide layer (e.g., aluminum oxide) and may be formed by UV ozone oxidation of a thin metal (e.g., aluminum) film on a sulfide glass solid electrolyte at room temperature. 
     Also provided herein are methods for protecting a sulfide glass solid electrolyte sheet, including such as sheet protected as described above, during Li deposition and to protected sulfide glass solid electrolyte sheets having a thin material layer coating for providing that protection (i.e., protective coating). The disclosure also provides electrode assemblies constructed from the instant protected sulfide glass solid electrolyte sheets as well as battery cells thereof and methods of making said protected sulfide glass structures, electrode assemblies and battery cells. 
     In one aspect the present disclosure provides a method for protecting a sulfide glass solid electrolyte sheet during Li deposition by coating at least one major surface of the glass sheet with a protective coating that improves the interface between the glass and a layer of Li metal evaporated onto the glass surface. In particular, the protective coating protects the glass surface from a rapid and deep reaction with highly reactive lithium metal from the vapor phase. Possible reactions include a reaction with the glass surface itself as well as with possible glass inclusions such as elemental sulfur and elemental boron or silicon. Preferably, the protective coating also protects the glass surface from reaction with moisture, especially when Li deposition does not immediately follow deposition of the protective coating. 
     Sulfide glasses are known to be very sensitive to moisture. Hydrolysis of glass surface occurs even in the atmosphere of a dry room or of an argon-filled glove box and leads to formation of H2S gas. During Li deposition, H2S that forms on the glass surface reacts with Li from the vapor phase as well as with initial portions of deposited Li and forms lithium sulfide. It leads to consumption of deposited electrochemically active Li metal and also increases the resistance of the Li/glass interface. The use of a protective coating eliminates or greatly reduces these negative effects and makes high rate Li deposition onto glass possible. 
     In various embodiments the protective coatings can be from ten nanometers to several micrometers in thickness and are continuous and pinhole free. In some embodiments the protective coating can be deposited onto the glass sheet just before Li deposition. In other embodiments, Li deposition does not immediately follow deposition of the protective coating and the coated glass is stored for some time in the same vacuum chamber, moved to another chamber, and/or packaged and shipped to another facility for Li deposition. In a particular embodiment, both sides of the glass sheet are covered with a protective coating (deposited sequentially or simultaneously) that protects the glass surface against reaction with moisture during glass storage and/or transportation. Prior to cell assembly the protective coating is removed from the glass surface opposing liquid electrolyte in a hybrid cell configuration or opposing the positive electrode in a fully solid-state cell. In a particular embodiment, the protective coating is removed with ion etching. 
     As noted above, in various aspects the present disclosure relates to a protected sulfide glass solid electrolyte sheet comprising a protective coating on at least a first major surface of the glass and methods of making the protected glass, and to a lithium electrode assembly fabricated by depositing Li metal onto the protective coating. 
     In various alternative embodiments, the protective coating may be a thin metal layer comprising one or more metals that alone or in combination readily alloy with Li metal but does not readily react with sulfur derived from the glass (e.g., from H2S or sulfur inclusions). In one embodiment the protective coating is a thin gold layer. Preferably the protective coating (e.g., gold coating) is sufficiently thick to provide a moisture barrier. Particularly suitable protective coating thicknesses range from about 10 to about 3000 nm (e.g., about 10 or 50 or 100 nm). Thinner gold layer protective coatings are contemplated (e.g., 1 - 5 nm). In various embodiments the protective gold coating is deposited onto both the first and second principal side surfaces of the glass sheet, and in embodiments the gold coating is deposited to cover all exposed surfaces of the glass sheet, including the first and second principal side surfaces as well as the lengthwise edges, and widthwise edges when present. In certain embodiments the gold coating is deposited only onto the first principal side surface. Gold is known to be chemically resistant to sulfur compounds and will not react with H2S, sulfide glass surface, and inclusions of elemental sulfur. Gold forms alloys with lithium. The thickness of the deposited gold layer can be chosen in such a way that the gold is completely consumed by the process of forming an alloy with deposited Li metal. In accordance with this embodiment, the Li-Metal alloy that forms as a result of lithium evaporation onto the protective metal layer coating may eventually react with the glass surface or with inclusions of elemental sulfur. However, with the presence of the protective coating, the reaction is not as rapid and deep when compared to lithium evaporation (i.e., vapor phase Li) onto unprotected glass. 
     In other embodiments, protective metal coating is composed of other suitable metals, such as indium, silver or tin, or more than one type of metal other than Li metal, for example, gold and silver, or gold and indium or gold and tin. In one embodiment the protective coating is a multi-layer. For instance, a first metal layer of gold followed by a second metal layer (e.g., indium, silver or tin). In such said embodiments, the first gold layer may be exceptionally thin (e.g., 1 - 10 nm). When applied as a first layer, thin gold (e.g., about 2 - 5 nm) provides a sufficient cap on the glass surface such that subsequent deposition of a second metal layer can be deposited with limited reaction to sulfur, as it (sulfur from the glass) is retained underneath the thin gold layer. When making an electrode assembly, additional metal layers (e.g., a second or third layer) further protect the glass against adverse reaction with vapor phase Li during lithium evaporation, and, when fully covering all glass surfaces, the protective coating may also provide a moisture barrier to enable transfer of the protected glass to another chamber, and/or to another facility for Li deposition. 
     In other embodiments, the protective coating is a metal sulfide layer that is deposited as a metal onto the glass surface (e.g., via vacuum evaporation), and during metal deposition, sulfur from the glass reacts with the vapor phase metal to form a metal sulfide protective coating on the glass surface(s). Accordingly, the metal(s) is selected for its ability to react with sulfur containing compounds, and in particular H2S, to form a metal sulfide compound(s). Particularly suitable metals for creating the metal sulfide protective coating include Ag, Sn, In, Al, Ge, Si, Cu, Ni, Mo, Fe and combinations thereof. 
     In a particular embodiment, the metal(s) selected to form the metal sulfide compound(s) are Li-alloy-forming metals other than gold, such as Ag, Sn, In, Al, Ge, Si and combinations thereof. When depositing the metal onto the glass surface, the amount of metal deposited is selected in a way that either guarantees full conversion of the metal(s) into metal sulfide(s) to form a single layer protective coating or leaves some fraction of the metal unreacted, thus forming a multi-layer protective coating of a metal sulfide layer serving as a first layer adjacent to and directly contacting the glass surface and a second layer that is a metal layer adjacent to and directly contacting the metal sulfide layer. To construct an electrode assembly, Li metal is deposited onto the protective coating. For the full conversion embodiment, the architecture of the electrode assembly is Li | metal sulfide(s) coating | glass, wherein the deposited Li metal reacts with the metal sulfide layer, resulting in a Li ion conducting Li metal sulfide among other products. For the multi-layer protective coating embodiment, the architecture of the electrode assembly is Li | Li metal alloy | metal sulfide | glass, as the vapor phase Li alloys with the metal. When deposited, vapor phase Li metal reactively alloys the metal layer of the protective coating, and that Li-metal alloy layer so formed subsequently reacts with the metal sulfide layer to form a Li ion conducting metal sulfide. 
     Continuing with reference to the full conversion embodiment as described above, in certain embodiments thereof the sulfide forming metal deposited onto the glass is selected such that it does not alloy, or readily alloy with Li metal, but does react with sulfur from the glass to form a metal sulfide protective coating. In such embodiments it is important to control the amount of metal deposited to ensure that it is fully consumed by the reaction with H2S to form the metal sulfide, otherwise unreacted metal would prevent direct contact between Li and the formed metal sulfides. Particularly suitable metal for this embodiment include Cu, Ni, Mo, Fe and combinations thereof. Reactions of deposited Li with metal sulfides, in particular a conversion-type reaction, can lead to formation of ionically conducting Li sulfides at the Li/glass interface. 
     In aspects the present disclosure provides methods for making a solid-state laminate electrode assembly. 
     In various embodiments the solid-state laminate electrode assembly comprises a lithium metal layer reactively bonded to a lithium ion conducting sulfide glass layer. Preferably, the reactive bond is sufficiently complete that it forms a continuous solid electrolyte interphase (SEI) at the boundary between the layers. 
     In various embodiments, to bring about a continuous SEI, the lithium metal layer should have a major surface, which, just prior to bonding (e.g., by laminating), is in a highly reactive state (i.e., it is substantially unpassivated). In various embodiments the method involves making a pristine lithium metal layer having a substantially unpassivated first major surface, and therefore highly reactive, and maintaining the highly reactive surface in its substantially unpassivated state until it has been reactively bonded with the sulfide glass layer. 
     In various embodiments the method comprises:
     A method for making a solid-state laminate electrode assembly, the method comprising the operations of
   i) providing a lithium metal laminate structure the laminate comprising:
   a. a lithium metal layer having a first major surface that is substantially unpassivated; and   b. an inert protective material layer that removably covers the lithium metal first major surface, the protective material layer in direct contact with the lithium first major surface;   
   ii) providing an inorganic solid electrolyte laminate structure, the laminate comprising:
   a. an inorganic lithium ion conducting sulfide glass layer having a first major surface and an opposing second major surface; and   b. an inert protective material layer that removably covers the sulfide glass first major surface, the protective material layer in direct contact with the sulfide glass;   
   iii) removing the inert protective material layer from the lithium metal first major surface;   iv) removing the inert protective material layer off the sulfide glass first major surface;   v) reactively bonding the sulfide glass layer with the lithium metal layer via their first major surfaces; and   wherein the reactive bond is complete and the interface between the sulfide glass layer and the lithium metal is defined by a continuous solid electrolyte interphase.   
   

     In various embodiments, the inert protective material layer on the sulfide glass first major surface is a liquid phase layer of a dry hydrocarbon liquid, and the inert protective material layer on the substantially unpassivated lithium metal first major surface is a liquid phase layer of a dry hydrocarbon liquid. 
     In various embodiments, the hydrocarbon liquid on the lithium metal surface is removed substantially immediately prior to the reactive bonding operation, and optionally the hydrocarbon liquid on the sulfide glass is removed substantially immediately prior to reactively bonding operation. 
     In various embodiments, the removal of the hydrocarbon liquid is accelerated by the application of one or more heat (conductive or convective), vacuum suction, blowing a jet of dry Ar or He, and blowing a jet of high vapor pressure protective liquid followed by vacuum suction. 
     In various embodiments, the operation of cleaning the first major surface of the sulfide glass layer under an inert plasma (e.g., Argon plasma), by ion etching; wherein the cleaning operation is performed after the liquid phase layer of protective fluid has been removed. 
     In various embodiments, the operation of treating the clean first major surface of the sulfide glass under a Nitrogen containing plasma, wherein the treatment modifies the surface composition of the sulfide glass by introducing Nitrogen into/onto the glass surface. 
     In various embodiments, the operation of treating the clean sulfide glass first major surface to form a precursor film consisting of 1 to 5 monolayers of a halogen (e.g., iodine) or an interhalogen, or nitrogen onto the clean glass surface, wherein the monolayer(s) react with lithium on bonding to form a solid electrolyte interphase. 
     In various embodiments, the operation of treating the clean sulfide glass first major surface to form a precursor film of Nitrogen molecules on the glass surface. 
     In various embodiments, the solid electrolyte interphase comprises Li3N. 
     In various embodiments, a method of making a lithium metal layer having a substantially unpassivated first major surface, and preferably a pristine surface, includes extruding lithium metal directly into a liquid phase of protective fluid (e.g., super dry liquid hydrocarbon). 
     In various embodiments, a method of making a lithium metal layer having a substantially unpassivated first major surface, and preferably a pristine surface, includes extruding lithium metal and substantially immediately covering the freshly formed lithium metal surfaces with a liquid phase protective fluid. 
     In various embodiments, the extrusion comprises at least two extrusions performed by roll reduction, and the as-extruded lithium metal layers are substantially immediately covered in liquid phase protective fluid right after each roll reduction operation and maintained under liquid phase protective fluid throughout the process. 
     In various embodiments, the extrusion comprises purifying a stock of lithium metal to remove non-metallic impurities so that the concentration of nitrogen in the purified lithium stock is not greater than 500 ppm, and extruding the purified lithium metal stock to form a lithium metal foil having a first and second major surface and thickness less than 50 um. 
     In various embodiments, the lithium metal layer is in the form of a long continuous roll, and the method further comprises the operation of placing the lithium metal roll into a hermetic canister filled with liquid phase protective fluid, the lithium metal layer completely immersed within the protective fluid. 
     In various embodiments, the substantially unpassivated first major surface of the lithium metal layer has never been in direct touching contact with a gas phase atmosphere or vacuum. 
     In various embodiments, a lithium metal laminate structure is provided. The laminate includes:
     i) a lithium metal layer having a first and second major surface, wherein the first major surface is substantially unpassivated; and   ii) a protective material layer that removably covers and protects the lithium first major surface in direct contact.   
 In various embodiments, the substantially unpassivated lithium metal surface is stable.
     In various embodiments, the protective material layer is a liquid phase hydrocarbon liquid, preferably super dry. 
     In various embodiments, a lithium metal laminate structure is formed via thermal evaporation of lithium metal onto a substrate, and then substantially immediately covering the fresh formed lithium metal layer with a protective material layer (e.g., a liquid phase hyrdrocarbon liquid). In some embodiments the substrate on which the lithium metal layer is formed is copper foil. In other embodiments the substrate may be a metallized polymeric film (e.g., a PET film metallized with Cu, Ni or the like). In a particular embodiment the liquid phase hydrocarbon is applied onto the first major surface of the evaporated lithium metal layer by gravure printing the hydrocarbon liquid (i.e., via a gravure cylinder). 
     In various embodiments, to achieve smooth lithium surface the evaporated lithium metal layer may be treated by ion bombarding its surface (e.g., using low-energy Argon ion bombardment). For instance, the thermal evaporator may be equipped with an ion gun that generates ions with energies of a few keV. The ion bombardment may be applied during evaporation of the lithium metal, or exclusively after the lithium metal layer has formed. The process is generally referred to as ion-beam assisted deposition (IBAD). In this instance, the ion bombardment is a process that takes place after the lithium metal layer has formed. IBAD is a process known for making optical quality mirrors, and is applied here for making a high quality and smooth lithium metal surface. Once evaporated and optionally smoothed by ion bombardment, the lithium metal surface is substantially immediately covered in protective fluid, thus forming a lithium metal laminate structure of the present disclosure. The protective fluid may be applied inside the vacuum chamber of the evaporator (and while under vacuum), or it may be applied in a dry box that is configured to receive the evaporated lithium metal layer. In various embodiments the layer of protective fluid is applied to the lithium metal surface using a gravure printing process, as described in more detail hereinbelow. 
     When the lithium metal layer is formed by evaporation (e.g., thermal evaporation) its thickness is generally not greater than 10 um, and more typically not greater than 5 um (e.g., it is about 5 um, or about 4 um, or about 3 um, or about 2 um, or about 1 um). In some embodiments the thickness of the evaporated lithium metal layer is ultra-thin, e.g., less than 1 um (e.g., about 100 nm, or about 200 nm, or about 300 nm, or about 400 nm or about 500 nm) thick. As described in more detail herein below, once the evaporated lithium metal layer is encapsulated by the protective liquid layer, it may be rolled or otherwise covered with a solid material release layer to form a lithium metal laminate structure having a wet-decal architecture as described in detail herein below. 
     In various embodiments the solid-state laminate electrode assembly of the present disclosure is formed by depositing lithium metal onto a freestanding (or freestandable) sulfide solid electrolyte glass layer (e.g., a sulfide glass sheet) or directly onto a nanofilm-encapsulated sulfide glass solid electrolyte sheet (as described herein below) using a physical vapor deposition technique such as evaporation or sputtering (e.g., thermal evaporation), the sulfide glass sheet (e.g., nanofilm-encapsulated) serves as the substrate for lithium deposition). 
     When referring to the sulfide glass sheet as “freestanding” or “freestandable” it is meant that the sheet is a self-supporting layer that displays a mechanical strength (e.g., tensile strength) sufficient to allow it (the sheet) to remain intact in the ab sence of a substrate (i.e., self-supporting), and thereby the freestanding solid electrolyte sheet is not dependent upon another self-supporting layer for its continuous intact existence (e.g., a positive or negative electrode layer or an inert carrier film). Accordingly, in various embodiments the instant freestanding solid electrolyte sulfide glass sheet is “substrate-less.” 
     In some embodiments it is contemplated that the lithium metal layer may be thermally evaporated directly onto the glass first major surface, or a precursor film (as described above and below) may be applied to the glass first major surface, and the lithium metal layer deposited onto the precursor film to form an engineered solid electrolyte interphase (SEI) having improved electrochemical properties. 
     When thermally evaporating the lithium metal layer onto the freestanding sulfide glass sheet (e.g., a nanofilm-encapsulated glass sheet, as described herein below), care is to be taken to ensure that the sulfide glass does not devitrify and the sheet’s first major surface is not damaged by the evaporation (e.g., thermally damaged). In various embodiments the sulfide glass substrate sheet (e.g., nanofilm-encapsulated) is actively cooled during thermal evaporation of lithium metal. Preferably, the temperature of the sulfide glass sheet is at a temperature of 100° C. or less during the evaporation process. By “actively cooled” it is meant that the sulfide glass sheet is cooled while the evaporation of lithium metal is taking place. In various embodiments the substrate (i.e., the sulfide glass sheet) is positioned in a material frame (e.g., a ceramic frame) and while lithium metal is coated onto the first major surface (or precursor film), the opposing second major surface is actively cooled (e.g., by flowing a cool inert gas in direct contact with the second major surface). Typically the cool inert gas is cold Argon, and preferably obtained from a cryogenic Argon tank. For instance, the inert gas (e.g., cool Argon gas) contacts the sulfide glass second major surface and it (the gas) is applied to the surface at a temperature that is no greater than 10° C., or no greater than 0° C., or no greater than -10° C., or no greater than - 20° C. When actively cooling the sulfide glass sheet during evaporation, the sheet is preferably release-ably sealed to the ceramic frame in order to prevent the cool Argon gas from releasing into the vacuum chamber of the evaporator or from diffusing into the evaporating lithium flux (e.g., the edges of the glass sheet glued to the frame, such as with an epoxy). In various embodiments several frames are incorporated into a cassette of frames, to allow for multiple evaporations in a single run. In other embodiments the sulfide glass sheet may be passively cooled, which is to mean cooled to a temperature below 15° C. prior to evaporating the lithium metal onto the glass first major surface. Typically when passively cooled the sulfide glass sheet is at a temperature that is less than 10° C. prior to evaporation, or less than 0° C., or less than -10° C., or less than -20° C. In some embodiments the substrate is both actively cooled and passively cooled as described above. In other embodiments the substrate is exclusively passively cooled (i.e., passively cooled and not actively cooled), or vice versa exclusively actively cooled. 
     In various embodiments, an inorganic solid electrolyte laminate structure is provided. The laminate includes:
     i) a lithium ion conducting sulfide glass layer having a first and second major surface; and   ii) a protective material layer that removably covers and protects the sulfide glass first major surface.   

     In various embodiments, the protective material layer is a liquid phase hydrocarbon liquid, preferably super dry. 
     In various embodiments, a method for storing a solid-state laminate electrode assembly is provided. The method includes making a solid-state laminate electrode assembly as described herein, and immersing the laminate electrode assembly into a bath of a liquid phase protective fluid (e.g., a super dry liquid hydrocarbon). 
     In various embodiments, a method for storing a lithium metal layer having a substantially unpassivated first major surface is provided. The method includes making the substantially unpassivated first major surface, and immersing the lithium metal layer into a bath of a liquid phase protective fluid (e.g., a super dry liquid hydrocarbon). 
     In various embodiments, a method for storing a sulfide glass layer having a clean first major surface is provided. The method includes cleaning the first major surface in an Argon plasma, and immersing the sulfide glass layer into a bath of a liquid phase protective fluid (e.g., a super dry liquid hydrocarbon) 
     In another aspect the present disclosure provides nanofilm-encapsulated sulfide based solid electrolyte structures that are resistant to chemical degradation by atmospheric moisture. In accordance with the present disclosure, the moisture resistant solid electrolyte structures are composed of a moisture sensitive and dense inorganic lithium ion conducting sulfide solid electrolyte layer (e.g., a lithium ion conducting sulfide glass sheet) encapsulated on all, or some, of its surfaces by a continuous inorganic nanofilm that is dense, pinhole free and conforms to the glass surfaces of the sulfide sheet, and thereon provides a moisture barrier that protects the encapsulated surfaces from reacting with ambient moisture during storage or manufacture. 
     In various embodiments the moisture barrier provided by the continuous nanofilm is sufficiently water impervious to prevent egress of hydrogen sulfide gas during manufacture in a controlled atmosphere dry box or dry room (e.g., the atmosphere having a dew point of -20° C. or lower, or -40° C. or lower, or -60° C. or lower). In various embodiments, the nanofilm is configured as a moisture barrier and does not impart a large area specific resistance (ASR); e.g., the ASR of the nanoencapsulated sulfide glass solid electrolyte sheet is less than 200 □-cm2, when measured in a battery cell at room temperature; and preferably less than 100 □-cm2, and even more preferably less than 50 □-cm2. 
     In various embodiments, the nanofilm-encapsulation is configured to impart water imperviousness and to enhance mechanical strength. For instance, in various embodiments the nanofilm-encapsulation increases the flexural strength of the sulfide glass sheet by greater than 30%, preferably greater than 50%, and even more preferably greater than 100%. 
     In various embodiments the nanofilm-encapsulated sulfide glass sheet, as described herein, and in the claims, is, itself, a discrete battery cell separator component, and thus not yet disposed in a battery cell or combined with an electroactive material layer (e.g., when forming a solid-state laminate electrode assembly). For instance, the discrete nanofilm-encapsulated sulfide glass sheet may be in the form of a continuous web, and optionally wound and disposed for storage and/or manufacture as a roll of battery separator. 
     In various embodiments, the nanofilm-encapsulated sulfide glass solid electrolyte sheet is made by depositing onto the sulfide glass sheet a continuous inorganic nanofilm that encapsulates, in direct contact, the first and second major opposing surfaces of the sulfide sheet, as well as one or more peripheral edge surfaces. In some embodiments, when the sulfide sheet is of a substantially rectangular shape, the continuous inorganic nanofilm is configured to encapsulate, in direct contact, the major opposing surfaces of the sulfide glass sheet, and the opposing lengthwise edge surfaces, but not necessarily the opposing widthwise edge surfaces. In other embodiments the sulfide glass sheet is fully encapsulated on all surfaces by the inorganic nanofilm, including all peripheral edge surfaces (lengthwise and widthwise edge surfaces). 
     In various embodiments, the continuous and conformal nanofilm is a continuous inorganic nanolayer having a substantially uniform composition and thickness as a function of its position on the surface of the glass sheet. 
     In various embodiments the continuous nanofilm is composed of two or more continuous inorganic nanolayers, which are configured, relative to each other and the surface of the sulfide glass sheet, to provide a moisture barrier and one or more performance advantages, including enhanced mechanical strength (e.g., a 30% increase in flexural strength), reduced interface resistance in contact with lithium metal, and/or improved chemical resistance to liquid electrolytes (e.g., the encapsulation leading to zero dissolution of sulfur ), and/or oxidative stability in direct contact with electroactive cathode materials. 
     In various embodiments the encapsulating nanofilm is formed onto the sulfide glass sheet by a technique known as atomic layer deposition (ALD), and to a thickness that is typically less than 100 nm (e.g., about 1 nm or less, or about 2 nm, or about 5 nm, or about 10 nm, or about 20 nm, or about 30 nm, or about 40 nm, or about 50 nm, or about 60 nm, or about 70 nm, or about 80 nm, or about 90 nm, or about 100 nm). In various embodiments, the surfaces of the sulfide glass sheet are cleaned by ion etching (e.g., in Argon plasma) prior to ALD deposition of the nanofilm, 
     In another aspect the present disclosure provides a solid-state laminate electrode assembly composed of the nano-encapsulated sulfide glass sheet structure, as described above, and a lithium metal layer on a first major surface of the sulfide glass sheet. The lithium metal layer is in direct intimate contact with the encapsulating nanofilm. 
     In various embodiments the lithium metal layer may be deposited onto the first major surface of the nano-encapsulated sulfide glass sheet by thermal evaporation of lithium metal directly onto the nanofilm. In other embodiments the lithium metal layer may be laminated to the first major surface of the encapsulated sulfide glass sheet structure, in direct contact with the surface of the nanofilm. When thermally evaporated the thickness of the lithium metal layer is generally not greater than 10 um, and more typically not greater than 5 um. 
     In another aspect, the present disclosure provides a battery cell that incorporates the nanofilm-encapsulated sulfide glass solid electrolyte structure as a solid electrolyte separator 
     In various embodiments the material composition of the nanofilm or nanolayer is an insulator in bulk form but is transparent or permeable to lithium ions as a nano layer. 
     In another aspect, the present disclosure provides methods for making solid-state laminate electrode assemblies include methods of forming a solid electrolyte interphase (SEI) by ion implanting nitrogen and/or phosphorous into the glass surface by ion implantation. 
     In various embodiments such a method for making a solid-state laminate electrode assembly includes the operations of providing a lithium ion conducting sulfide glass substrate, the substrate comprising a sulfide glass solid electrolyte sheet having room temperature Li ion conductivity of at least 10-5 S/cm, the sulfide glass substrate having first and second major surfaces; injecting nitrogen and/or phosphorous into the first surface of the sulfide glass substrate, wherein the nitrogen and/or phosphorous penetrates the glass surface forming an implanted zone; and, evaporating lithium metal onto the implanted zone of the sulfide glass substrate; wherein at least a portion of the evaporated lithium reacts with the injected nitrogen and/or phosphorous to form a solid electrolyte interphase (SEI) layer comprising lithium and one or both of nitrogen and phosphorous. 
     Sulfide glass solid electrolytes that are suitable for use herein as a sulfide glass solid electrolyte sheet, as well as methods for making the sulfide glass sheet, depositing Li metal and electrode compositions and structures are described in US Pat. No.: 10,164,289 and US Pat. No.: 10,147,968. Both of these patents are hereby incorporated by reference for their disclosures relating to such electrolytes and methods. 
     These and other aspects of the present disclosure are described in further detail below, including with reference to the drawings. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG.  1    is a process flow diagram for making a solid-state laminate electrode assembly in accordance with one embodiments of the present disclosure. 
         FIGS.  2 A-D  illustrate cross sectional depictions of standalone alkali metal laminate structures in accordance with various embodiments of the present disclosure. 
         FIGS.  2 E-H  illustrate cross sectional depictions of standalone inorganic solid electrolyte laminate structures in accordance with various embodiments of the present disclosure. 
         FIGS.  2 I-P  illustrate cross sectional depictions of nanofilm-encapsulated sulfide glass separator sheets in accordance with various embodiments of the present disclosure. 
         FIG.  2 Q  is a process flow diagram illustrating various process embodiments of making a nanofilm-encapsulated sulfide glass solid electrolyte structure in accordance with the present disclosure. 
         FIGS.  3 A-E  illustrate cross sectional and top down depictions of lithium metal layers and lithium metal surfaces. 
         FIGS.  4 A-G  illustrate apparatus and method for making a lithium metal layer having substantially unpassivated surfaces, in accordance with various embodiments of the present disclosure. 
         FIGS.  4 H-J  illustrate apparatus, methods and tools for making a lithium metal layer by evaporation and having substantially unpassivated surfaces, in accordance with various embodiments of the present disclosure. 
         FIG.  4 K  illustrates apparatus and process for making vacuum die extruded lithium metal layers in accordance with an embodiment of the present disclosure. 
         FIGS.  5 A-B  illustrate a lithium roll assembly cartridge according to one embodiment of the present disclosure. 
         FIG.  6 A  illustrates an apparatus and method for cleaning and treating an inorganic solid electrolyte layer, in accordance with an embodiment of the present disclosure. 
         FIG.  6 B  illustrates a cross sectional depiction of an inorganic solid electrolyte layer coated with a thin precursor film, in accordance with one embodiment of the present disclosure. 
         FIG.  7    illustrates a cross sectional depiction of a solid-state laminate electrode assembly in accordance with one embodiment of the present disclosure. 
         FIG.  8 A  illustrates an apparatus and method for making a solid-state laminate electrode assembly in accordance with one embodiment of the present disclosure. 
         FIGS.  8 B-C  illustrates apparatus, method and tool for making a solid-state laminate electrode assembly in accordance with one embodiment of the present disclosure. 
         FIG.  8 D  illustrates cross sectional depictions of solid-state laminate electrode assemblies in accordance with one embodiment of the present disclosure. 
         FIG.  8 E  illustrates an arrangement of a combination apparatus (or tool) suitable for thin film fabrication methods described herein, including ALD tool, a lithium thermal evaporation tool, and an Argon plasma ion etch tool for cleaning sulfide glass surfaces. 
         FIG.  8 F  is a process flow diagram illustrating methods for making solid-state laminate electrode assemblies in accordance with embodiments of the present disclosure. 
         FIG.  9    illustrates a roll assembly cartridge containing a solid-state laminate electrode assembly according to one embodiment of the present disclosure. 
         FIG.  10    illustrates a cross sectional depiction of a battery cell in accordance with one embodiment of the present disclosure. 
         FIG.  11    illustrates a cross sectional depiction of a battery cell in accordance with one embodiment of the present disclosure. 
         FIG.  12    illustrates a protected sulfide glass solid electrolyte sheet of this disclosure. 
         FIG.  13    illustrates an electrode assembly of this disclosure. 
         FIG.  14    illustrates an alternative embodiment of a protected sulfide glass solid electrolyte sheet of this disclosure. 
         FIG.  15    illustrates an alternative embodiment of a protected sulfide glass solid electrolyte sheet of this disclosure. 
         FIG.  16    illustrates an alternative embodiment of an electrode assembly of this disclosure. 
         FIG.  17    illustrates an alternative embodiment of a protected sulfide glass solid electrolyte sheet of this disclosure. 
         FIG.  18    illustrates an alternative embodiment of an electrode assembly of this disclosure. 
         FIG.  19    illustrates a battery cell in accordance with various embodiments of this disclosure. 
         FIG.  20    illustrates a cross-sectional depiction of a protected sulfide solid electrolyte glass sheet in accordance with embodiments of the present disclosure. 
         FIG.  21    illustrates a method of making a converted compound layer according to various embodiments of the present disclosure. 
         FIGS.  22 A-D  illustrates coating and a coated electrolyte, electrolyte assembly and battery cell in accordance with various embodiments of the present disclosure. 
         FIG.  23    illustrates a mosaic target in accordance with an embodiment of the present disclosure. 
     
    
    
     DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS 
     Reference will now be made in detail to specific embodiments of this disclosure. Examples of the specific embodiments are illustrated in the accompanying drawings. While this disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit this disclosure to such specific embodiments. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of this disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of this disclosure. This disclosure may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order to not unnecessarily obscure this disclosure. 
     Introduction 
     This disclosure generally relates to the fabrication of batteries, battery components and battery component materials, and to associated materials and components for fabricating batteries, as well as battery cells and battery cell structures. In a particular example, the disclosure relates to nitrogen rich lithium phosphorus nitride (Li-P-N) thin films on a solid electrolyte surface, and to high-quality physical vapor deposition (PVD) targets formed of a mechanically robust and precisely shaped ceramic body composed of a moisture resistant target material having a nitrogen rich chemical makeup of lithium, phosphorus, and nitrogen as constituent elements. In various embodiments, the moisture resistant nitrogen rich Li-P-N target (e.g., sputtering target) can be readily handled in a dry room environment, or handled in ambient air, without adverse reaction with moisture. In some embodiments, the nitrogen rich Li-P-N sputtering targets are particularly suitable for fabricating thin protective films that may be utilized, for example, to protect the surface of a solid electrolyte layer and as an interlayer between a solid electrolyte and lithium metal in a battery cell. The disclosure also relates to methods of producing and fabricating thin nitrogen rich Li-P-N films, sputtering targets, surface protected solid electrolytes and battery cells thereof. 
     The present disclosure describes solid-state laminate electrode assemblies and various methods for making the solid-state laminate electrode assemblies. 
     In various embodiments the solid-state laminate electrode assembly comprises a lithium metal layer reactively bonded to a lithium ion conducting sulfide glass layer. Preferably, the reactive bond is sufficiently complete that it forms a continuous solid electrolyte interphase (SEI) at the boundary between the layers. 
     In various embodiments, to bring about a continuous SEI, the lithium metal layer should have a major surface, which, just prior to bonding (e.g., by laminating), is in a highly reactive state (i.e., it is substantially unpassivated). In various embodiments the method involves making a pristine lithium metal layer having a substantially unpassivated first major surface, and therefore highly reactive, and maintaining the highly reactive surface in its substantially unpassivated state until it has been reactively bonded with the sulfide glass layer. 
     In various embodiments, the present disclosure provides methods for making a solid-state laminate electrode assembly. Such a method includes:
     ii) providing a lithium metal laminate structure the laminate comprising:
   a. a lithium metal layer having a first major surface that is substantially unpassivated; and   b. an inert protective material layer that removably covers the lithium metal first major surface, the protective material layer in direct contact with the lithium first major surface;   
   ii) providing an inorganic solid electrolyte laminate structure, the laminate comprising:
   c. an inorganic lithium ion conducting sulfide glass layer having a first major surface and an opposing second major surface; and   d. an inert protective material layer that removably covers the sulfide glass first major surface, the protective material layer in direct contact with the sulfide glass;   
   iii) removing the inert protective material layer off the lithium metal first major surface;   iv) removing the inert protective material layer off the sulfide glass first major surface;   v) reactively bonding the sulfide glass layer with the lithium metal layer via their first major surfaces; and   wherein the reactive bond is complete and the interface between the sulfide glass layer and the lithium metal is defined by a continuous solid electrolyte interphase.   

     In various embodiments the reactive bonding operation is a lamination process performed in a chamber filled with a dry gas (e.g., dry Argon). Typically the laminating operation involves applying both heat and pressure. 
     In various embodiments the inert protective material layer removably covering one or both of the sulfide glass first major surface and the substantially unpassivated lithium metal surface is a liquid phase protective fluid. 
     In various embodiments the liquid phase protective fluid removably covering the lithium metal surface is removed just prior to the reactive bonding operation (e.g., the period of time between removing the liquid phase protective fluid and reactive bonding is less than 10 seconds, and preferably less than 5 seconds, and even more preferably less than 2 seconds). 
     In various embodiments to ensure that the interface formed between the lithium metal layer and the lithium ion conducting sulfide glass is electrochemically operable or otherwise optimized, an SEI may be engineered by coating a first major surface of the sulfide glass with a thin precursor film that reacts with lithium metal during the bonding operation to form a solid electrolyte interphase. 
     In some embodiments the sulfide glass surface may be treated under a Nitrogen containing plasma to incorporate Nitrogen into the surface of the glass, and then forming a lithium nitride. 
     In various embodiments the method further comprises the operation of cleaning the first major surface of the sulfide glass under an Argon plasma, by ion etching, this operation performed after removing the inert protective material layer off of the sulfide glass but before reactive bonding. 
     In various embodiments the method further comprises the operation of treating the clean sulfide glass first major surface to modify its surface composition. In various embodiments the surface composition is modified by placing the clean first major surface of the sulfide glass under a Nitrogen containing plasma, wherein the treatment modifies the surface composition of the sulfide glass by introducing Nitrogen into/onto the surface. 
     In various embodiments the method further comprises the operation of coating the clean sulfide glass first major surface with a thin precursor film having a composition that will react in direct contact with lithium metal. 
     In various embodiments the thin precursor film is formed by condensing between 1 to 5 monolayers of a Halogen (e.g., iodine) or Interhalogen or Nitrogen onto the clean sulfide glass surface; wherein the iodine monolayers leads to reactive wetting during the reactive bonding operation. 
     In various embodiments the method further comprises coating the clean sulfide glass surface to form a precursor film that reacts with lithium during the reactive bonding operation to form a solid electrolyte interphase between the lithium metal layer and sulfide glass layer. 
     In various embodiments the inert protective material layer removably covering one or both of the sulfide glass first major surface and the substantially unpassivated lithium metal surface is a liquid phase protective fluid. 
     In one aspect the present disclosure provides methods for making a pristine lithium metal layer having a substantially unpassivated first major surface, as defined herein below. In various embodiments the opposing second major surface of the pristine lithium metal layer is adhered to a current collector (e.g., a copper foil) 
     In various embodiments the pristine lithium metal layer is in the form of a long continuous roll of lithium that is immersed in liquid phase protective fluid for storage and/or downstream processing of battery cells (e.g., the pristine lithium metal layer at least 100 cm in length). 
     In various embodiments the method involves making the pristine lithium metal layer in a protective inert fluid, and maintaining the pristine lithium metal layer in protective fluid (e.g., protective liquid) to prevent directly exposing the surface to the ambient gaseous atmosphere (including dry Argon of a glove box or dry Air of a dry room). In various embodiments the protective fluid is an inert liquid or the vapor of an inert liquid (i.e., protective vapor). In various embodiments the lithium metal layer is in the form of a long continuous ribbon (e.g., more than 50 cm in length). 
     In various embodiments the method for making the substantially unpassivated lithium metal surface includes an extrusion operation that produces a fresh substantially unpassivated lithium first major surface inside or surrounded by protective fluid (e.g., a protective and super dry liquid hydrocarbon). By use of the term super dry it is meant that the amount of moisture in the liquid hydrocarbon is not greater than 0.1 ppm. In various embodiments the pristine lithium metal layer and its substantially unpassivated surface is extruded directly into liquid phase protective fluid (i.e., protective liquid), and then optionally the method further includes winding the lithium metal layer into a long continuous roll while it is immersed in liquid phase protective fluid. 
     In various embodiments the extrusion operation is die extrusion of lithium ingot directly into a super dry liquid hydrocarbon bath. In various embodiments the extrusion operation is a roller extrusion wherein the lithium metal foil thickness is roll reduced in protective liquid, and in the process forms fresh lithium substantially unpassivated lithium metal surfaces, wherein the area of the fresh surfaces so formed is proportional to the reduction in thickness of the lithium layer. In various embodiments multiple roll reduction operations are performed (e.g., 2, 3, 4 or 5 or more) in order to produce the desired thickness and to perfect the substantially unpassivated surface (e.g., a pristine surface). In various embodiments, the stock foil used for the roll reduction process has been pre-passivated, to improve reproducibility of the starting surface condition. In a particular embodiment a lithium ingot is die extruded directly into protective fluid to form a pristine lithium metal layer, and then that layer is immediately roll reduced in protective fluid to the desired thickness, and throughout the process the substantially unpassivated lithium metal surface remains covered or immersed in liquid phase protective fluid. The pristine lithium metal as formed may then be wound into a long continuous roll of pristine lithium metal, the winding performed in protective fluid (e.g., the winding performed inside liquid phase protective fluid). 
     In various embodiments the substantially unpassivated lithium metal surfaces are stored in a canister of protective liquid, or they are formed and immediately transferred into the canister, without exposing the surfaces to the ambient gaseous environment. 
     In another aspect the present disclosure provides a standalone electrochemical material laminate structure for maintaining a major surface of a battery active material layer in a substantially unpassivated and/or substantially uncontaminated condition during handling, storage and/or battery cell fabrication. 
     In various embodiments the battery active material layer reacts with water and/or Oxygen, and even under fairly dry ambient conditions, such as that of a dry air room or a dry Argon filled glove box the battery material surfaces chemically degrade or passivate rather quickly. The laminate structures of the present disclosure protect the battery material surfaces by encapsulating them underneath an inert removable layer, which inhibits moisture and/or oxygen from reaching the surfaces. 
     Accordingly, the standalone electrochemical material laminate structures of the present disclosure are particularly useful for making, storing and transporting moisture sensitive battery active material layers, and for making downstream battery cells and laminate electrode assemblies from those material layers. 
     In accordance with the present disclosure, a standalone electrochemical material laminate structure may be composed of two or more continuous material layers, wherein at least one of the material layers (i.e., a first material layer) is a “battery active solid material” having a clean (i.e., substantially uncontaminated) and/or substantially unpassivated surface, and another material layer (i.e., a second material layer) is a “protective material” that is inert, not battery active, and removably covers, in direct contact, a first major surface of the battery active material. 
     When referring to a material as “battery active” it generally means that the material is active in an electrochemical sense and useful in a battery cell (i.e., it is either an electro-active material or an electrolyte material). As used herein, the term “battery active solid material layer” means either a solid alkali metal or an inorganic solid electrolyte having utility as a continuous solid layer in a battery cell (e.g., a lithium metal layer or a Li-ion conducting sulfide glass sheet, respectively). 
     In contrast to the battery active material layer, the protective material layer is inert and not battery active. By use of the term “inert” it means that the referenced inert material does not chemically react in contact with the battery active solid material on which it is intended to protect. And when referring to the protective material layer as “not battery active,” it is meant that the material layer is not useful in a battery cell, and is furthermore not intended for use in a battery cell, and not active in a battery/electrochemical sense (i.e., not an electroactive material or alkali metal ion conductor). 
     In accordance with the present disclosure the protective material layer: i) provides an encapsulating barrier against direct touching exposure between the first major surface of the battery active material layer and the ambient gaseous atmosphere or contaminants in a vacuum chamber about the layer; ii) is inert in direct contact with the first major surface; and iii) is readily removed without physically damaging the surface. To achieve these objectives, in various embodiments the protective material layer is an inert liquid (e.g., a super dry hydrocarbon liquid) that encapsulates the surface on which it is applied, and may be evaporatively removed in the absence of solid to solid touching contact 
     In a first embodiment, the battery active material layer is an electroactive alkali metal layer having a substantially unpassivated first major surface (e.g., a pristine lithium metal layer), and in such embodiments the standalone electrochemical material laminate structure is generally referred to herein as a standalone alkali metal laminate structure; e.g., a standalone lithium metal laminate structure. 
     In a second embodiment, the battery active material layer is an inorganic solid electrolyte layer having a substantially uncontaminated first major surface (e.g., a lithium ion conducting sulfide glass sheet), and in such embodiments the standalone electrochemical material laminate structure is generally referred to herein as a standalone solid electrolyte laminate structure; e.g., a standalone sulfide glass laminate structure. 
     By use of the term “standalone” when referring to an electrochemical material laminate structure, such as a standalone alkali metal laminate structure or a standalone solid electrolyte laminate structure, it is meant to emphasis that the battery active material layer in the standalone laminate is a discrete battery active material layer that has not yet been combined or coupled with a second battery active material layer, or yet been placed in a battery cell. 
     In another aspect the present disclosure provides methods for making lithium metal layers having substantially unpassivated surfaces and preventing passivation by encapsulating them with inert liquid. In various embodiments the methods include making a lithium metal foil having substantially unpassivated surfaces by die extruding a lithium ingot into a bath of super dry liquid hydrocarbons. In various embodiments the as made substantially unpassivated lithium metal foil may be further reduced in thickness by roller reduction and applying hydrocarbon liquid onto the freshly formed surfaces to ensure that they remain substantially unpassivated. In various embodiments a pre-passivated lithium metal layer of thickness (t) may be roller reduced in a roller mill using multiple roll reduction operations while at all times maintaining liquid hydrocarbon on the freshly formed lithium metal layer surfaces. By using pre-passivated lithium metal (e.g., passivated by exposure to CO2), reproducibility is improved because the initial surface condition of the lithium is itself reproducible, as opposed to using lithium metal that is passivated in a less or uncontrolled fashion. Moreover, the area of freshly formed lithium is proportional to the decrease in thickness of the layer. 
     In another aspect the present disclosure provides methods for making inorganic lithium ion conducting sulfide glass sheets having substantially uncontaminated surfaces, and for preventing hydrolysis of those surfaces by encapsulating them underneath an inert super dry hydrocarbon fluid (e.g., liquid). For instance, in various embodiments the inorganic sulfide glass sheets are cleaned by ion etching in an Ar plasma to etch away any contaminated surface(s), and then substantially immediately after the ion etching operation, the cleaned sulfide glass sheet may be immersed in a liquid hydrocarbon bath, or the clean surface encapsulated by a protective liquid layer, as described above. In various embodiments, the surface composition of the sulfide glass may be modified during or immediately after cleaning by using an Argon/Nitrogen plasma mixture for incorporating Nitrogen into the surface of the sulfide glass sheet, or the surfaces may be treated sequentially, using a first ion etch in argon plasma, followed by a second treatment in a nitrogen containing plasma (e.g., pure Nitrogen or an Argon/Nitrogen mixture). 
     In yet another aspect the present disclosure provides methods of making a strongly adhered fully solid-state inorganic laminate electrode assembly having a substantially contaminate free inorganic interface. In various embodiments the method includes providing a first battery active material as a component of a lithium metal laminate structure (e.g., a lithium metal layer having a first major surface which is substantially unpassivated and protected by an inert hydrocarbon liquid layer); providing a second battery active material layer as a component of an inorganic solid electrolyte laminate structure (e.g., a lithium ion conducting sulfide glass sheet having a clean first major surface that is devoid of hydrolysis reaction products and protected by an inert hydrocarbon liquid layer); removing the inert hydrocarbon liquid layers; and then, substantially immediately thereafter, reactively bonding the substantially unpassivated lithium metal surface to the clean inorganic sulfide glass surface, to form a strongly adhered laminate having a clean inorganic interface with a low area resistance (preferably, less than 50 □-cm2). Preferably the peel strength of the laminate electrode assembly is greater than the tensile strength of its lithium metal layer, such that any attempt to peel off the lithium from the laminate results in the lithium tearing prior to peeling. 
     In various embodiments, an improved laminate interface is formed by laminating the fluid protected lithium metal surface to a solid electrolyte sheet using techniques whereby the fluid is removed substantially immediately prior to, or during, the laminating operation, as the solid electrolyte comes into direct contact with the fluid and the lithium metal layer. In various embodiments, the laminating operation effects a three phase boundary of lithium metal layer, solid electrolyte, and protective fluid, and causes the fluid to be removed from the surface substantially instantaneously as the solid electrolyte layer reactively adheres to the pristine lithium metal layer surface. 
     In another aspect, the present disclosure relates to methods and reagents to form a thin, dense and lithium ion conductive layer between a lithium metal layer and an inorganic solid electrolyte layer (e.g., a lithium ion conducting sulfide glass). The layer is sometimes referred to herein as a solid electrolyte interphase (SEI) as it is formed by reacting a first major surface of the lithium metal layer with a coating on the glass surface that allows for the glass electrolyte to be optimized for high ionic conductivity and processability, regardless of its chemical compatibility with lithium metal. 
     In another aspect the present disclosure provides methods of making battery cells by combining the fully solid-state inorganic laminate electrode assembly of the present disclosure with a positive electrode (e.g., a lithium ion intercalating positive electrode). 
     A list of suitable hydrocarbons which may be used as protective fluid (e.g., inert liquid) in accordance with the various embodiments and aspects of the present disclosure is provided below, as well as their structural formulas and vapor pressure (and/or boiling point) values. In various embodiments, the protective fluid is selected from a group of saturated hydrocarbons with the number of carbon atoms from 5 to 15. In one particular case, the protective fluid is isododecane. The protective fluids may be a combination of these various fluids. The fluids generally contain no dissolved or dispersed chemicals (e.g., salts, lubricants and/or greases) that would coat the surface of the lithium metal layer or solid electrolyte layer with a solid film or residue. Accordingly the protective fluid is devoid of any dissolved salts (e.g., lithium salts). 
     Suitable protective fluids are chemically inert to Li metal or Li alloys and contain less than 0.1 ppm of moisture, less than 1 ppm of moisture, less than 5 ppm of moisture, less than 10 ppm of moisture. In the case when a protective fluid is used in combination with a glass coating designed to form a solid electrolyte interphase (SEI) upon contact with Li, the protective fluid is chosen to be non-reactive with the glass coating. 
     Protective Fluids 
     Saturated Hydrocarbons (Alkanes) C n H 2n+2   
     Straight-Chain Alkanes C 5  — C 15   
     n-Pentane C 5 H 12  BP = 36° C., Vapor Pressure: 434 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     n-Hexane C 6 H 14  BP = 69° C., Vapor Pressure: 121 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     n-Heptane C 7 H 16 BP= 99° C., Vapor Pressure: 46 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     n-Octane C 8 H 18  BP = 125° C., Vapor Pressure: 11 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     n-Nonane C 9 H 20  BP= 151° C., Vapor Pressure: 3.8 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     n-Decane C 10 H 22  BP= 174° C., Vapor Pressure: 2.7 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     n-Undecane C 11 H 24  BP= 196° C., Vapor Pressure: 0.4 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     n-DodecaneC 12 H 26  BP =216° C., Vapor Pressure: 0.14 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     Branched-Chain Alkanes C 5  — C 15   
     Isopentane C 5 H 12  BP = 28° C., Vapor Pressure: 577 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Isohexane C 6 H 14  BP = 61° C., Vapor Pressure: 172 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Isoheptane C 7 H 16  BP = 90° C., Vapor Pressure: 66 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Isooctane C 8 H 18  BP = 99° C., Vapor Pressure: 41 mmHg at 21° C. 
     
       
         
         
             
             
         
       
     
     Tetraethylmethane C 9 H 20  BP = 146° C., Vapor Pressure: 7.3 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     Isodecane C 10 H 22 BP= 167° C., Vapor Pressure: 2.3 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     3-MethyldecaneC 11 H 24 BP= 188° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     Isododecane C 12 H 26  BP = 180° C., Vapor Pressure: 0.301 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Cycloalkanes C 6  — C 8  C n H 2n   
     Cyclohexane C 6 H 12  BP = 81° C., Vapor Pressure: 78 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Cycloheptane C 7 H 14  BP = 118° C., Vapor Pressure: 22 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Cyclooctane C 8 H 16  BP = 149° C., Vapor Pressure: 16 mmHgat37.7° C. 
     
       
         
         
             
             
         
       
     
     Unsaturated Acyclic Hydrocarbons C n H 2(n-m-1) , 
     
         
         n = number of carbon atoms 
         m = number of double bonds 
       
    
     Alkenes C 6  — C 11 , C n H 2n   
     1-Hexene C 6 H 12  BP = 64° C., Vapor Pressure: 155 mmHg at 21° C. 
     
       
         
         
             
             
         
       
     
     1-Heptene C 7 H 14  BP = 94° C., Vapor Pressure: 101 mmHg at 37.7° C. 
     
       
         
         
             
             
         
       
     
     1-Octene C 8 H 16  BP = 122° C., Vapor Pressure: 36 mmHg at 37.7° C. 
     
       
         
         
             
             
         
       
     
     1-Nonene C 9 H 18  BP = 146° C., Vapor Pressure: 11 mmHg at 37.7° C. 
     
       
         
         
             
             
         
       
     
     1-Docene C 10 H 20 BP= 172° C., Vapor Pressure: 1.67 mmHgat25° C. 
     
       
         
         
             
             
         
       
     
     1-Undecene C 11 H 22  BP = 192° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     1-Dodecene C 12 H 24  BP = 214° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     Alkadienes: C 6  — C 12  C n H 2n—2   
     1,5-Hexadiene C 6 H 10  BP = 60° C., Vapor Pressure: 367 mmHg at 37.7° C. 
     
       
         
         
             
             
         
       
     
     2,4-Hexadiene C 6 H 10  BP = 82° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     1,6-Heptadiene C 7 H 12 BP= 90° C., Vapor Pressure: N/A 
     1,7-Octadiene C 8 H 14  BP = 118° C., Vapor Pressure: 19 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     1,8-Nonadiene C 9 H 16 BP= 141° C., Vapor Pressure: 7 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     1,9-Decadiene C 10 H 18  BP = 169° C., Vapor Pressure: 4 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     1,10-Undecadiene C 11 H 20  BP = 187° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     1,11-Dodecadiene C 12 H 22  BP = 207° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     Unsaturated Cyclic Hydrocarbons C n H 2(n-m) , 
     
         
         n = number of carbon atoms 
         m = number of double bonds 
       
    
     Cycloalkenes C 6  — C 8 , C n H 2n—2   
     Cyclohexene C 6 H 10  BP = 83° C., Vapor Pressure: 160 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Cycloheptene C 7 H 12  BP = 113° C., Vapor Pressure: 22 mmHg at 20° C. 
     
       
         
         
             
             
         
       
     
     Cyclooctene C 8 H 14  BP = 145° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     Cycloalkadienes C 6  — C 8 , C n H 2n—4   
     1,3-Cyclohexadiene C 6 H 8  BP = 80° C., Vapor Pressure: 56 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     1,4- Cyclohexadiene C 6 H 8  BP = 88° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     1,3-Cycloheptadiene C 7 H 12  BP = 120° C., Vapor Pressure: N/A 
     
       
         
         
             
             
         
       
     
     1,3-Cyclooctadiene C 8 H 14  BP = 143° C., Vapor Pressure: 13.4 mmHg at 25° C. 
     
       
         
         
             
             
         
       
     
     Generally, the protective inert liquid layer is devoid of dissolved and/or dispersed chemicals (e.g., salts, lubricants and/or greases) that would coat the surface of the battery active material layer with a solid film or leave behind a sticky residue. Accordingly, the protective inert liquid layer is generally devoid of dissolved salts (e.g., lithium salts, or more generally alkali metal salts). 
     In order to be inert in direct contact with the battery active material layer, the liquid hydrocarbon(s) should have a very low concentration of moisture. Preferably the concentration of moisture in the inert liquid hydrocarbon layer is less than 10 ppm of water, more preferably less than 5 ppm of water, even more preferably less than 1 ppm of water, and yet even more preferably less than 0.1 ppm of water (i.e., super dry). In various embodiments the inert liquid is actively dried in the presence of sacrificial alkali metal surfaces (e.g., pieces/chips of lithium or sodium metal) that getter oxygen, water and nitrogen impurities. Moreover, the liquid hydrocarbons may be passed through a drying a chamber in order to maintain very low moisture levels. The drying chamber may contain drying agents and oxygen getters. Examples of drying agents for liquid hydrocarbons include molecular sieves (3A, 4A, or 5A depending on the hydrocarbon type), magnesium oxide, zinc chloride, calcium sulfate, calcium chloride, calcium hydride, and alumina (neutral or basic). In various embodiments, the cumulative area of the sacrificial alkali metal surfaces in direct contact with the inert liquid is greater than the first major surface of the battery active material layer on which the inert liquid covers in direct contact, for instance when the battery active material layer is disposed in a protective liquid bath, as described in more detail herein below. 
     Depicted Embodiments 
     In one aspect the present disclosure provides methods for making a solid-state laminate electrode assembly. In various embodiments, the solid-state laminate electrode assembly is a lithium metal layer reactively bonded with a lithium ion conducting sulfide glass layer. 
     With reference to  FIG.  1    there is illustrated process flow diagram  5  for making a solid-state laminate electrode assembly in accordance with various embodiments of the present disclosure. 
     The process includes initial operations  10  and  20 , for making or providing a first and a second standalone electrochemical material laminate structure, respectively. Notably, first and second electrochemical material laminate structures are not the same. At this point, before continuing to describe the process flow diagram, it is prudent to digress for a moment and address what is meant by the term standalone electrochemical material laminate structure. 
     As used herein, the term electrochemical material laminate structure means a laminate of two or more continuous material layers, wherein at least one of the material layers (i.e., a first material layer) is a “battery active solid material layer” having a clean (i.e., substantially uncontaminated) and/or substantially unpassivated first major surface, and another material layer (i.e., a second material layer) is a “protective material layer” that is inert, not battery active, and removably covers, in direct intimate contact, the first major surface of the battery active material layer. In various embodiments the protective material layer is a liquid phase layer of a protective fluid, such as a super dry hydrocarbon liquid that is spread out evenly over the first major surface of the battery active material layer. 
     Generally, the battery active material layer is highly reactive with water and/or oxygen, and its surfaces chemically degrade or passivate rather quickly, even under dry or vacuum conditions, including that of a dry air room suited for handling lithium metal (e.g., having a dew point between -20 to - 40° C.) or a dry Argon filled glove box (e.g., having a low moisture and oxygen content of between 1 to 5 ppm). Accordingly, the electrochemical laminate structure is the laminate that is used to shield a battery active material layer against adverse reactions with the environment in which it (the battery active material layer) is made, processed and/or stored. And by the term “solid battery active material layer” it is meant either a solid alkali metal layer (e.g., typically embodied herein as a lithium metal layer) or an inorganic solid electrolyte layer (e.g., typically embodied herein as a lithium ion conducting sulfide glass). When the battery active material layer is a lithium metal layer, the laminate structure is referred to generally as an alkali metal laminate structure (or more specifically in this case as a lithium metal laminate structure), and when the battery active material layer is an inorganic lithium ion conducting sulfide glass, the laminate structure is referred generally as a solid electrolyte laminate structure (or more specifically in this case as a sulfide glass laminate structure). Furthermore, by use of the term “standalone” when referring to an electrochemical material laminate structure, such as a standalone alkali metal laminate structure or a standalone solid electrolyte laminate structure, it is meant to emphasis that the battery active material layer in the standalone laminate is a discrete battery active material layer that has not yet been combined or coupled with a second battery active material layer, or yet been placed in a battery cell. For instance, when standalone lithium laminate structures are absent of an electrolyte and standalone sulfide glass solid electrolyte laminate structures are absent of battery electroactive materials. 
     Continuing with reference to  FIG.  1    the first electrochemical material laminate structure, which is provided or made in process operation  10  is a standalone lithium metal laminate structure, and the second electrochemical material laminate structure, which is provided in process operation  20 , is a standalone sulfide glass laminate structure. Once the laminate structures are provided (or made), the protective material layer on their respective first major surfaces is removed during process operations  12  and  22 , and done without physically damaging the surfaces. As mentioned above, in various embodiments the protective material layer is an inert liquid phase layer of a super dry liquid hydrocarbon. Moreover, the liquid hydrocarbon employed herein as a protective material layer is selected, in part, on its ability to remain on the surface of the lithium metal or sulfide glass layer until such time that it is to be controllably removed; accordingly it cannot be allowed to evaporate off by happenstance. Processes for accelerating and controllably removing the protective liquid layer off of the battery active material layer are generally performed in a chamber designed for that purpose. Such processes include one or more of heating, vacuum suction, blowing a jet of dry inert gas, blowing a jet of high vapor pressure protective fluid followed by vacuum suction, as well as rinsing the surfaces progressively with protective fluids having progressively higher vapor pressures. 
     Once the protective material layer has been removed, it is important to minimize any exposure to gaseous or vacuum environments in order to maintain the respective battery active material layer surfaces clean and unpassivated. Accordingly, in some embodiments the chamber or conduit through which the battery active material layers are translated may be filled with vapor phase protective fluid right up until the layers are combined for lamination, according to process operation  30 , wherein the layers are reactively bonded to each other. 
     In various embodiments, once the liquid phase layer of protective fluid has been removed from the surface of the sulfide glass, the glass first major surface may be processed and/or treated prior to laminating with lithium metal in order to engineer a solid electrolyte interphase (SEI) with improved electrochemical properties, or when the sulfide glass is not chemically compatible with lithium metal. As described in more detail herein below, the sulfide glass may undergo cleaning process 24A, exemplified by an ion etch treatment under an Ar plasma followed by surface treating process 24B, wherein the cleaned glass surface may be coated with a thin lithium metal reactive precursor film or treated to modify the surface composition of the glass (e.g., by placing the glass first major surface under a Nitrogen containing plasma). 
     The material laminate structures, methods and processes briefly described above with reference to process flow diagram in  FIG.  1    are now described in more detail herein below, beginning with a description of the various architectures embodied for the standalone material laminate structures, followed by methods for making lithium metal layers having substantially unpassivated surfaces, as well as methods for treating the sulfide glass to engineer a solid electrolyte interphase. 
     Standalone Electrochemical Material Laminate Structure 
     In one aspect the present disclosure provides a standalone electrochemical material laminate structure for maintaining a major surface of a battery active material layer in a substantially unpassivated and/or substantially uncontaminated condition during storage and/or battery cell component fabrication (e.g., fabrication of a fully solid-state laminate electrode assembly). 
     In accordance with the present disclosure, the standalone electrochemical material laminate structure is composed of two or more continuous material layers, wherein at least one of the material layers (i.e., a first material layer) is a “battery active solid material layer” having a clean (i.e., substantially uncontaminated) and/or substantially unpassivated first major surface, and another material layer (i.e., a second material layer) is a “protective material layer” that is inert, not battery active, and removably covers, in direct contact, the first major surface of the battery active material layer. 
     In various embodiments the battery active material layer is highly reactive with water and/or Oxygen, and its surfaces will chemically degrade or passivate rather quickly, even under fairly dry conditions of a dry Air room (e.g., having a dew point of -20° C.) or a dry Argon filled glove box (e.g., having a low moisture and oxygen content of between 1 to 5 ppm). 
     In accordance with the present disclosure the protective material layer: i) minimizes, and preferably prevents, direct touching exposure between the first major surface of the battery active material layer and the ambient gaseous atmosphere or vacuum environment about the layer (e.g., during handling, processing and/or storage); ii) is inert in direct contact with the first major surface; and iii) is readily removed without physically damaging the surface. Accordingly, in various embodiments the protective material layer is an inert liquid (e.g., a super dry hydrocarbon liquid) that encapsulates the surface on which it is applied, and may be evaporatively removed in the absence of solid to solid touching contact. 
     In a first inventive embodiment, the battery active material layer is an electroactive alkali metal layer having a substantially unpassivated first major surface (e.g., a pristine lithium metal layer), and in such embodiments the standalone electrochemical material laminate structure is generally referred to herein as a standalone alkali metal laminate structure; e.g., a standalone lithium metal laminate structure. Preferably, the first major surface is pristine. 
     In a second inventive embodiment, the battery active material layer is an inorganic solid electrolyte layer (e.g., a lithium ion conducting sulfide glass sheet), and in such embodiments the standalone electrochemical material laminate structure is generally referred to herein as a standalone solid electrolyte laminate structure; e.g., a standalone sulfide glass laminate structure. In various embodiments the sulfide glass layer has a first major surface that is clean (i.e., substantially uncontaminated). 
     The standalone electrochemical material laminate structure of the present disclosure can be constructed using a number of different architectures, some of which are described in more detail herein below 
     With reference to  FIGS.  2 A-D  and  FIGS.  2 E-H  there are illustrated cross sectional depictions of standalone electrochemical material laminate structures in accordance with various embodiments of the present disclosure. The main differences between the structures shown in  FIGS.  2 A-D  and those shown  FIGS.  2 E-H  are the battery active material layer. Specifically, in  FIGS.  2 A-D  the battery active material layer is lithium metal, and the electrochemical material laminate structure is a lithium metal laminate structure. In  FIGS.  2 E-H  the battery active material layer is a lithium ion conducting sulfide glass, and the electrochemical material laminate structure is an inorganic solid electrolyte laminate structure. The laminate structures may take on a variety of shared architectures and these architectures are now described with reference to a battery active material layer. Thereafter, details particular to the lithium metal layer and to the sulfide glass layer are provided. 
     With reference to  FIG.  2 A  and  FIG.  2 E  there are illustrated fully encapsulated electrochemical material laminate structures  100 A/ 200 E in accordance with various embodiments of the present disclosure. Structure  100 A/ 200 E is composed of: i) freestanding battery active material layer  101 / 201  having first and second major surfaces ( 101   i / 201   i  and  101   ii / 201   ii ) and lengthwise edge surfaces ( 101   iii / 201   iii  and  101   iv / 201   iv ); and ii) inert liquid layer  102 / 202  encapsulating the major surfaces and the lengthwise edge surfaces (e.g., a super dry liquid hydrocarbon layer). In various embodiments inert liquid layer  102 / 202  is a super dry hydrocarbon that fully wets out the first and second major opposing surfaces and lengthwise edge surfaces ( 101   i ,  101   ii ,  101   iii , and  101   iv  as well as  201   i ,  201   ii ,  201   iii , and  201   iv ). 
     With reference to  FIG.  2 B  and  FIG.  2 F  there is illustrated a substrate supported electrochemical material laminate structure in accordance with various embodiments of the present disclosure. Structure  100 B/ 200 F is composed of battery active material layer  101 / 201  and material backing layer  103 / 203 , which may be rigid or flexible. In various embodiments layer  103 / 203  is a substrate onto which the battery active material layer is formed, or it (the backing layer) may be applied to second major surface 101ii/201ii after layer  101 / 201  has already been formed. Inert liquid layer  102 / 202  encapsulates first major surface  101   i / 201   i , and may additionally encapsulate its lengthwise edge surfaces, as shown. In various embodiments backing layer  103  extends beyond layer  101 / 201 , and the inert liquid wets out the lengthwise edges, as shown. In various embodiments, backing layer  103 / 203  is electronically insulating, and used generally as a supporting layer  101 / 201  during handling, storage and processing (e.g., as an interleave to facilitate winding and unwinding). For example, when the battery active material layer is sulfide glass solid electrolyte layer  201 , backing layer  103  may be an inert organic polymer (e.g., a polyethylene or polypropylene film). In other embodiments, when the battery active material layer is lithium metal layer  101 , backing layer  103  (flexible or rigid) may be electronically conductive, and thereon serve as a current collector in a battery cell. For instance, backing layer  103  may be a metal foil or mesh (e.g., copper), or it (backing layer  103 ) may be a thin copper film deposited on a polymer support layer (e.g., a polyester film). When backing layer  103  is intended to serve as a current collector, standalone electrochemical material laminate structure 100B is sometimes referred to herein as having electrode architecture. 
     With reference to  FIG.  2 C  and  FIG.  2 G  there is illustrated standalone electrochemical material layer structure  100 C/ 200 G, which, in accordance with various embodiments of the present disclosure has, what is termed herein, a wet-decal architecture, and for this reason structure 100C/200Gis sometimes referred to herein more simply as a wet-decal or decal (e.g., Li-decal 100C or sulfide glass decal 200G). Laminate structure  100 C/ 200 G includes solid material release layer  104 / 204  covering but not touching battery active material layer surface  101   i / 201   i , and inert liquid layer  102 / 202   sandwiched there between, and encapsulating the surface on which it is applied ( 101   i / 201   i ). 
     Preferably, the inert liquid of layer  102 / 202  completely wets out surface  101   i / 201   i  as well as the surface of release layer  104 / 204 , and this leads to the formation of a liquid bridge between the layers and an associated wet adhesive force that assists in maintaining the release layer on the battery active material during handling and processing. The degree of wettability may be determined by the contact angle (□ □. Accordingly, in various embodiments one criterion that may be used for selecting the protective liquid is based, in part, on its ability to fully wet out the battery active material surface on which it is disposed. To effect wetting the contact angle that the liquid makes with the solid surface should be in the range of  0  □ ≤ □ □ □ □ □ □ □ □ □ and preferably □ is near  0  □ □ for complete wet out □ □ ε.γ., □ □ □ □□  0  □ ). Preferably the ability of the inert liquid to wet out both surface  101   i / 201   i  and layer  104 / 204  is sufficient to spread the inert liquid layer evenly and intimately over surface  101   i / 201   i , to encapsulate it (the first major surfaces) and prevent the solid release layer from touching the battery active material. Preferably, inert liquid layer  102 / 202  is thin enough to bring about a tight liquid bridge that is capable of maintaining the solid release on the battery active material during handling and processing. 
     Continuing with reference to  FIG.  2 C  and  FIG.  2 G , in various embodiments the average thickness of protective liquid layer  102 / 202  is not greater than 50 □ m, or not greater than 25 □m, or not greater than 10 □m, or not greater than 5 □m, but sufficiently thick and uniform, nonetheless, to prevent contact between the release layer and surface  101   i  (e.g., 50 □m &gt; t &gt; 5 □m; or 5 □ m &gt; t &gt; 100 nm). In various embodiments, inert liquid layer  102 / 202  has an average thickness in the range of 1 □m &gt; t &gt; 100 nm; or in the range of 5 □ m &gt; t &gt; 1 □m; or in the range of 50 □m &gt; t &gt; 5 □m. However, the present disclosure is not limited as such, and it is contemplated that structure  100 C/ 200 C may have pockets or isolated locations that are not covered by protective liquid, and in such embodiments, it is especially important that release layer  104 / 204  is inert in contact with the battery active material. 
     The wet decal architecture, as described above, has a number of advantages, including: i) protecting surface  101   i / 102   i  against physical damage during handling; ii) enhancing the utility and/or the ability to use medium to high vapor pressure inert liquids by lessening their effective evaporation rate; iii) improving protection against degradation of surface  101   i / 201   i  against impurity molecules from the ambient atmosphere, as the release layer itself provides an additional barrier against contaminating molecules entering the protective liquid from the ambient atmosphere; iv) extending storage shelf life and service lifetimes due to the additional barrier properties and lower evaporation rate of the inert liquid layer; and finally v) the solid release layer may serve as an interleave for winding or stacking the laminate structures. 
     With reference to  FIG.  2 D  and  FIG.  2 H , in various embodiments the wet-decal architecture is sealed along its lengthwise edges by seal  113 / 213 , the seal providing an additional barrier against diffusion of impurity molecules from the ambient atmosphere seeping into the inert liquid layer and for minimizing evaporation of the inert liquid out from the laminate. When sealed, the lengthwise edges are preferably also covered in direct contact with inert liquid. Lengthwise edge seal  113 / 213  may be made by heat and pressure applied between release layer  104 / 204  and backing layer  103 / 203 , which, in various wet-decal embodiments is simply a second release layer, similar or the same as layer  104 / 204 . In embodiments wherein structure  100 D/ 200 H includes current collector layer  103 , an additional sealable backing layer may be placed behind the current collecting layer, for sealing the lengthwise edges. During downstream processing, when the release layer needs to be removed, the edge seal may be broken by slicing with a sharp edge. 
     In various embodiments the laminate thickness, as measured from the second major surface of the battery active material layer  101   ii / 201   ii  to the top surface of inert liquid layer  102 / 202  is no greater than 1 mm thick, and more typically no greater than 500 um thick. For instance, in various embodiments the laminate thickness (as defined above) is less than 500 um, and typically less than 200 um, and in some embodiments less than 100 um, or less than 50 um (e.g., between 5 - 100 um). The laminate thickness, as defined above, does not include the thickness of the solid release layer, or backing layer when present. 
     Nanofilm-Encapsulated Sulfide Glass Solid Electrolyte Structures 
     With reference to  FIGS.  2 I- P  there are illustrated cross sectional depictions of nanofilm-encapsulated sulfide glass solid electrolyte structures, in accordance with various embodiments of the present disclosure. With reference to  FIG.  2 I , nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 I is composed of: i) sulfide glass solid electrolyte sheet  201 -Z having first and second major opposing surfaces ( 201   i -Z and  201   ii -Z) and opposing lengthwise edge surfaces  201   iii -Z/ 201   iv -Z; and ii) continuous inorganic nanofilm  202 -Z- 2 I which encapsulates the sulfide glass surfaces in direct contact. Not shown in  FIG.  2 I  are the opposing widthwise edge surfaces of sulfide sheet  201 -Z. In various embodiments, the opposing widthwise edges are also encapsulated by nanofilm  202 -Z- 2 I, and in such embodiments solid electrolyte structure  200 - 2 I is referred to herein as fully encapsulated (i.e., all surfaces of glass sheet  201 -Z are encapsulated by nanofilm  202 -Z- 2 I). In some embodiments, the widthwise edges are not encapsulated, but may ultimately be shielded from the ambient atmosphere by a polymeric edge sealant (also not shown). 
     Continuing with reference to  FIG.  2 I , encapsulating nanofilm  202 -Z- 2 I is a conformal pinhole free inorganic material layer that encapsulates, in direct contact, sulfide sheet surfaces  201   i -Z,  201   ii -Z,  201   iii -Z, and  201   iv -Z. The nanofilm is conformal so its surfaces adjacently align with the surfaces of the sulfide glass sheet on which it (the nanofilm) encapsulates. Accordingly, in a likewise fashion to that of sulfide glass sheet  201 -Z, the nanofilm may be characterized similarly, as having first and second opposing major surfaces ( 202   i -Z and  202   ii -Z), opposing lengthwise edge surfaces  202   iii -Z and  202   iv -Z, and opposing widthwise edge surfaces, not shown. Moreover, when describing certain aspects of the nanofilm, such as its composition, thickness, performance and function, it is expedient, for descriptive purposes, to differentiate specific portions of the continuous nanofilm, and in particular to distinguish among those portions of the nanofilm that are adjacent the first and second sulfide glass major surfaces and those which are adjacent the peripheral edge surfaces. As shown in  FIG.  2 I , portion  202   a -Z and portion  202   b -Z refer to those portions of nanofilm  202 -Z- 2 I which are adjacent sulfide glass major surfaces  201   i -Z and  201   ii -Z, and portions of the nanofilm that encapsulate the edges of the sulfide glass sheet are referred to as edge encapsulating portions (e.g., lengthwise and widthwise nanofilm edge portions). 
     In various embodiments, thickness of nanofilm  202 -Z- 2 I is a tradeoff between enhancing the moisture barrier properties by using a thicker film, and ensuring that the nanofilm is sufficiently thin to be transparent or permeable to Li-ions, so to allow lithium ions to move across the solid electrolyte separator without effectuating a large area specific resistance (ASR); e.g., the ASR of the separator is no greater than  200  □-cm2, when measured in a battery cell at room temperature, and preferably no greater than 100 □-cm2, and even more preferably no greater than 50 □-cm2. Other considerations regarding nanofilm thickness include time of fabrication, reliability and yield. 
     In various embodiments, the first and second major portions of continuous nanofilm 202-Z-2I each has substantially uniform thickness, typically in the range of 1 nm to 100 nm; e.g., [(1 nm ≤ t &lt; 5 nm); (5 nm ≤ t &lt; 10 nm); (10 nm ≤ t &lt; 30 nm); (30 nm ≤ t &lt; 50 nm); (50 nm ≤ t &lt; 100 nm)]. 
     In various embodiments, the first and second major portions of nanofilm 202-Z-2I (i.e., portion 202a-Z and portion 202b-Z) have uniform thickness of about 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 10 nm, or about 20 nm, or about 30 nm or about 40 nm or about 50 nm, or about 60 nm, or about 70 nm or about 80 nm or about 90 nm or about 100 nm). 
     Generally, when referring to the nanofilm thickness, it is meant the thickness of the nanofilm adjacent to the first and second major surfaces (i.e., the thickness of the nanofilm major portions  202   a -Z and  202   b -Z), as it is these surfaces which adjacently oppose the electrodes in a battery cell and therefore function electrochemically. Whereas the primary benefit provided by the edge portion of the nanofilm is to effect a moisture barrier and preferably enhance mechanical strength by blunting surface defects at or near the edge of the sulfide glass sheet, and so it (the edge portion of the nanofilm) should be sufficiently thick to provide a water impervious barrier (as described above). As a result of the conformal nature of the nanofilm, the thickness of its edge portion(s) are generally a function of the thickness of the nanofilm first and second major portions, and the edge portion thickness is generally similar to or greater than the thickness of the major nanofilm portions, because, as described in more detail below, the edge regions may be coated more than once when forming the continuous nanofilm. Accordingly, in various embodiments the nanofilm has an edge portion thickness that is substantially equal to the sum of the first and second nanofilm major portions  202   a -Z and  202   b -Z. 
     In various embodiments nanofilm  202 -Z- 2 I is a continuous and conformal film having substantially uniform composition and first and second major portion thicknesses less than 1000 nm, and more typically less than 500 nm, and even more typically less than 200 nm. Typically, the nanofilm first and second major portion thicknesses are between 100 nm to 0.1 nm (e.g., between 10 nm to 1 nm). 
     With reference to  FIGS.  2 J -  2 P  there are illustrated cross sectional depictions of various embodiments of nanofilm-encapsulated sulfide glass solid electrolyte structures of the present disclosure wherein the nanofilm is configured to have a varied thickness and/or a varied composition relative to the position of the nanofilm along the sulfide sheet surface on which it encapsulates. In other words, nanofilm first major portion  202   a -Z has a first composition and a first thickness, and nanofilm second major portion  202   b -Z has a second composition and a second thickness. 
     With reference to  FIGS.  2 J- 2 K , separator structures  200 - 2 J and 200-2 K are composed of sulfide glass solid electrolyte sheet  201 -Z encapsulated by continuous inorganic nanofilm  202 -Z- 2 I and  202 -Z- 2 J, respectively. In accordance with these embodiments, the conformal nanofilm has a substantially uniform composition throughout and a thickness that is engineered to vary relative to the sulfide sheet surface on which it encapsulates. For solid electrolyte structure  200 - 2 J, nanofilm thickness (Ti) refers to the substantially uniform nanofilm thickness adjacent sulfide sheet surface  201   i -Z (i.e., the thickness of nanofilm portion  202   a -Z), and it is significantly greater than nanofilm thickness (Tii), which is the substantially uniform nanofilm thickness adjacent sulfide sheet surface  201   ii -Z (i.e., the thickness of nanofilm portion  202   b -Z) And for solid electrolyte structure  200 - 2 K shown in  FIG.  2 K , Tii (thickness of nanofilm portion  202   b -Z) is significantly greater than Ti (thickness of nanofilm portion  202   a -Z) Typically, when the thickness of the nanofilm along the major surfaces of the sulfide sheet are different, they are nonetheless generally substantially uniform. In various embodiments the absolute value of the difference between Ti and Tii is between 1 - 5 nm, or between 5 - 10 nm, or between 10 - 20 nm, or between 20 - 50 nm, or between 50 - 100 nm. 
     With reference to  FIG.  2 L  there is illustrated nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 L wherein sulfide glass solid electrolyte sheet  201 -Z is encapsulated by two continuous and conformal nanolayers (first nanolayer:  202 -Z-A) and (second nanolayer:  202 -Z-B), which, in combination, form continuous nanofilm  202 -Z- 2 L. Continuous nanolayer  202 -Z-A encapsulates in direct contact sulfide sheet first major surface Z 101   i  (thus forming major nanofilm portion  202   a -Z) and continuous nanolayer  202 -Z-B encapsulates, in direct contact, sulfide sheet first major surface Z 101   ii  (thus forming major nanofilm portion  202   b -Z). In accordance with this embodiment, nanofilm  202 -Z- 2 L is configured to have an asymmetric architecture wherein the material composition of first nanolayer  202 -Z-A is different than the material composition of second nanolayer  202 -Z-B (i.e., the material composition of the first major nanofilm portion is different than the material composition of the second major nanofilm portion. With reference to solid electrolyte structure  200 - 2 L, the asymmetric nanofilm is a contiguous planar composite of first and second nanolayers, as opposed to a stacked multi-layer, which it is not as the nanolayers do not overlap on either major surface of the sulfide glass sheet. Rather the contiguity of the nanolayers is realized by an overlap at the edge portions of the glass sheet. 
     Additional nanofilm-encapsulated sulfide glass solid electrolyte structures having asymmetric architectures are shown in  FIGS.  2 M,  2 N, and  2 O , and described in more detail below. 
     With reference to  FIG.  2 M  there is illustrated nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 M wherein sulfide glass solid electrolyte sheet  201 -Z is encapsulated by two continuous and conformal nanolayers (first nanolayer:  202 -Z-A) and (second nanolayer:  202 -Z-B), which, in combination, form continuous nanofilm  202 -Z- 2 M. Continuous nanolayer  202 -Z-B encapsulates in direct contact sulfide sheet first major surface  201   i -Z and sulfide sheet second major surface  201   ii -Z. And continuous nanolayer  202 -Z-A encapsulates, in direct contact, nanolayer  202 -Z-B, in that region of nanofilm  202 -Z- 2 M which is adjacent to sulfide sheet  201   i -Z and does not encapsulate (and preferably does not contact) nanolayer  202 -Z-B in that region of the nanofilm adjacent to sulfide sheet surface  201   ii -Z. In accordance with this embodiment, the material composition of first nanolayer  202 -Z-A is different than the material composition of second nanolayer  202 -Z-B. And with reference to  FIG.  2 N , nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 N is similar to structure  200 - 2 M, as shown in  FIG.  2 M , except that for structure  200 - 2 N, nano layer  202 -Z-B encapsulates nanolayer  202 -Z-A adjacent sulfide glass sheet surface  201   ii -Z, and nanolayer  202 -Z-B does not encapsulate (and preferably does not contact) nanolayer  202 -Z-A in that region of nanofilm  202 -Z- 2 N which is adjacent to sulfide sheet surface  201   i -Z. 
     With reference to  FIG.  2 O  there is illustrated nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 O wherein sulfide glass solid electrolyte sheet  201 -Z is encapsulated by two continuous and conformal nanolayers (first nanolayer:  202 -Z-A) and (second nanolayer:  202 -Z-B), which, in combination, form continuous nanofilm  202 -Z- 2 O. Continuous nanolayer  202 -Z-A encapsulates in direct contact sulfide sheet first major surface  201   i -Z, and continuous nanolayer  202 -Z-B encapsulates, in direct contact, nanolayer  202 -Z-A, in that region of nanofilm  202 -Z- 2 O which is adjacent to sulfide sheet  201   i -Z and encapsulates sulfide glass sheet surface  201   ii -Z in direct contact. Nanolayer  202 -Z-A, however, does not encapsulate (and preferably does not contact) sulfide glass sheet surface  201   ii -Z. And with reference to nanofilm-encapsulated structure  200 - 2 P illustrated in  FIG.  2 P , sulfide glass solid electrolyte sheet  201 -Z is encapsulated on glass sheet surface  201   ii -Z by nanolayer  202 -Z-B and is encapsulated on glass sheet surface  201   i -Z by nanolayer  202 -Z-A, which also encapsulates nanolayer  202 -Z-B in that region of nano film  202 -Z-P which is adjacent to sulfide sheet surface  201   ii -Z. 
     In various embodiments sulfide glass solid electrolyte sheet  201 -Z is in the form of a ribbon (e.g., a long narrow sheet), having substantially parallel lengthwise edges and a thickness in the range of  5  um to  500  um, and more typically in the range of  10  um to  100  um, and even more typically in the range of 20 - 50 um. In various embodiments sulfide glass solid electrolyte sheet  201 -Z is in the form a discrete sheet, typically at least 1 cm wide and at least 2 cm long (e.g., at least 2 cm wide and at least 5 cm long). Particularly suitable sulfide glass solid electrolyte sheets are described in Applicant’s pending patent applications US Pat. Application No.: 14/954,816 filed Nov. 30, 2015 and titled Standalone Sulfide Based Lithium Ion-Conducting Glass Solid Electrolyte and Associated Structures, Cells and Methods, and US Pat. Application No.: 14/954,812 filed Nov. 30, 2015 and titled Vitreous Solid Electrolyte Sheets of Li Ion Conducting Sulfur-Based Glass and Associated Structures, Cells and Methods; incorporated by reference herein for their glass composition and processing disclosures. For instance, sulfide glass compositions described therein, and which are particularly useful as the sulfide glass composition for sheet 201-Z include the following specific compositional examples: 0.7Li2S-0.29P2S5-0.01P2O5; 0.7Li2S-0.28P2S5-0.02P2O5; 0.7Li2S-0.27P2S5-0.03P2O5; 0.7Li2S-0.26P2S5-0.04P2O5; 0.7Li2S-0.25P2S5-0.05P2O5; 0.7Li2S-0.24P2S5-0.06P2O5; 0.7Li2S-0.23P2S5-0.07P2O5; 0.7Li2S5S-0.22P2S5-0.08P2O5; 0.7Li2S-0.21P2S5-0.09P2O5; 0.7Li2S-0.2P2S5-0.1P2O5; 0.7Li2S-0.29B2S3-0.01B2O3; 0.7Li2S-0.28B2S3-0.02B2O3; 0.7Li2S-0.27B2S3-0.03B2O3; 0.7Li2S-0.26B2S3-0.04B2O3; 0.7Li2S-0.25B2S3-0.05B2O3; 0.7Li2S-0.24 B2S3-0.06B2O3; 0.7Li2S-0.23B2S3-0.07B2O3; 0.7Li2S-0.22B2S3-0.08B2O3; 0.7Li2S-0.21 B2S3-0.09B2O3; 0.7Li2S-0.20B2S3-0.1B2O3; 0.7Li2S-0.29B2S3-0.01P2O5; 0.7Li2S-0.28 B2S3-0.02P2O5; 0.7Li2S-0.27B2S3-0.03P2O5; 0.7Li2S-0.26 B2S3-0.04P2O5; 0.7Li2S-0.25 B2S3-0.05P2O5; 0.7Li2S-0.24B2S3-0.06P2O5; 0.7Li2S-0.23B2S3-0.07P2O5; 0.7Li2S-0.22 B2S3-0.08P2O5; 0.7Li2S -0.21B2S3-0.09P2O5; 0.7Li2S-0.20B2S3-0.1P2O5; 0.7Li2S-0.29 B2S3-0.01SiS2; 0.7Li2S -0.28B2S3-0.02SiS2; 0.7Li2S-0.27 B2S3-0.03SiS2; 0.7Li2S-0.26 B2S3-0.04SiS2; 0.7Li2S -0.25B2S3-0.05SiS2; 0.7Li2S-0.24 B2S3-0.06SiS2; 0.7Li2S-0.23 B2S3-0.07SiS2; 0.7Li2S-0.22B2S3-0.08SiS2;0.7Li2S-0.21B2S3-0.09SiS2; 0.7Li2S-0.20B2S3-0.1SiS2. 
     Particularly suitable silicon sulfide glass compositions include (1-x)(0.5Li2S-0.5SiS2)-xLi4SiO4; (1-x)(0.6Li2S-0.4SiS2)-xLi4SiO4; (1-x)(0.5 Li2S-0.5SiS2)-xLi3BO3; (1-x)(0.6Li2S-0.4SiS2)-xLi3BO3; (1-x)(0.5Li2S-0.5SiS2)-xLi3PO4; (1-x)(0.6Li2S-0.4SiS2)-xLi3PO4; wherein x ranges from 0.01 - 0.2. Specific examples include: 0.63Li2S-0.36SiS2-0.01Li3PO4; 0.59Li2S-0.38SiS2-0.03Li3PO4; 0.57Li2S-0.38SiS2-0.05Li3PO4; and 0.54Li2S-0.36SiS2-0.1Li3PO4. 
     In various embodiments the composition of sulfide glass sheet 201-Z is of the type having composition: xLi2S-yP2S5-zSiS2, xLi2S-yB2S3-zSiS2, xLi2S-yP2S5-zSiO2, xLi2S-yB2S3-zSiO2, xLi2S-yB2S3-zB2O3, or xLi2S-yP2S5-zP2O5; wherein x+y+z = 1 and x=0.4-0.8, y=0.2-0.6, and z ranging from 0 to 0.2 (e.g., about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06,0.07, 0.08, 0.09, 0.1, 0.11, 0.12,0.13, 0.14, 0.15, 0.16,0.17, 0.18, 0.19, 0.2), and particularly x+y+z = 1 and x=0.6-0.7, y=0.2-0.4, and z ranging from 0 to 0.2 (e.g., z is between 0.01-0.2, such as about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13,0.14, 0.15, 0.16, 0.17,0.18, 0.19, 0.2); and more particularly x+y+z = 1 and x=0.7, y=0.2-0.3, and z ranging from 0 to 0.2 (e.g., z is between 0.01-0.2, such as about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14,0.15, 0.16, 0.17, 0.18,0.19, 0.2). 
     In various embodiments the composition of sulfide glass sheet 201-Z is of the type having composition: xLi2S-ySiS2-zP2S5 or xLi2S-ySiS2-zP2O5; wherein x+y+z = 1 and x=0.4-0.6, y=0.2-0.6, and z ranging from 0 to 0.2 (e.g., z is between 0.01-0.2 such as about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2), and particularly wherein x+y+z = 1 and x=0.5-0.6, y=0.2-0.5, and z ranging from 0 to 0.2 (e.g., z is between 0.01-0.2 such as about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2). 
     As described above, in exemplary embodiments sulfide based solid electrolyte sheet 201-Z is a continuous vitreous sheet of sulfide glass (e.g., a monolithic sheet of sulfide glass); however, the present disclosure is not limited to nanofilm-encapsulated sulfide sheets of glass, but is meant to include other moisture sensitive sulfide based solid electrolyte layers, such as sheets composed of Li ion conducting sulfide ceramics and glass ceramics materials that benefit from an encapsulating-nanofilm, as described herein. For instance, it is contemplated herein that moisture sensitive sulfide solid electrolyte sheet 201-Z may be formed as a continuous sheet of sulfide glass that is subsequently crystallized or partially crystallized to form a ceramic or glass-ceramic sulfide sheet, or the ceramic/glass-ceramic sulfide sheet may be crystallized during glass sheet formation. In alternative embodiments, sulfide based solid electrolyte layer 201-Z may be a sulfide sheet formed by powder/particle compaction of Li ion conducting sulfide particles, including sulfide glass particles, sulfide glass-ceramic particles, polycrystalline sulfide ceramic particles and combinations thereof. Such materials include thio-Lisicons and LGPS type ionic conductors. For example, Li4GeS4, Li3PS4, Li4SiS4, Li3.25Ge0.25P0.75S4, Li4+xSi1-xAlxS4 and Li4+xGe1-xGaxS4, Li4-xSi1-xPxS 4 with x=0.6, Li10GeP2S12, Li7P3 S11, Li11AlP2S12, Li10SnP2S12. Sulfide based solid electrolyte structures made by particle compaction are described in U.S. Pat. Pub. No.: 20120177997; U.S. Pat. Pub. No.: 20130164631; and U.S. Pat. Pub. No.: 20160133989, and as described herein, may be improved upon by encapsulating one or more of the sulfide surfaces with an encapsulating nanofilm, as described throughout this disclosure. 
     Nanofilm Composition and Thickness 
     The choice of material layer compositions for the inorganic nanofilm is informed by the ability of that material, in dense ultra-thin form, to impart the desired functionality and/or advantage, such as moisture imperviousness, improved mechanical strength, enhanced chemical resistance to liquid electrolytes and oxidative stability in direct contact with cathode electroactive materials (e.g., intercalation materials having a voltage versus lithium metal that is greater than about 2.5 V, or greater than about 3 V or greater than about 3.5 V). 
     In various embodiments the material composition of the nanofilm or nanolayer is an insulator in bulk form, but is transparent or permeable to lithium ions as a nano layer. 
     In various embodiments the nanofilm composition is a binary metal/semi-metal oxide or metal/semi-metal nitride; the binary nature generally simplifies nanofilm deposition, and so is preferable, however the present disclosure is not limited as such. Particularly suitable compositions include the following and their combinations, aluminum oxide, boron oxide, zirconium oxide, yttrium oxide, hafnium oxide, and niobium oxide, tungsten oxide, titanium oxide, tantalum oxide, molybdenum oxide, zinc oxide, silicon oxide, vanadium oxide, chromium oxide, and silicon nitride, aluminum nitride, boron nitride, tungsten nitride, titanium nitride, chromium nitride, tantalum nitride, copper nitride, gallium nitride, indium nitride, tin nitride, zirconium nitride, niobium nitride, hafnium nitride, tantalum nitride. Multi-component nanofilm compositions (e.g., tertiary, ternary, and quaternary compositions) are also contemplated herein, including oxides and nitrides of one or more metals/semi-metals, including aluminum, boron, zirconium, yttrium, hafnium, niobium, tungsten, titanium, tantalum, vanadium, chromium, molybdenum, zinc, and silicon. Moreover, the above listed compositions may be combined with lithium to form lithium containing nanofilm compositions, including: lithium metal/semi-metal oxides, such as lithium aluminum oxide, lithium aluminum silicon oxide, lithium tantalum oxide and lithium niobium oxide; and lithium metal/semi-metal nitrides, such as lithium aluminum nitride, lithium silicon nitride, lithium boron nitride and combinations thereof. In another embodiment, the nanofilm may be a moisture resistant sulfide, such as zinc sulfide. 
     In particular embodiments, the nanofilm is a phosphorous oxide or oxynitride, such as a lithium phosphorous oxide (e.g., Li3PO4) and lithium phosphorous oxynitride (i.e., a LiPON type nanofilm) with various stoichiometries, including Li2PO2N. 
     In particular embodiments, the nanofilm is a phosphorous nitride (e.g., P3N5 or PN), and in embodiments thereof may be a lithium phosphorous nitride devoid of oxygen; i.e., a ternary lithium phosphorous-nitride compound (e.g., LiPN2, Li4PN3, Li7PN4). 
     In various embodiments, the nanofilm composition is that of an intrinsic Li ion conducting material. Intrinsic lithium ion conducting materials comprise lithium ions, and are generally understood in the art as lithium ion conducting solid electrolyte materials. An intrinsic Li ion conducting material is, itself, Li ion conductive, and typically has a room temperature conductivity of at least 10-7 S/cm, and its ability to conduct Li ions does not depend on a second material (e.g., a material layer onto which it is coated). Examples of intrinsic Li ion conducting material compositions which are suitable herein for use as the material of the nanofilm or that of a nanolayer include lithium phosphorous oxynitride (e.g., LiPON), lithium titanates, lithium lanthanium titanates, lithium phosphate (e.g., Li3PO4), lithium nitrate (LiNO3), lithium silicates, lithium tantalum oxide (e.g., LiTaO3), lithium aluminum oxide (e.g., LiAlOx), lithium niobium oxide (e.g, LiNbO3), lithium nitride (Li3N), lithium silicon aluminum oxide, lithium germanium aluminum oxide, and lithium germanium silicon aluminum oxide. In contradistinction, nanofilm materials that are devoid of lithium, are not intrinsic lithium ion conductors (e.g., metal oxides and metal nitrides devoid of lithium as well as phosphorous nitrides devoid of oxygen and lithium). 
     With reference to  FIG.  2 I , in various embodiments, the nanofilm composition is an inert binary metal oxide (e.g., alumina, hafnia, zirconia), and the thickness of the alumina nanofilm is in the range of 1 nm to 100 nm (e.g., about 1 nm, or about 2 nm or about 5 nm, or about 10 nm, or about 20 nm or about 30 nm or about 40 nm or about 50 nm or about 60 nm or about 70 nm or about 80 nm or about 90 nm or about 100 nm). In particular embodiments, the inert metal oxide nanofilm fully encapsulates all surfaces of the sulfide glass sheet and has a thickness in the range of about 1 nm to 5 nm (e.g., about 1 nm, or about 2 nm, or about 3 nm, or about 4 nm, or about 5 nm. It is also contemplated herein that some amount of moisture barrier benefit is provided from an exceptionally thin fully encapsulating nanofilm, having thickness less than 1 nm (e.g., about 0.1 nm, or about 0.2 nm, or about 0.3 nm, or about 0.4 nm, or about 0.5 nm, or about 0.6 nm, or about 0.7 nm, or about 0.8 nm, or about 0.9 nm). In another particular embodiment, the inert nanofilm may be employed to provide superior moisture barrier properties for protecting the sulfide glass during storage. In such said embodiments, thicker nanofilms generally provide an improved barrier; for instance, inert nanofilms with enhanced barrier properties are contemplated herein to have thickness in the range of 5 nm to 10 nm, or 10 nm to 20 nm, or 20 - 30 nm, or 30 - 40 nm, or 40 - 50 nm, or 50 - 60 nm or 60 - 70 nm, or 70 - 80 nm, or 80 - 90 nm or 90 - 100 nm. In various embodiments, prior to incorporating the solid electrolyte structure into a battery cell and/or prior to depositing lithium metal onto the first major surface of the nanofilm, the nanofilm thickness adjacent the first and/or second major surfaces of the sulfide glass sheet is reduced or entirely removed (e.g., by plasma etching that portion of the nanofilm). As described in more detail herein below, when making a solid-state laminate of the present disclosure, the procedure to remove the nanofilm is performed just prior to depositing lithium metal onto the first major surface of the glass sheet (e.g., an inert binary metal oxide nanofilm (e.g., alumina) of thickness greater than 5 nm is entirely removed by Argon plasma etching prior to depositing lithium metal onto that surface). 
     With reference to nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 L shown in  FIG.  2 L , nanofilm  202 -Z- 2 L is configured to have an asymmetric architecture wherein the thickness and/or composition of the nanofilm first major portion is different than that of the nanofilm second major portion. In various embodiments, the asymmetric architecture nanofilm is composed of two nanolayers: i) first nanolayer  202 -Z-A, which is an inert material layer having a thickness and composition that provides a moisture barrier and a low resistance interface in direct contact with lithium metal (e.g., the ASR of the solid electrolyte structure is less than 50 □ -cm2, and preferably less than 25 □-cm2; and ii) second nanolayer  202 -Z-B having thickness and composition suitable for it to serve as a moisture barrier and to provide an inert surface, which, when configured in a battery cell, opposing the cathode, is chemically compatible in direct contact with cathode electroactive material having an electrochemical potential of 3 Volts or greater versus lithium metal, and therewith prevents oxidation of the sulfide glass and/or prevents dissolution of sulfide glass material into the liquid electrolyte of the battery cell. 
     Continuing with reference to  FIG.  2 L , in a particular embodiment first nanolayer  202 -Z-A is an inert metal nitride and second nanolayer  202 -Z-B is an inert metal oxide (e.g., a binary metal nitride and a binary metal oxide). In a specific embodiment thereof inert metal nitride nanolayer  202 -Z-A is devoid of lithium metal (e.g., silicon nitride), and reactively converts to a lithiated composition when contacted with lithium metal during fabrication of a solid-state laminate electrode assembly, as described in more detail herein below. For instance, silicon nitride (e.g., SiN, Si3N4, SiNx) converts to Li2SiN2 to form a low resistance interface between the lithiated silicon nitride nanolayer and the as-deposited lithium metal layer, which is typically formed by evaporation. In various embodiments thickness of first major portion  202   a -Z of silicon nitride nanolayer  202 -Z-A is in the range of 1 to 100 nm (e.g., in the range of 1 nm to 10 nm). Continuing with reference to nanofilm-encapsulated sulfide glass solid electrolyte structure  200 - 2 L, in a specific embodiment second nanolayer  202 -Z-B is an inert metal oxide such as aluminum oxide, zirconium oxide, and niobium oxide, with thickness in the range of 0. 1 nm to 100 nm. In particular embodiments, the thickness of inert metal oxide nanolayer  202 -Z-B is in the range of 0.1 nm to 1 nm, or in the range of 1 nm to 10 nm. 
     Continuing with reference to  FIG.  2 L , in another particular embodiment first nanolayer  202 -Z-A is a phosphorous nitride devoid of oxygen (e.g., P3N5) that reactively lithiates in direct contact with lithium metal (e.g., upon lithium evaporation), to form a lithiated phosphorous nitride devoid of oxygen (e.g., LiPN2, Li4PN3, Li7PN4, Li3N and Li3P mixed phase, or a combination thereof). In various embodiments thickness of first major portion  202   a -Z of the P3N5 nanolayer  202 -Z-A is in the range of 1 to 100 nm (e.g., in the range of 1 nm to 10 nm). 
     With reference to the encapsulated sulfide glass solid electrolyte structures described and illustrated in  FIGS.  2 I-  2 P , in various embodiments all surfaces of the sulfide glass solid electrolyte sheet 201-Z are encapsulated in directed contact by the nanofilm. 
     In various embodiments, to achieve the requisite conformal and encapsulating features, the continuous encapsulating nanofilm and its associated nanolayers are deposited/coated onto the surfaces of the sulfide glass sheet via the technique known as atomic layer deposition (ALD), including PEALD (plasma enhanced atomic layer deposition). ALD is a vapor phase deposition process, and generally consists of multiple coatings of chemical precursors that react with each other, and the sulfide sheet, to form a monolayer on the sheet surface. Forming the nanofilm using an ALD process allows for precise and accurate control of thickness and conformality, which is an attribute that allows the continuous nanofilm to form and encapsulate the edge and corner surfaces of the sulfide solid electrolyte sheet. Two reviews on ALD include: i) a journal article published in Materials Today, Volume 17, Number 5, June 2014 by Richard W. Johnson, Adam Hultqvist, and Stacey F. Bent entitled “A brief review of atomic layer deposition: from fundamentals to applications;” and ii) a journal article published in Chem. Rev.  2010 , 110, 111-131 by Steven M. George, and entitled “Atomic Layer Deposition: An Overview,” both of which are incorporated by reference herein for their disclosures relating to ALD techniques. When the sulfide sheet takes the form of a continuous web (e.g., a continuous web of Li ion conducting vitreous sulfide glass), ALD techniques for continuous roll-to-roll deposition may be used, and are described in U.S. Pat. No.: 9,598,769 entitled “Method and System for Continuous Atomic Layer Deposition;” U.S. Pat. No.: 8,304,019 entitled “Roll-to-Roll Atomic Layer Deposition Method and System;” U.S. Pat. Pub. No.; 2007/0281089 entitled “Systems and Methods for Roll-to-Roll Atomic Layer Deposition on Continuously Fed Objects;” U.S. Pat. Pub. No.: 2015/0107510 entitled “Coating a Substrate Web by Atomic Layer Deposition.” In various embodiments, immediately prior to depositing the nanofilm (or nanolayers) the surfaces of the sulfide based solid electrolyte sheet are cleaned by plasma etching. 
     With reference to  FIG.  2 Q  there is illustrated a process flow chart illustrating methods for making various embodiments of nanofilm-encapsulated sulfide glass solid electrolyte structures in accordance with the present disclosure. The methods include an initial operation (operation 1) of providing (e.g., making) a sulfide glass solid electrolyte sheet. In various embodiments, the sheet is a strip of sulfide glass having a length to width aspect ratio of at least 2, or at least 3 or at least 4 or at least 5 or at least 10. In particular embodiments the sulfide sheet of glass is provided as a web. In a second operation (operation 2), organic residue is removed from the surfaces of the glass sheet by any suitable technique, for example by plasma etching, such as Argon plasma etching. Thereafter the encapsulating-nanofilm is deposited via atomic layer deposition (ALD) onto the sulfide glass sheet, and the operations for making the nanofilm vary depending on the final architecture of the nanofilm-encapsulated sulfide solid electrolyte structure, and in particular the construction of the nanofilm. 
     In various embodiments the deposition of the nanofilm takes place in two operations. With respect to process A, as shown in  FIG.  2 Q , the third operation (operation 3a) involves depositing a first nanolayer via ALD onto the first major surface of the sulfide glass sheet as well as the peripheral edge surfaces of the glass. The fourth operation (operation 4a) involves depositing a second nanolayer via ALD onto the second major surface of the sulfide glass sheet, and the peripheral edge portions of the first nanolayer. Depending on the composition and thickness of the nanolayers, process A may yield a number of different nanofilm architectures, and three embodiments are illustrated in the process flow diagram, Solid electrolyte structure 2P1 is formed when the second nanolayer has the same composition and thickness as the first nanolayer (solid electrolyte structure 2Q1 is similar solid electrolyte structure  200 - 2 I shown in  FIG.  2 I ). Solid electrolyte structure 2Q2 is formed when the second nanolayer has a different composition than that of the first nanolayer, and is similar to solid electrolyte structure  200 - 2 L, shown in  FIG.  2 L . Solid electrolyte structure 2Q3 is formed when the second nanolayer has the same composition as the first nanolayer, but a different thickness (solid electrolyte structure 2P3 is similar to solid electrolyte structure  200 - 2 J or  200 - 2 K, as shown in  FIGS.  2 J and  2 K  respectively. With respect to process B, as shown in  FIG.  2 Q , the third and fourth operations (operation 3b and operation 4b) involve depositing a first and second nanolayer via ALD onto the first and second major surfaces of the sulfide glass sheet, respectively. The first and second nanolayers also providing encapsulation of the peripheral glass edge surfaces. The fifth operation (operation 5b) for process B involves depositing a third nanolayer that encapsulates the major surface of the first or the second nanolayer, wherein the third nanolayer has a different composition than that of the first and second nanolayer. In accordance with process B, the solid electrolyte structure 2Q4 thus formed is similar to solid electrolyte structures  200 - 2 M and  200 - 2 N, as shown in  FIGS.  2 M and  2 N , respectively. With respect to process C, as shown in  FIG.  2 Q , the third operation (operation 3c) involves depositing a first nanolayer via ALD onto the first major surface of the sulfide glass sheet and the peripheral edge surfaces. This is followed by operation 4c, which involves depositing a second nanolayer via ALD onto the second major surface of the sulfide glass sheet, and the peripheral edge portions of the first nanolayer, and further wherein the second nanolayer has a different composition than that of the first nanolayer. This is followed by operation 5c, which involves depositing a third nanolayer via ALD onto the first nanolayer, wherein the third nanolayer has the same composition as that of the second nanolayer. In accordance with process C, solid electrolyte structure 2Q5 thus formed, is similar to solid structures  200 - 2 O and  200 - 2 P, as shown in  FIGS.  2 O and  2 P , respectively. 
     Liquid Phase Protective Fluid Layer 
     With reference to  FIGS.  2 A-D and  2 E-H , in accordance with the present disclosure one function of protective material layer  102 / 202  (e.g., inert liquid layer) is to removably cover and protect (e.g., encapsulate) at least the first major surface of the battery active material layer, and thereon provide a degree of protection against facile degradation caused by direct exposure of the lithium metal layer or sulfide glass layer to ambient gaseous atmospheres during handling, processing and/or storage. By use of the term “removably cover and protect” when describing the protective inert liquid layer it is meant that the layer: i) covers the first surface of the battery active material in a manner that sufficiently protects the surface against chemical attack; ii) remains on the first surface during handling and storage; and iii) can be controllably removed without damaging the battery active material layer. By use of the term “controllably remove” or “controllably removed” when referring to the protective material layer it is meant that the laminate structure is engineered to facilitate removal of the protective material layer in a controlled fashion, and is otherwise not easily removed (e.g., by happenstance, such as incidental evaporation during handling and processing of downstream components). Accordingly, the chemical make-up and physical properties of the protective material layer is properly selected to enable its controlled removal without damaging the battery active material layer, and the laminate structure engineered to ensure that the inert material layer stays intact as a protective layer for the desired time frame. 
     In various embodiments protective material layer  102 / 202  is an inert liquid that intimately covers and spans substantially the first major surface of the battery active material layer (i.e., it is a continuous inert liquid layer). Accordingly, in various embodiments the composition of the inert liquid is selected, in part, based on it having a lower surface energy than the battery active material layer surface, and therefore capable of wetting out the battery active first major surface, and, thus, intimately covering it in direct contact, the liquid flowing and spreading out evenly to span substantially the entire surface (i.e., encapsulate the surface); e.g., encapsulate the first major surface. 
     Preferably inert liquid layer  102 / 202  readily wets the first major surface of the battery active material layer. In various embodiments, the wetting angle (□ □ □ that the inert liquid makes in contact with the battery active material layer is less than 90° (e.g.,  0  ≤ □ □ □ □ □ □ □ □ □ □ preferably less than 60°, more preferably less than 30°, even more preferably □ □is less than 10°, and yet even more preferably about 0°. Accordingly, in various embodiments, the ability of the inert liquid layer to wet the battery active material layer surface is sufficient to encapsulate the one or more surfaces that it covers in direct contact. 
     Generally, the thickness of inert liquid layer  102 / 202  is less than 1 mm. In embodiments the thickness of the continuous inertliquid layer is in the range of 500 to 1000 um; or in the range of 200 to 500 um; or in the range of 100 to 200 um; or in the range of 50 to 100 um; or in the range of 20 - 50 um; or in the range of 10 - 20 um or in the range of 5 - 10 um; or in the range of 1 - 5 um; or, in some embodiments, it is contemplated that it may be less than 1 um. 
     In various embodiments, in order to retain inert liquid layer  102 / 202  on the surface of the battery active material layer during handling and processing, and controllably remove it (the inert liquid layer) without imparting damage or leaving behind a chemical residue, the inert liquid is selected based on a combination of its vapor pressure and boiling point. 
     In various embodiments, in order to mitigate uncontrolled evaporation of inert liquid layer  102 / 202 , while facilitating its controlled removal, the inert liquid of the protective material layer (i.e., the inert liquid layer) is selected, in part, based on having a room temperature vapor pressure in the range of 0.1 - 10 mmHg (e.g., 0.1 - 1 mmHg), and/or based, in part, on having a boiling temperature in the range of 100 - 200° C. 
     In various embodiments, the inert liquid of protective material layer  102 / 202  is selected based on having a sufficiently low vapor pressure at room temperature (e.g., less than 10 mmHg, or less than 1 mmHg). 
     In various embodiments, the inert liquid of protective material layer  102 / 202  is selected based on having a sufficiently high boiling point temperature (e.g., greater than 100° C., or greater than 150° C. or greater than 200° C.). 
     In various embodiments the inert liquid of protective material layer  102 / 202  is selected based on having a room temperature vapor pressure that is less than 10 mmHg and a boiling point temperature greater than 100° C. 
     In various embodiments protective material layer  102 / 202  is composed of one or more inert hydrocarbon liquids (e.g., isododecane). Particularly suitable hydrocarbon liquids for use as a protective material layer are saturated hydrocarbons (e.g., having a number of carbon atoms per molecule ranging from 5 to 15). 
     In various embodiments the inert hydrocarbon liquid is a saturated hydrocarbon liquid. 
     In some embodiments the protective inert liquid saturated hydrocarbon is a straight chain alkane (typically having between 5 and 15 carbon atoms per molecule), such as n-Pentane, n-Hexane, n-Heptane, n-Octane, n-Nonane, n-Decane, n-Undecane, n-Dodecane. 
     In some embodiments the protective inert liquid saturated hydrocarbon is a branched chain alkane (typically having 5 to 15 carbon atoms per molecules), such as isopentane, isohexane, isoheptane, isooctane, tetraethylmethane, isodecane, 3-methyldecane, isododecane. 
     In some embodiments the protective inert liquid saturated hydrocarbon is a cycloalkane, such as cyclohexane, and cycloheptane, cyclooctane. 
     In some embodiments the protective inert liquid hydrocarbon is an unsaturated acyclic hydrocarbon (e.g., CnH2(n-m-1) wherein n is the number of carbon atoms and m is the number of double bonds), such as alkenes (e.g., 1-Hexane, 1-Octane, 1-Nonene, 1-Docene, 1-Undecene, 1-Dodecene, or Alkadienes (e.g., 1,5-Hexadiene; 2,4-Hexadiene; 1,6-Heptadiene; 1,7-Octadiene; 1,8-Nonadiene; 1,9-Decadiene; 1,10-Undecadiene; and 1,11-Dodecadiene. 
     In various embodiments the inert hydrocarbon liquid is an unsaturated hydrocarbon liquid. 
     In some embodiments the protective inert liquid is an unsaturated cyclic hydrocarbon (e.g., of the type CnH2(n-m) wherein n is the number of carbon atoms and m is the number of double bonds), such as Cyclohexane, Cycloheptane, and Cyclooctene). 
     In some embodiments the protective inert liquid is an unsaturated cyclic hydrocarbon (e.g., one or more Cycloalkadienes), such as 1,3-Cyclohexadiene; 1,4-Cyclohexadiene; 1,3-Cycloheptadiene; and 1,3-Cyclooctadiene). 
     Generally, protective inert liquid layer  102 / 202  is devoid of dissolved and/or dispersed chemicals (e.g., salts, lubricants and/or greases) that would coat the surface of the battery active material layer with a solid film or leave behind a sticky residue. Accordingly, the protective inert liquid layer is generally devoid of dissolved salts (e.g., lithium salts, or more generally alkali metal salts). 
     In order to be inert in direct contact with the battery active material layer, the liquid hydrocarbon(s), and, more generally, the protective inert liquid layer should have a very low concentration of moisture. Preferably the concentration of moisture in the inert liquid hydrocarbon layer is less than 10 ppm of water, more preferably less than 5 ppm of water, even more preferably less than 1 ppm of water, and yet even more preferably less than 0.1 ppm of water (i.e., super dry). In various embodiments the inert liquid is actively dried in the presence of sacrificial alkali metal surfaces (e.g., pieces/chips of lithium metal) that getter oxygen, water and nitrogen impurities. In various embodiments, the cumulative area of the sacrificial alkali metal surfaces in direct contact with the inert liquid is greater than the first major surface of the battery active material layer on which the inert liquid covers in direct contact, for instance, when the battery active material layer is disposed in a protective liquid bath, as described in more detail hereinbelow. 
     Standalone Alkali Metal Laminate Structures 
     In accordance with the standalone electrochemical material laminate structure embodiments described with reference to  FIGS.  2 A - D , the laminate structures 100A-D are alkali metal laminate structures wherein battery active material layer  101  is an alkali metal layer having substantially unpassivated first major surface  10  1i, and preferably surface  101   i  is pristine. 
     In various embodiments alkali metal layer  101  is a dense alkali metal layer. In various embodiments it is a lithium metal layer or sodium metal layer. It is also contemplated that the alkali metal layer may be a lithium metal alloy or a sodium metal alloy, which may include one or more of the following alloying elements, including Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb. In various embodiments alkali metal layer  101  is a lithium metal layer. 
     In various embodiments thickness of lithium metal layer  101  is typically no greater than 50 microns, and more typically no greater than 25 microns (e.g., 50 µm ≥ t &gt; 30 µm; or 30 µm ≥ t &gt; 20 µm; or 20 µm ≥ t &gt; 10 µm; or 10 µm ≥ t ≥ 5 µm). In some embodiments lithium metal layer  101  is a thin film coating on a current collector having a scant amount of lithium, with thickness no greater than 5 um thick, and typically thinner, such as about 4 µm or about 3 µm or about 2 µm or about 1 µm, or less than 1 µm (e.g., 5 µm &gt; t ≥ 0.1 µm). For example, the thin film of lithium metal may be coated by evaporation onto a copper current collector in a vacuum chamber, and then prior to backfilling the chamber with a dry inert gas, such as argon or helium, the first major surface of the coated film is immersed in protective liquid or coated with a layer of inert protective liquid. 
     In accordance with the present disclosure, in various embodiments, lithium metal surface  101   i  is substantially unpassivated and preferably pristine, as defined herein below. And even more preferably, lithium metal surface  101   i  is 100% unpassivated. Preferably, lithium metal surface  101   i  is 100% unpassivated and molecularly or atomically clean. 
     Continuing with reference to the lithium metal laminate structures described herein above with reference to  FIGS.  2 A-D , in various embodiments first major surface  101   i  of lithium metal layer  101  is substantially unpassivated (or pristine), and is able to remain substantially unpassivated (or pristine) for a duration of at least 10 seconds, or at least 1 minute, or at least 5 minutes, or at least 10 minutes when it (the laminate structure) is disposed in a dry chamber having a water and oxygen content of about 1 to 10 ppm (e.g., about 5 ppm). 
     By use of the term “pristine surface” with reference to alkali metal layer  101  (e.g., a lithium metal layer), it is meant a substantially unpassivated lithium metal surface that is also sufficiently clean to i) facilitate complete reactive bonding to an opposing solid electrolyte layer, wherein the adherence created by the complete bond is sufficiently strong to prevent mechanical non-destructive release or delamination between the layers; and ii) effectuate a sufficiently uncontaminated interface (with the solid electrolyte layer) that is conductive to Li ions and does not result in a prohibitively large interface resistance (preferably no greater than 50 □ -cm2) between the alkali metal layer (e.g., a lithium metal layer) and the solid electrolyte layer (e.g., a sulfide glass layer). 
     By “substantially unpassivated” when referring to an alkali metal layer surface (e.g., a lithium metal surface) it is meant that the surface is predominately defined by a continuous unpassivated and substantially unoxidized surface region that accounts for at least 70% of the area of the referenced lithium metal surface (e.g., first major surface  101   i ). When referring to a lithium metal layer surface as pristine it is meant that the continuous unpassivated and substantially unoxidized surface region accounts for at least 90% of the area of the referenced lithium metal surface, and preferably at least 95%, and even more preferably the pristine surface is entirely unpassivated (i.e., 100% of the surface is unpassivated). In various embodiments, as described in more detail herein below, the substantially unpassivated or pristine surface may contain a certain amount of discrete passivated surface portions (i.e., passivated islands). 
     By “sufficiently clean” when referring to the pristine lithium metal surface, it is meant that the continuous unpassivated and substantially unoxidized surface region, as described above, is not poisoned by an unduly thick non-self-limiting surface-layer, which, if otherwise present would preclude complete reactive bonding and strong adherence to a reactive solid electrolyte layer (e.g., as defined with respect to peel strength), and would degrade electrochemical interface properties (e.g., as defined by interface resistance, and uneven plating and stripping reactions). Notwithstanding the preference to eliminate any poisoning of the pristine surface, a minimal non-self-limiting surface-layer covering the continuous unpassivated region may be acceptable, as described in more detail herein below. 
     Top down and cross sectional depictions of alkali metal layers (e.g., lithium metal layers) having pristine surfaces in accordance with various embodiments of the present disclosure are depicted in  FIGS.  3 A-D ; and for comparison, passivated lithium metal layer  3 E- 101  is depicted in  FIG.  3 E . 
     Briefly, in  FIG.  3 A , lithium metal layer  3 A- 101  is shown having pristine surface  3 A- 101   i  that is 100% unpassivated, and molecularly or atomically clean; in  FIG.  3 B , pristine surface  3 B- 101   i  of lithium metal layer  3 B- 101  contains a certain amount of passivating islands  3 B- 160  dispersed on continuous unpassivated region  3 B- 165 ; in  FIG.  3 C , the pristine surface of lithium metal layer  3 - 101 C is covered by minimal surface-layer  3 C- 181 , which defines the surface of its unpassivated region, and has an average thickness that is preferably less than 10 nm; and in  FIG.  3 D  pristine surface 3D-101i includes passivating islands 23D-160 and minimal surface-layer 3D-181 which defines the surface of its unpassivated region. Prior to describing these embodiments in more detail, it is instructive, for the purpose of comparison, to first depict the make-up of a fully passivated lithium layer. 
     With reference to  FIG.  3 E , a depiction of fully passivated lithium metal layer 3E-101 which may be a lithium metal foil that was made by extrusion and/or roller reduction in a dry air, dry oxygen and/or dry CO2 gaseous environment (e.g., dry air room), or it (layer  3 E- 101 ) may be an evaporated thin lithium film deposited on a current collector (not shown) under vacuum in a chamber, and then breaking the vacuum by bleeding a stream of dry air, dry oxygen and/or dry CO2 (e.g., dry air) into the chamber. The exposure to dry air immediately upon making the lithium foil/film results in the formation of passivation film 3E-179, which is a dense substantially self-limiting film of lithium oxide, and it may be several hundred angstroms thick (e.g., about 500A), or thicker, when formed in a dry room atmosphere (i.e., dry air). The exact stoichiometry of the passivating film is difficult to ascertain, and so is generally referred to as Li2Ox. Alternatively, if formed in the presence of dry CO2 gas, the composition of the passivating film is primarily lithium carbonate. By use of the term substantially self-limiting it is meant that the passivating film, formed as such, is sufficiently dense and thick to effectively block further reactions and thereby mitigate subsequent film growth. For instance, lithium passivating film 3E-179, once completely formed, is chemically stable to exposure to dry room air unless subjected to an atmosphere having a prohibitively high concentration of a reactive impurity such as water, which is known to breakdown lithium passivating films overtime. 
     With reference to  FIG.  3 -A , pristine surface  3 A- 101   i  of lithium metal layer 3A-101 is 100% unpassivated and substantially unoxidized, and absent of even a minimal surface-layer contaminant. 
     With reference to  FIG.  3 B , pristine surface  3 B- 101   i  of alkali metal layer  3 B- 101  contains passivated islands  3 B- 160  dispersed throughout continuous unpassivated and substantially unoxidized surface region  3 B- 165 . The cumulative area of the islands is less than 10% of the total area of the first major surface, and preferably the cumulative area is less than 5%, and even more preferably less than 1%. Preferably, the area size of the islands does not exceed 1 mm2, and more preferably does not exceed 0.5 mm2, and even more preferably does not exceed 0.1 mm2. In certain embodiments the method of making alkali metal layer  3 B- 101  results in first major surface 3B-101i that is characterized as predominately unpassivated (as opposed to pristine), wherein the area of continuous unpassivated region  3 B- 165  accounts for less than 90%, but at least 70%, of the area of first major surface  3 B- 101   i . 
     With reference to  FIG.  3 C , pristine surface  3 C- 101   i  of alkali metal layer  3 C- 101  is defined, in part, by the presence of non-self-limiting minimal surface-layer 3 C-181 composed of an ionically and/or covalently bonded compound which forms as a result of alkali metal atoms of the continuous unpassivated region oxidizing in contact with reactive impurity molecules derived from the external environment about the alkali metal layer structure, and especially oxygen, nitrogen and/or water impurities which may be present in the ambient gas or ambient vacuum of the external environment in which the alkali metal layer is formed, stored and/or handled, and/or as impurities in the protective liquid in which it (the pristine surface) is preserved. In various embodiments, minimal surface-layer  3 C- 181  is a compound product of the alkali metal atoms reacting with one or both of oxygen and water present as an impurity, and generally derived from the ambient gas of the external environment; for instance, surface-layer 3 C-181, an alkali metal oxyhydroxide compound (e.g., lithium oxyhydroxide). Minimal surface-layer  3 C- 181  is not necessarily continuous as shown in  FIG.  3 C , and may be spread out as discrete sections over the continuous unpassivated region. When present, surface-layer  3 C- 181  is minimal and exceptionally thin, having an average thickness that is less than 200 Å, and more preferably less than 100 Å, and even more preferably less than 50 Å or less than 40 Å or less than 30 Å. Even more preferably, the pristine surface is characterized as molecularly clean, which is to mean that the average thickness of surface-layer  3 C- 181  is less than 25 Å, and even more preferably the pristine surface is atomically clean, with surface-layer  3 C- 181   181  having an average thickness of less than 10 Å. 
     With reference to  FIG.  3 D , lithium metal layer  3 D- 101  has pristine surface  3 D- 101   i  which is similar to that shown in  FIG.  3 C  in that the unpassivated surface region is defined by a minimal surface-layer  3 D- 181 , similar to  3 C- 181  (as described above and shown in  FIG.  3 C ), but also containing passivating islands  3 D- 160 , similar to the passivating islands described above with reference to  FIG.  3 B . 
     Methods of Making Pristine Lithium Metal Layers and Lithium Metal Layers Having Substantially Unpassivated Surfaces 
     As described above, the present disclosure provides methods and apparatus’ for making lithium metal layers having substantially unpassivated and preferably pristine surfaces, and, in particular, for making lithium metal layers wherein at least one major surface is maintained in its pristine or substantially unpassivated condition under, or immersed in, a protective fluid (e.g., a protective liquid). 
     With reference to  FIGS.  4 A-D  there are illustrated apparatus&#39;  400 A-D for the manufacture of lithium metal layer  101 , having first and second major opposing surfaces 101i/101ii, wherein at least first surface  101   i  is formed in direct contact with protective fluid  102  (e.g., super dry inert hydrocarbon liquid, vapor or combination thereof), and therewith surfaces  101   i  and 101ii are substantially unpassivated, and in some embodiments pristine. 
     Apparatus′  400 A-D may be divided into two main sections or regions. First section  410   i  (typically a staging section) is where the initial stock of lithium metal  430  (e.g., an ingot or foil of lithium) is positioned for entry or disposition into second section 410ii (surface generating section), and, in particular, surface forming chamber  450  wherein lithium layer  101  and/or its pristine first surface  101   i  (and optionally  101   i ) are formed in direct contact with protective fluid  402  (e.g., super dry inert hydrocarbon liquid as described above). Chamber  450  includes enclosure  451 , and is equipped with surface forming device  452 , and interior environmental controls not shown. Once created, as-formed lithium layer  101  may be wound and/or stored in protective liquid of the same or different composition as that in which the layer itself (or at least its first surface) was generated. As shown in  FIG.  4 A , as formed lithium layer  101  is wound to form lithium roll  401 -R. The winding may be performed inside chamber  450  (as shown), or lithium layer  101  may be fed to a separate downstream chamber for subsequent winding and storage in roll form. 
     In various embodiments, a lithium decal (as shown in  FIG.  2 D ) may be formed by interleaving one or a pair of solid release layers (e.g., a polyolefin sheet or film) into the roll during winding. As described above, in a lithium decal of the present disclosure, the solid release layer is positioned on the first and/or second major surface where it keeps the inert liquid in place, ensures that the liquid spreads evenly over surface  101   i , mitigates evaporative losses because it (the solid release) enhances barrier properties, provides physical protection against contact damage, enables the use of protective liquids having relatively high vapor pressures, and serves as an interleave when stacking or rolling the layer(s) to avoid sticking. Once the decal is wound, surface  101   i  is encapsulated by a protective liquid layer, and in some embodiments the liquid may be caused to form a sheath about the layer, which encapsulates both first and second surfaces. 
     With reference to  FIGS.  4 A-B  and  FIG.  4 D , in various embodiments, both first and second major opposing surfaces (101i and 101ii; see figure inserts) are formed in direct contact with protective liquid by action of surface forming device  452  having surface forming component(s)  456   a / b  that directly contact lithium metal layer  101  as it forms. As shown, surface forming device  452  may be a roller reduction mill that reduces thickness of the lithium metal layer and in so doing produces substantially unpassivated lithium surfaces by extruding initial stock  430 , or lithium layer  405  (as shown in  FIG.  4 A ), between rollers  456   a / b . When roller reducing a lithium metal foil, the area of the new surface created is proportional to the decrease in thickness. 
     Surface forming device  452  contacts protective liquid  402  such that as lithium metal layer  101  is formed, or surface  101   i  and/or surface  101   i  is created, the as-formed surfaces substantially instantaneously become immersed in protective fluid (e.g., inert liquid). Once the layer is formed, the inert liquid is caused to remain on the freshly created lithium layer surfaces (e.g., by using a solid release layer on that surface), typically fully encompassing (i.e., encapsulating) the surface, and thereon protecting it (the pristine surface) from direct contact with lithium reactive constituents that may be present as contaminants in of the ambient environment about the layer. In various embodiments, the protective fluid in which pristine lithium metal surface  101   a  is formed may be exchanged with protective fluid having a different composition for downstream processing and/or storage. For instance, surface  101   i  formed in or under a first protective liquid having a first vapor pressure or boiling point and that first inert liquid is replaced by a second inert liquid having a second vapor pressure or boiling point (e.g., the second liquid having a higher vapor pressure and lower boiling point than the first liquid, or vice-versa). 
     In various embodiments, surface forming device  452  is fully, or at least partially, immersed in protective fluid  402 . For instance, active surface forming component  456 , may be fully submerged or encompassed inside a bath of protective liquid. To contain protective liquid  102 , surface generating section  410   ii  includes enclosure  451  (e.g., an environmental chamber). In various embodiments, the surface forming device, and in particular its surface forming components, are also housed in the enclosure. 
     In various embodiments protective fluid  402  is a liquid at room temperature (i.e., 18° C. to 25° C.) and standard pressure (1 atm), and is primarily contained in the enclosure as a liquid. In various embodiments the interior environment of the enclosure is substantially filled by inert liquid, and as described above, and in more detail herein below, in various embodiments surface forming component  456  is immersed in the inert liquid phase protective fluid, and specifically that portion of the surface forming component which directly contacts lithium metal surface  101   i  is immersed in the liquid phase. Accordingly, surface  101   i , or both surfaces  101   i  and  101   bii , are formed in direct contact with liquid phase protective fluid, and preferably the as-formed surfaces are fully encompassed/encapsulated by the liquid phase, and as such the surfaces are formed in the absence of direct contact with a gaseous phase environment (e.g., dry air or an inert gas phase environment, including one or more noble gases), and thus also not formed in a vacuum environment. For instance, the lithium metal layer and/or its associated surfaces are fully formed immersed in a protective liquid. For example, formed inside a bath of protective liquid or inside a chamber filled with protective vapor of an inert liquid. 
     As described in more detail herein below, once formed within the protective liquid, lithium metal layer  101 , or its first and/or second major surface(s)  101 / 101   ii  are maintained in the protective liquid for subsequent winding to form a roll of lithium metal foil  101 -R (typically on a spool) and/or storage. By this expedient, as-formed lithium metal layer  101 , and/or surface  101   i , or both surfaces  101   i  and  101   ii , have never been exposed to a gaseous phase environment or to a vacuum environment. In such embodiments, the lithium metal foil and its associated pristine surfaces, are formed, and thereafter stored in a pristine state, never exposed in direct contact with a gaseous atmosphere. For example, the foils so formed are maintained pristine during storage inside a bath of protective liquid for more than 24 hours, or more than 1 week, or more than 1 month. The pristine foils may then be sold and/or transported as such to a facility for manufacture of downstream battery cell components, including solid-state electrode laminates and battery cells of the present disclosure. In various embodiments the lithium foils are stored under protective liquid, and are preferably never been exposed in direct contact with gaseous atmospheres, including dry noble gases such as dry Argon gas, or dry Helium gas, or some combination thereof, or even dry air (i.e., air having a very low moisture content, such as that typical of a dry room). When rolled with a solid release layer, the release removably covers and protects the substantially unpassivated lithium metal surface  101   i , and optionally its opposing surface  101   ii . When a solid release is used the inert liquid layer is formed and sandwiched between the solid release layer and the lithium metal layer, and this laminate structure is sometimes referred to herein as a wet-decal architecture, or more simply a wet-decal. Preferably, the inert liquid is capable of wetting out both the lithium metal surface and the release layer. 
     In alternative embodiments the interior environment of chamber  450  is primarily composed of protective fluid as a vapor. In such embodiments, the vapor molecules may condense on the as-formed lithium metal surfaces. When a vapor phase protective fluid is used, the enclosure is typically vacuum evacuated, followed by evaporating the protective liquid inside the chamber to form the inert vapor. Notably, when referring to vapor phase protective fluid it is not meant a noble gas such as Argon or Helium, or the like. By protective fluid in the vapor phase it is meant vapor of the inert liquid. 
     With reference to  FIG.  4 A  there is illustrated apparatus  400 A for making pristine lithium metal layer  101  in protective fluid  402 ; for example, a super dry liquid hydrocarbon. With particular reference to  FIG.  4 A , initial lithium metal stock  430  (e.g., a lithium ingot) is extruded via die press  440  to form relatively thick freshly extruded lithium layer  405  (typically in the range of 75 to 500 um thick). Specifically, lithium ingot  430  is loaded and pressed against extrusion die  444  via plunger  442  and die plate  443 , as is known in the art for making extruded lithium foil from lithium ingots in a gaseous dry room atmosphere. 
     As-formed, layer  405  is generally substantially upassivated and preferably pristine upon exiting die  444 . If formed in direct contact with a gaseous dry room environment the freshly made lithium metal surface would immediately start chemically reacting with the oxygen and carbon dioxide in the dry room, which would passivate the exposed surfaces. With respect to various embodiments of the present disclosure, because layer  405  is formed directly in protective liquid  102 , its major opposing surfaces  105   a / 105   b  are fully covered in direct contact with protective liquid  102  substantially immediately upon formation (e.g., in less than one second). In the instant embodiment, thickness of layer  405  is reduced in a subsequent roll reduction operation, as shown in section 410ii of  FIG.  4 A . Once formed, layer  405  is caused (e.g., by a pulling tension) to enter roll reduction device  452 , which can be a rolling mill having reduction work rolls  456   a / 456   b , both of which are immersed in protective liquid inside enclosure  451 . Work rolls 456a-b may be made of compatible metal or plastic (e.g., polyacetal), or plastic coated metal rolls. Because the work rolls are immersed in protective hydrocarbon liquid, the issue of lithium metal sticking to the rolls is mitigated. In various embodiments roll reduction reduces the lithium layer down to a thickness of no greater than 50 um. Thin lithium metal layer  101  is formed upon exiting the roller mill; the roller reduction operation effectively transforms pristine lithium layer  405  (e.g.,  500  um thick) to thinner layer  101  having fresh surfaces  101   i  and  101   ii  formed in direct contact with protective liquid  402 . Once formed, layer  101  may be transferred from chamber  450  to a distinct/discrete winding chamber, or the winding device may be incorporated in chamber  450 , and layer  101  subsequently wound to yield lithium foil roll  401 -R, which, in its wound condition, remains directly exposed in contact with protective liquid (e.g., the protective liquid forming a thin layer of liquid between the lithium metal layer and a solid release layer, not shown). As described in more detail hereinbelow, and with reference to a lithium roll package assembly of the present disclosure, wound roll  401 -R may be stored in a functional canister containing protective liquid of the same or different composition as that of protective liquid  402 , and a sealable port for ease of dispensing the lithium layer during battery cell or battery cell component manufacture. In various embodiments a solid release layer is positioned on the substantially unpassivated lithium surface (e.g., during winding or stacking), and the laminate structure so formed has, what is termed herein, a wet-decal architecture as described in more detail herein below. 
     In an alternative embodiment, a thin lithium foil may be formed by direct extrusion of the lithium metal stock into a vacuum chamber, as described below with reference to  FIG.  4 K . 
     Continuing with reference to  FIGS.  4 A-D , in various embodiments lithium metal layer  101  is a thin lithium metal layer, typically of thickness no greater than 50 µm, and more typically no greater than 25 µm (e.g., the thickness (t) of layer  101  is in the range of: 25 µm ≥ t &gt; 20 µm; or 20 µm ≥ t &gt; 15 µm; or 15 µm ≥ t &gt; 10 µm; or 10 µm ≥ t &gt; 5 µm). The standalone lithium metal layer may be self-supporting (if thicker than about 20 µm) or supported on a substrate layer. As described in more detail herein below, in various embodiments the lithium metal layer may be supported on a thin substrate layer that also serves as a current collector, the combination of current collector and thin lithium metal layer is sometimes referred to herein as having an electrode architecture. 
     As shown in  FIG.  4 B , in an alternative embodiment, initial lithium stock  430  may be a continuous foil of lithium (e.g., in the form of wound roll  430 -R). As stock  430  is already in foil form, it may be contained inside a chamber that is configured for entry into chamber  450  via portal  455 , or the layer may be exposed to the ambient external environment about chamber  450  (e.g., a dry box or dry room environment), and in this instance the stock layer would have passivated surfaces. In operation, stock foil  430  is unwound and caused, by pulling tension, to extrude through work rolls  456   a / b  immersed in protective liquid  402 . As described above, once foil  430  is extruded through roller reduction mill  452 , it is wound in a similar fashion as described above, to form lithium roll 401-R immersed in protective liquid. In various embodiments stock lithium foil  130  may be pre-passivated (e.g., by exposing its surfaces to dry CO2), and by this expedient improve reproducibility of the surface condition of the initial stock foil. 
     As shown in  FIG.  4 C , in yet another alternative embodiment stock foil  430  may be surface treated inside chamber  450  to expose a fresh lithium surface in direct contact with protective fluid  402  (e.g., ground with an abrasive element such as a brush or rough polymeric sheet). For instance, surface forming device  456  (e.g., an abrasive brush) may be positioned over stock foil  430  as it enters the chamber, and caused to engage with a surface of stock layer  430  to form pristine layer  101  and its associated pristine surface  101   i . In this embodiment the stock foil does not undergo a significant reduction in thickness, as the transformation of the foil from stock  430  to pristine layer  101  is based on forming pristine surface  101   i  in direct contact with protective fluid  402  (e.g., liquid phase, vapor phase, or both). As shown in  FIG.  4 C , in various embodiments the stock may be a laminate of lithium layer  430  and a current collecting layer  461  in direct contact with the second surface of layer  430 . In other embodiments, the stock is a lithium foil, and one or both surfaces are formed in the protective fluid, (e.g., by brushing/grinding). 
     With reference to  FIG.  4 D  there is illustrated yet another alternative apparatus for making pristine lithium metal layer in the presence of protective fluid, and in accordance with the instant disclosure. The apparatus is similar to that described above for fresh surfaces produced by roll reduction, except in this embodiment the work rolls  456   a / b  are positioned at the interface between the staging section  110   i  and surface forming section  110   ii . Lithium stock foil  430  is configured for entry into the chamber via roller mill  455 . In particular, work rolls  456   a / b  effectively provide the portal into chamber  450 , and the protective liquid is distributed to completely cover the freshly extruded surfaces (e.g., by spraying the inert liquid from nozzles  457  onto one or both surfaces  101   i / ii ). Chamber  450  maybe held undera dynamic vacuum with the protective fluid, in vapor form, or the chamber environment may be a combination of protective fluid in vapor form (i.e., protective vapor) and a dry noble gas such as argon or helium. 
     As described above, in various embodiments protective fluid  402  is a liquid. In some embodiments the interior environment of the chamber is held under a dynamic vacuum with protective fluid in the vapor phase. In some embodiments the protective fluid is present in the chamber in both the vapor and liquid phases. In some embodiments the chamber is substantially filled with liquid phase protective fluid (e.g., more than 90% of chamber volume is accounted for by protective liquid). Generally the protective fluid is a hydrocarbon composed of one or more hydrocarbon molecules that do not react in direct contact with lithium atoms. 
     With reference to  FIG.  4 E  there is illustrated another embodiment in accordance with the instant disclosure for a process and apparatus  400 E for fabricating pristine lithium metal layer  101  using a series of roller reduction mills (e.g., two or more). Apparatus  400 E is generally disposed in a closed environmentally controlled chamber, similar or the same as chamber  451 , as described above. Liquid phase protective fluid  402  is applied directly onto the major opposing surfaces of lithium stock  430  (e.g., by dripping or spraying), and is configured for extrusion rolling (i.e., roller reduction). Care should be taken to ensure that the major surfaces are entirely covered with protective liquid throughout the process. Additionally, protective liquid  402  is dispensed from fluid reservoir  432  for application directly onto work roll pairs  456   a / 456   b  and  456   c / 456   d . A further application of the protective liquid is dispensed onto surface  101   i  of the as-formed lithium metal layer  101  to ensure that the entirety of that surface is coated with a sufficient amount of protective liquid layer  102  to encapsulate the surfaces and provide sufficient protection for conveyance of the lithium foil  101  downstream for laminating processes, or for disposition into a canister for storage as a Li roll package assembly, as described below with reference to  FIG.  6   . 
     With reference to  FIG.  4 F  there is illustrated top down views and cross sectional views qualitatively depicting the evolution of a lithium surface resulting from multiple roll reduction operations performed in protective liquid in accordance with various embodiments of the present disclosure. The initial lithium foil is stock and may be pre-passivated as shown (e.g., by treatment with carbon dioxide on its surface to form a lithium carbonate passivation layer). After the first roll reduction, the lithium thickness is reduced (as shown in the cross section depiction), and the lithium carbonate passivating layer has been broken apart to expose fresh lithium metal surfaces and scattered passivated islands. Because the operations are performed in protective liquid, and the lithium metal layer is maintained covered in protective liquid throughout the entire process, the fresh formed surfaces can remain unpassivated. With each consecutive roll reduction the thickness of the layer decreases and the area of the unpassivated surface region increases (also the passivated islands become smaller in size and area). As noted above, the decrease in lithium thickness is proportional to the increase in the unpassivated surface region. Accordingly, in various embodiments the method of making a thin lithium metal layer having a pristine surface includes: i) determining a final lithium metal layer thickness; determining the thickness of the stock of pre-passivated lithium metal layer necessary to create a pristine surface (i.e., at least 90% of the surface is defined by the unpassivated surface region); roll reduce the stock lithium metal foil under protective liquid. For instance, if the desired lithium metal thickness is 25 um, starting with a 50 um passivated lithium foil will produce a surface that is just 50% passivated and 50% unpassivated, which is insufficient for forming a pristine first major surface. To create a pristine lithium metal layer that is 25 um thick from pre-passivated lithium metal foil requires that the stock foil be at least 250 um thick. 
     With reference to  FIG.  4 G , stock lithium foil  430  may be simultaneously roller extruded and laminated to substrate layer  490  (e.g., a copper current collecting layer) using roller reduction mill  452  equipped with fluid dispensing reservoir  432  and work rolls  456   a / b  as described above. Once processed, laminate structure  100 B (as described with reference to  FIG.  1 B ), has an electrode architecture that is composed of lithium metal layer  101  laminated with copper current collector  490 F as the backing layer behind second major surface  101   ii . First major surface of layer  101  is entirely covered, in direct contact, with liquid phase protective fluid  102  (i.e., it is encapsulated). As-formed, laminate  100 B may be subsequently wound and disposed into canister  571  (as shown in  FIGS.  5 A-B ) to form laminate roll package assembly for storage and ultimately downstream production of a lithium battery cell. In various embodiments the lithium metal layer may be roller extruded directly onto an inorganic solid electrolyte layer serving as substrate, such as a lithium ion conducting sulfide glass layer or nanofilm-encapsulated sulfide glass solid electrolyte structure, the roll extrusion exposing substantially unpassivated lithium metal directly onto the sulfide glass to effect a reactive bond between the layers. 
     In accordance with the methods and apparatus’ shown in  FIGS.  4 A-F , the process operations of: i) roller reducing the thickness of stock lithium metal foil; ii) forming freshly extruded lithium metal surfaces; iii) and laminating the second major surface  101   b  to a copper current collector, may be performed in a conventional dry box or dry chamber having a noble gas atmosphere (e.g., argon or helium), with the interior environment of the dry box at low moisture content, preferably less than 10 ppm water, more preferably less than 5 ppm, even more preferably less than 1 ppm, and yet even more preferably less than 0.1 ppm. However, the embodiment is not limited to the apparatus being disposed in a conventional dry box, and in a manner similar to that shown in  FIGS.  4 A-D , apparatus&#39;  400 E/ 400 F may be configured inside an environmentally controlled chamber, similar to that of chamber  450 , with an interior atmosphere primarily composed of protective fluid (e.g., protective vapor). 
     With reference to  FIG.  4 H  there is illustrated, in a cross sectional depiction, another embodiment in accordance with the instant disclosure for a process and apparatus 400H for fabricating pristine lithium metal layer  101  by evaporating (e.g., thermal evaporation) the layer on current collecting substrate  103 . Unit  410 H is the evaporator, and the vacuum chamber is not shown. In various embodiments, current collecting substrate  103  is a copper foil or a metallized plastic such as PET metallized with a thin layer of copper. Substrate  103  is actively cooled during the thermal evaporation by flowing cool Argon gas onto the second surface of the substrate. Optionally, the first surface of the lithium metal layer is smoothed by ion bombardment, and the apparatus includes an ion gun (not shown), which emits low energy Argon ions onto the evaporated lithium surface (i.e., its first major surface). When actively cooling the substrate with Argon gas, substrate  103  is inserted into ceramic frame  404 H. Substrate  103  maybe releasably sealed to the frame (e.g., via a glue or epoxy) in order to prevent the Argon gas from reaching the opposing side of the substrate. With reference to  FIG.  4 I , there is illustrated in top down view cassette  400 I composed of plurality of ceramic frames 404H and substrates  103  fitted to each frame for making multiple components. 
     With reference to  FIG.  4 J , once lithium metal layer  101  has been evaporated, its first major surface is covered by protective liquid layer  102 , which may be applied onto the lithium metal surface by a gravure printing process, using gravure roll cylinder  405 J having recessed cells that take-up protective fluid and apply it to the surface of the lithium metal layer is it passes through the rollers. Once protective liquid  102  is applied, it flows to cover the entire lithium metal surface. The gravure cylinder is partially immersed in trough  407 J filled with protective liquid that provides a reservoir for filling the recessed cells of roll  405 J with fluid. The lithium metal layer is sandwiched between the rollers and the surface tension of the protective liquid provides the force to extract the liquid from the cells and onto the lithium metal surface. Thereafter, the lithium metal laminate structure thus formed (i.e., Cu foil substrate  103 /thermally evaporated lithium metal layer  101 /protective liquid layer  102 ) may be sandwiched between solid material release layers  104  for further protection. 
     With reference to  FIG.  4 K  there is illustrated further apparatus and process for making vacuum die extruded lithium metal layers in accordance with an embodiment of the present disclosure. Apparatus 400K may be divided into two main sections or regions. First section  410   i  (typically a staging section) is where the initial stock of lithium metal  430  (e.g., an ingot or foil of lithium) is positioned for entry or disposition into second section  410   k  ii (surface generating section). Lithium metal layer  401   k  (e.g., foil) is fabricated by die extrusion of stock lithium metal  430  (e.g., an ingot of lithium) directly into vacuum chamber  450   k . Specifically, lithium ingot  430  is loaded and pressed against extrusion die  444  via plunger  442  and die plate  443 , and extrusion die  444  is configured with vacuum chamber  450   k  such that extruded foil  401  k is formed under vacuum  402   k . The vacuum die extruded lithium metal layer  401   k , having first and second major opposing surfaces  401   k  i/401k ii which are substantially unpassivated, and in some embodiments pristine. 
     Once formed, vacuum die extruded lithium layer  401   k  may be substantially immediately laminated to a second material layer, or one or both major surfaces may be covered in protective fluid as described above (e.g., by using a gravure printing process). The fresh surfaces formed as a result of the extrusion are substantially unpassivated, and preferably the vacuum chamber is sufficiently clean and at a sufficient vacuum level that the fresh surface(s) formed as a result of the vacuum extrusion (e.g., the first and/or second major surface) is pristine. A winding device may be incorporated in chamber  450   k , and layer  401   k  may subsequently be wound to yield lithium foil roll 401k-R, which, in its wound condition, may remain directly exposed in contact with protective liquid (e.g., the protective liquid forming a thin layer of liquid between the lithium metal layer and a solid release layer, not shown). 
     In various embodiments, lithium metal stock  430  is ultra-purified to allow for lithium metal layer  401   k  to be formed as a thin foil having thickness less than 50 um (e.g., about 45 um, or about 40 um, or about 35 um or about 30 um or about 25 um or about 20 um or about 15 um or about 10 um). To achieve such thin lithium metal layers in the form of a continuous foil (e.g., of at least 50 cm length, or at least 100 cm length) or web, lithium metal stock  430  should be purified to remove oxides and nitrides of lithium, and in particular to remove non-metallic impurities, especially oxygen and nitrogen. Purification of lithium ingot  430  may be realized by one or more processes, including low temperature filtration, vacuum distillation, cold-trapping and gettering with an active metal. To achieve die extruded lithium foil thickness less than 50 um, inclusions (e.g., particles of nitrides and oxides) should be removed from the lithium metal stock  430 . Preferably, the ingot is absent of lithium nitride and/or lithium oxide inclusions having a size dimension greater than 1 um, and more preferably there are no such inclusions with a size dimension of 500 nm, and even more preferably with a size dimension of 100 nm, and even more preferably there are no such inclusions with a size dimension of 20 nm, and yet even more preferably ingot  430  is absent of any particle inclusions. Preferably, the oxygen and/or nitrogen impurity levels present in ingot  430  are less than 1000 ppm, more preferably less than 500 ppm, even more preferably less than 250 ppm, and yet even more preferably less than 100 ppm, less than 50 ppm, less than 20 ppm, and less than 10 ppm. In various embodiments, the method for purifying lithium metal stock  430  involves removing nitrogen and/or oxygen using an active metal getter. Particularly suitable active metal getters are titanium (e.g., titanium sponge), zirconium, beryllium and yttrium. Suitable methods for removing oxygen and nitrogen impurities from lithium metal are described in a report to the U.S. Atomic Energy Commission by E.E. Hoffman of Oak Ridge National Laboratory entitled “The Solubility of Nitrogen and Oxygen in Lithium and Methods of Lithium Purification,” dated Mar. 17, 1960, for example. In that report purification of lithium metal is motivated by its use as a heat transfer material for cooling nuclear reactors. The use of a purified lithium metal stock, as described above, may also be used for making lithium metal foils as described herein with reference to  FIG.  4 A . 
     In various embodiments, vacuum die extruded lithium layer  401   k  may be laminated to a second material layer inside the vacuum chamber wherein it (the die extruded lithium metal foil) is formed. Performing the operations of lithium foil formation and lamination in the same vacuum chamber mitigates the need for transferring materials and the potential that any such transfer could lead to surface contamination. In a particular embodiment the second material layer is a current collector layer (e.g., copper foil or a copper metalized polymer film). In another embodiment the second material layer is a lithium ion conducting solid electrolyte, such as a sulfide glass solid electrolyte sheet or a nanofilm-encapsulated sulfide glass solid electrolyte structure as described herein. 
     With reference to  FIGS.  5 A-B  there is illustrated a lithium metal roll assembly cartridge  500  (sometimes referred to herein as a lithium roll assembly package) in accordance with various embodiments of the present disclosure. Cartridge  500  includes Li decal laminate  100 C in roll form  100 C-Roll, and entirely immersed in protective inert liquid  502 , which is itself contained in canister  571 . The cartridge also includes sealable port  572  and associated sealing cap  573 .  FIG.  5 A  shows cartridge  500  in a hermetically closed state.  FIG.  5 B  illustrates a mechanism for removing Li-decal laminate  100 C from the canister, via sealable port  572 , with sealing cap  573  configured to assist in dispensing the decal out of the canister. Cartridge  500  is suitable for storing the decal over extended time periods, including hours, days, or even weeks. The interior volume of canister  571  is substantially entirely filled with protective liquid, and may include moisture and oxygen gettering material, such as high surface area lithium metal in the form of numerbable metal pieces immersed in the protective liquid. 
     Preferably cartridge  500  is sufficiently hermetic, and the protective liquid sufficiently dry (e.g., super dry), that lithium metal layer  101  is able to maintain its substantially unpassivated or pristine surface condition for at least 60 minutes, or at least 5 hours, or at least 10 hours, or at least 24 hours, or at least several days, weeks, or months (e.g., more than 3 days, more than 7 days, or more than 30 days). 
     Standalone Solid Electrolyte Laminate Structures 
     In accordance with the standalone electrochemical material laminate structure embodiments described with reference to  FIGS.  2 E - H , in various embodiments battery active material layer  201  is an inorganic alkali metal ion conducting solid electrolyte layer, and the laminate structure in such embodiments is referred to herein as an inorganic solid electrolyte laminate structure (e.g., a lithium ion conducting sulfide glass laminate structure). The room temperature alkali metal ion conductivity of the inorganic solid electrolyte layer is at least 10-6 S/cm, preferably at least 10-5 S/cm, and even more preferably at least 10-4 S/cm (e.g., between 10-5 S/cm and 10-4 S/cm or between 10-4 S/cm and 10-3 S/cm), with room temperature defined as 18° C. - 25° C. 
     Continuing with reference to  FIGS.  2 E-H  in various embodiments inorganic alkali metal ion conductive solid electrolyte layer  201  is an inorganic lithium ion conductive solid electrolyte layer. In particular embodiments the inorganic lithium ion conductive solid electrolyte layer is an inorganic glass. In embodiments it is an oxide glass (in the absence of sulfur). In various embodiments inorganic solid electrolyte layer  201  is a lithium ion conductive sulfide glass. In various embodiments the inorganic solid electrolyte layer is moisture sensitive and chemically reacts in contact with water, and in particular the surface of the solid electrolyte layer degrades in the presence of the ambient atmosphere of a dry room (e.g., having a dew point at or below -20° C.) or in some embodiments that of a dry Argon glove box (e.g., having between 0.1 to 10 ppm of water). In various embodiments, solid electrolyte layer  201  is a moisture sensitive Li ion conductive sulfide glass comprising lithium, sulfur and one or more of boron, silicon, and/or phosphorous. Particular sulfide solid electrolyte glasses that can benefit from incorporation into a solid electrolyte laminate structure of the present disclosure include those described in U.S. Pat. Publication No.: 20160190640, which is hereby incorporated by reference for all that it contains; for example: 0.7Li2S-0.29P2S5-0.01P2O5; 0.7Li2S-0.28P2S5-0.02P2O5; 0.7Li2S-0.27P2S5-0.03P2O5; 0.7Li2S-0.26P2S5-0.04P2O5; 0.7Li2S-0.25P2S5-0.05P2O5; 0.7Li2S-0.24P2S5-0.06P2O5; 0.7Li2S-0.23P2S5-0.07P2O5; 0.7Li2S5S-0.22P2S5-0.08P2O5; 0.7Li2S-0.21P2S5-0.09P2O5; 0.7Li2S-0.2P2S5-0.1P2O5; 0.7Li2S-0.29B2S3-0.01B2O3; 0.7Li2S-0.28B2S3-0.02B2O3; 0.7Li2S-0.27 B2S3-0.03B2O3; 0.7Li2S-0.26B2S3-0.04B2O3; 0.7Li2S-0.25B2S3-0.05B2O3; 0.7Li2S-0.24 B2S3-0.06B2O3; 0.7Li2S-0.23B2S3-0.07B2O3; 0.7Li2S-0.22B2S3-0.08B2O3; 0.7Li2S-0.21 B2S3-0.09B2O3; 0.7Li2S-0.20B2S3-0.1B2O3; 0.7Li2S-029B2S3-0.01P2O5; 0.7Li2S-0.28B2S3-0.02P2O5; 0.7Li2S-0.27B2S3-0.03P2O5; 0.7Li2S-0.26B2S3-0.04P2O5; 0.7Li2S-0.25 B2S3-0.05P2O5; 0.7Li2S-0.24B2S3-0.06P2O5; 0.7Li2S-023B2S3-0.07P2O5; 0.7Li2S-0.22B2S3-0.08P2O5; 0.7Li2S-0.21B2S3-0.09P2O5; 0.7Li2S-0.20B2S3-0.1P2O5; 0.7Li2S-0.29 B2S3-0.01SiS2; 0.7Li2S -0.28B2S3-0.02SiS2; 0.7Li2S-0.27 B2S3-0.03SiS2; 0.7Li2S-0.26 B2S3-0.04SiS2; 0.7Li2S -0.25B2S3-0.05SiS2; 0.7Li2S-0.24 B2S3-0.06SiS2; 0.7Li2S-0.23 B2S3-0.07SiS2; 0.7Li2S-0.22B2S3-0.08SiS2; 0.7Li2S-0.21B2S3-0.09SiS2; 0.7Li2S-0.20B2S3-0.1SiS2. 
     In other embodiments inorganic solid electrolyte layer  201  may incorporate a polycrystalline ceramic or a glass-ceramic layer (e.g., a garnet solid electrolyte layer). These include Li6BaLa2Ta2O12; Li7La3Zr2O12, Li5La3Nb2O12, Li5La3M2O12 (M=Nb, Ta)Li 7+xAxLa 3-xZr2O12 where A may be Zn. These materials and methods for making them are described in U.S. Pat. Application Pub. No.: 2007/0148533 (Appl. No: 10/591,714) and is hereby incorporated by reference in its entirety and suitable garnet like structures, are described in International Patent Application Pub. No.: WO/2009/003695 which is hereby incorporated by reference for all that it contains. Suitable ceramic ion active metal ion conductors are described, for example, in US Patent No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes. These include phosphate Li ion conductors such as LiM2(PO4)3 where M may be Ti, Zr, Hf, Ge) and related compositions such as Li those into which certain ion substitutions are made including Li1+xTi2-xAlx(PO4)3 and the like which are known in the lithium battery arts. 
     Generally, the thickness of the inorganic sold electrolyte layer is in a range that is sensible for use in a battery cell, and generally depends, in part, on its ionic conductivity. In various embodiments the thickness of the solid electrolyte layer is in the range of 200 - 1 um thick, and more typically in the range of 100 - 5 µm, and even more typically in the range of 50 - 10 µm thick (e.g., about 10 µm or about 15 µm or about 20 µm or about 25 µm or about 30 µm or about 35 µm or about 40 µm or about 45 µm or about 50 µm thick). 
     Solid Electrolyte Interphase (Engineered SEI) 
     With reference to  FIG.  6 A , there is illustrated an apparatus  600  and method for cleaning a sulfide solid electrolyte glass layer and treating its surface to engineer a solid electrolyte interphase (SEI). The apparatus includes environmental chamber  650  having a very low moisture and oxygen content (e.g., less than 1 ppm), supply roll 605-R of sulfide glass sheet in roll form, web carrier for translating sheet  201  through cleaning chamber  620  and surface treatment chamber  630 . Cleaning chamber  620  is a plasma treatment chamber for ion etching the glass under Argon plasma. The ion-etching/plasma etching operation removes products of sulfide glass hydrolysis by etching off a thin layer of glass from the surface, typically in the range of 0.5 to 10 nm. Once surface  201   i  has been etched clean, it may be brought substantially immediately into cartridge  680  which is canister  681  filled with super dry hydrocarbon protective liquid  602 , as described and listed above. Cartridge  680  receives the cleaned glass by rolling to form sulfide glass roll 610-R. Once immersed in the protective liquid, the cleaned surface can be preserved as such. Cartridge  680  is suitable for storing the decal over extended time periods, including hours, days, or even weeks. The interior volume of canister  571  is substantially entirely filled with protective liquid, and may include moisture and oxygen gettering material, such as high surface area lithium metal in the form of numerous metal pieces immersed in the protective liquid. 
     In various embodiments the sulfide glass surface  201   i  is not chemically compatible in contact with lithium metal, and so coatings on the glass surface are described herein which are useful for creating a solid electrolyte interphase (SEI), the SEI forming as a result of the coating reacting with the sub stantially unpassivated lithium metal surface during the operation of reactive bonding (e.g., during lamination of the layers, typically using heat and pressure). 
     In various embodiments, after ion etching, sulfide glass layer  201  is translated via the carrier web into surface treating chamber  630 . In various embodiments surface treating chamber  630  is a second plasma unit, and glass  201  is subjected to nitrogen plasma and/or a Nitrogen/Argon plasma mixture, the process cleans the glass and also modifies the glass surface composition by introducing Nitrogen into/onto the surface. Thereafter, the glass is wound into roll  610 -R and immersed in protective liquid  602 , as described above. In alternative embodiments, as opposed to bringing the cleaned and Nitrogen treated glass into protective fluid (e.g., liquid or vapor phase), it is stored in a dry oxygen free argon filled enclosure. 
     Continuing with reference to  FIG.  6 A , in another embodiment, protective liquid  602  contains dissolved reactive species such as Nitrogen and Halogens (e.g., iodine), which treat the glass surface as it (the glass layer) is immersed in protective hydrocarbon liquid. Additional reactive species such as Nitrogen and Halogens may be injected into the canister as well. In yet another embodiment, the glass surface may be cleaned and surface treated in the same chamber. For example, inside chamber  620  the glass surface is cleaned with Argon plasma, and then the argon gas in the chamber is displaced by protective fluid in the vapor phase containing sulfide glass reactive species such as Nitrogen or Halogens (e.g., iodine I2 and iodine compounds). 
     In various embodiments the sulfide glass first major surface is treated in chamber  630  to form a thin precursor film that reacts with lithium metal to form an engineered solid electrolyte interphase (SEI). Various processes, reagents and treatments for engineering the SEI are described below. 
     With reference to  FIG.  6 B , in various embodiments a thin precursor film  640  may coated onto the clean first major surface of sulfide glass  201  to effect a solid electrolyte interphase via reaction with lithium metal during lamination, and preferably via reaction with pristine lithium metal surface. 
     In one embodiment precursor layer  640  is a halogen or interhalogen (diatomic or multi-atomic). For instance a monolayer, or several monolayers (e.g., up to 5 monolayers) of iodine or bromine molecules on the solid electrolyte glass surface is formed by condensation from the gas or liquid phase (e.g., gaseous or liquid phase iodine). 
     In one embodiment precursor layer is nitrogen. For example, a monolayer or several monolayers (e.g., up to 5 monolayers) of nitrogen molecules on the surface of the solid electrolyte gas is formed by condensation of nitrogen onto the solid electrolyte surface (from a gas or liquid phase). In a particular embodiment the nitrogen coated onto the surface of the solid electrolyte glass via a liquid carrier, such as liquid hydrocarbons, containing dissolved nitrogen molecules. The liquid hydrocarbons should be dry, as defined above, especially if the solid electrolyte is sensitive to moisture. Preferably the solubility of nitrogen in the hydrocarbon is large. For instance, the liquid carrier (e.g., liquid hydrocarbon) having a room temperature solubility of greater than 1 mole (nitrogen molecule) per mole of the liquid hydrocarbon, and preferably a ratio that is greater than 1.1, and even more preferably greater than 1.2. Particularly suitable liquid hydrocarbons include n-Octane, n-Nonane, n-Decane, n-Undecane, and n-Dodecane. 
     In other embodiments the solid electrolyte surface may be coated with a precursor of SO 2  or sulfur molecules, as described in more detail herein below. 
     While lithium is primarily referenced as the akali metal layer material herein, it should be understood that other alkali metals or alloys of lithium may also be used. 
     Examples: Coatings on Glass Electrolyte Surface to Form SEI via Reaction With Li 
     1. Halogens or Interhalogens (Diatomic or Multi-Atomic) 
     A monolayer, a few layers or condensed films are formed by iodine or bromine molecules on a glass surface from gas phase or from liquid phase. Halogen coating on the glass surface helps to improve wettability of Li metal towards glass (reactive wetting). In this case, the SEI formed on the clean Li surface consists of LiHal, in particular LiI or LiBr. 
     a. Halogen adsorption from the gas phase onto a glass surface at elevated temperatures, room temperature, or low temperatures. 
     In order to minimize the coating thickness the source of iodine or bromine vapor is not a molecular halogen, but a halogen-containing compound having a lower halogen vapor pressure. The coating thickness can be optimized by using halogen-containing compounds with appropriate vapor pressure and by adjusting duration and temperature of the coating process. Among the compounds that are used as sources of halogen vapor are solid polyhalogens. Solid polyiodides with various cations described in (Per H. Svensson, Lars Kloo, Chemical Reviews,  2003 , Vol. 103, No. 5) can be used as iodine sources (these compositions are incorporated by reference herein). Applicable polyhalogens include quaternary ammonium-polyhalogen compounds, in particular, tetraalkylammonium polyhalogens, inorganic polyiodides, such as RbI 3  CsI 3  and Cu-(NH 3 ) 4 ]I 4 , charge transfer complexes between dioxane, pyridine, polyvinyl, pyrrolidone, polyethyleneoxide and halogens (as acceptors), such as poly(2vinylpyridine)iodine and poly(4-vinylpyridine)bromine complexes. Other examples include metal-halogen compounds, for instance, CuI. 
     b. Halogen coating of a glass surface from the liquid phase 
     The glass surface is coated with halogens by its treatment in solutions containing molecular halogens (iodine, bromine) or polyhalogens that are dissolved in dry (less than 1ppm of moisture), non-polar solvents. In the preferred case, the solvents are selected from a group of unsaturated hydrocarbons or benzene and its homologues. In another case, the solvents are halogenated hydrocarbons, in particular, carbon tetrachloride. In another case, the solvent is carbon disulfide. The glass surface is brought into contact with or the glass is immersed into a solvent containing dissolved coating material (halogens or polyhalogens). Then the solvent is allowed to evaporate. In one case, Li-Mg or Li-Ca alloys (solid solution range) are used instead of Li metal. As a result, the SEI consists of LiI or LiBr doped with corresponding halides of Mg or Ca and has increased Li ion conductivity due to formation of Li cation vacancies (Schottky defects). In one case, both the glass surface and Li are treated in Halogen vapor containing atmosphere. As a result, the halogen coating (preferentially, a very thin coating that consists of one or two molecular layers) is formed on the glass surface and a thin layer of LiHal is formed on the Li surface. After Li lamination onto glass, halogen molecules react with LiHal layer on Li forming an SEI consisting of a LiHal layer with increased thickness. 
     2. Nitrogen 
     A monolayer, a few layers or condensed films formed by nitrogen molecules on a glass surface from gas phase or from liquid phase at RT or low temperatures. At RT only one or two layers of nitrogen molecules are adsorbed onto metal surfaces. Nitrogen can be adsorbed onto glass surfaces either in pure Nitrogen atmosphere (the volume having been previously evacuated to high vacuum) or in a mixed nitrogen / inert gas atmosphere (Ar/N 2 ). In order to coat a long strip of glass, either a flow of pure nitrogen or a flow of carrier gas (Ar) mixed with nitrogen can be used. 
     In various embodiments, the resulting SEI is, or includes, Li3N with a high Li ion conductivity. 
     In various embodiments the molecular nitrogen precursor layer is formed by coating the surface of the solid electrolyte glass sheet with a thin layer of a liquid hydrocarbon containing an amount of dissolved nitrogen molecules. In various embodiments the mole ratio of nitrogen molecules dissolved in the hydrocarbon carrier liquid is at least 0.05 moles of Nitrogen molecules per mole of liquid hydrocarbon (N2-moles/liq.hyd-moles),for instance, at least 0.1 N2-moles/liq.hyd-moles, at least 0.2 N2-moles/liq.hyd-moles, at least 0.3 N2-moles/liq.hyd-moles, at least 0.4 N2-moles/liq.hyd-moles, at least 0.5 N2-moles/liq.hyd-moles, at least 1.0 N2-moles/liq.hyd-moles. Particular suitable liquid hydrocarbon carriers are n-Octane, n-Nonane, n-Decane, n-Undecane, and n-Dodecane. 
     When using a liquid carrier containing dissolved nitrogen molecules, the SEI formed when the nitrogen coated solid electrolyte layer is directly contacted with lithium metal is a lithium nitride compound (e.g., Li3N), preferably fully reduced and highly conductive to lithium ions. As described above, the formation of the SEI may be effected during the lamination operation, and the liquid hydrocarbons on the surface of the solid electrolyte layer and/or the lithium metal layer removed prior to and/or as a result of bond laminating the layers together. 
     3. So2 
     a. SO2adsorption from the gas phase onto a glass surface at elevated temperatures, RT or low temperatures. SO2can be adsorbed onto glass surfaces either in pure SO2atmosphere (the volume having been previously evacuated to high vacuum) or in a mixed SO2 / inert gas atmosphere (Ar / SO2). 
     b. SO2coating of a glass surface at low temperature using liquid SO2. In various embodiments, the resulting SEI is, or includes, Li2S2O4, which is a known Li ion conductor. 
     4. Sulfur 
     a. Sublimation onto glass surface. S8 ring sulfur is known to be the dominant sublimation phase. 
     b. Glass surface oxidation leading to formation of an elemental S layer. In various embodiments, the resulting SEI is, or includes, Li2S. 
     Solid-State Laminate Electrode Assembly 
     With reference to  FIG.  7    there is illustrated standalone fully solid-state laminate electrode assembly  700  in accordance with various embodiments of the present disclosure. Laminate electrode assembly  700  is a laminate of alkali metal layer  101  having first major surface  101   i  and ii) inorganic alkali metal ion conducting solid electrolyte layer  201  having first major surface  201   i . In various embodiments the alkali metal layer is a lithium metal layer and the inorganic solid electrolyte layer is an inorganic lithium ion conducting sulfide glass sheet, also as described above. In various embodiments, laminate  700  is formed by reactively bonding layer  101  (lithium metal) with layer  201  (sulfide glass) to form inorganic interface  705  (also referred to herein as the solid electrolyte interphase (SEI)) as⅘ described in more detail herein below. The thickness of laminate  700  generally ranges from about 100 um down to as thin as about 5 um, and typically has a thickness in the range of 10 to 50 um. Preferably, the lithium ion resistance across the interface is less than 50 □ -cm2, and more preferably less than 25 □ -cm2. 
     The quality of inorganic interface  705  can be an important aspect for determining how well the laminate electrode assembly will operate in a battery cell. Preferably, inorganic interface  705  is substantially uncontaminated by organic material, including organic residues of any inert liquid that may have been used in making, storing and processing of the laminate structures. In various embodiments the inorganic interface may be further characterized as “sufficiently uncontaminated by passivated alkali metal,” by which it is meant that at least 70% of the geometric area of the solid-state interface is uncontaminated by the presence of passivated alkali metal, such as patches of passivated alkali metal film (i.e., filmy patches), as well as pieces of passivated alkali metal that break off during battery cell cycling and/or handling, and could become trapped at the interface in the form of solid flakes, flecks or material bits of passivated alkali metal. Preferably, at least 80% of the geometric area of the solid-state interface is uncontaminated as such, and more preferably at least 90%, and even more preferably at least 95%, and yet even more preferably the entire geometric area of the solid-state interface is uncontaminated by the presence of passivated alkali metal flakes, flecks, filmy patches or material bits. To achieve an inorganic interface that is sufficiently uncontaminated by passivated alkali metal, surface  101   i  of lithium metal layer  101  should be substantially unpassivated prior to bonding, and preferably the lithium metal layer surface is pristine. Additionally, the surface of the sulfide glass should be cleaned (e.g., by ion etching) immediately prior to bonding in order to remove solid products of sulfide glass hydrolysis. 
     When the reactive bond between the layers is continuous and complete, the laminate should exhibit exceptional adherence. In various embodiments the reactively bonded solid-state interface imparts exceptionally high peel strength to the standalone solid-state laminate electrode assembly (i.e., room temperature peel strength). For instance, the room temperature peel strength of the solid-state laminate electrode assembly is significantly greater than the tensile strength of the lithium metal layer to which it is bonded, such that during room temperature peel strength testing the lithium metal layer starts to deform, or tears, prior to peeling. 
     Methods of Making a Solid-State Laminate Electrode Assembly 
     With reference to  FIG.  8 A  there is illustrated a process and apparatus  800  for making a fully solid-state laminate electrode assembly  700  in accordance with various embodiments of the present disclosure. The process takes place in an environmentally controlled chamber  850 , and involves: i) providing a lithium metal laminate structure for processing into chamber  850 , the laminate structure (as described above with reference to  FIGS.  1 A-D ), the laminate structure composed of lithium metal layer  101  removably covered by protective inert liquid layer  102 , which encapsulates first major surface  101   i , and second major surface 101ii is held adjacent to current collector layer  103 ; providing for processing into chamber  850  an inorganic solid electrolyte laminate structure (as described above in various embodiments with reference to  FIGS.  2 A-D , the laminate composed of sulfide glass layer  201  having first major surface  201   i  encapsulated by protective liquid layer  202 . As shown in  FIG.  8 A , sulfide glass layer is supported on its second major surface 102ii by web carrier  805 , which is not a component of the sulfide glass laminate structure. When the laminate structures include a solid release layer, it is removed on a take-up roll not shown. Both layers  101  and  201  enter chamber  830  for removing the inert liquid layer  102  and  202  respectively. Removal of the inert liquid layer can involve a series of operations which may be performed sequentially and/or in parallel. In various embodiments one or more of the following operations is taken to remove the inert liquid layer, including: applying heat to the layers (convectively and/or conductively), applying a vacuum suction over the respective layers, applying a jet of dry gas (Ar or He preferably) and/or a jet of a high vapor pressure hydrocarbon, replacing a low vapor pressure fluid with another higher pressure fluid, or some combination thereof. 
     Once the liquid layer has been removed from sulfide glass surface  201   i , the surface may be cleaned in ion etching chamber  820 , for example, using Argon plasma (as described above with reference to chamber  620  in  FIG.  6   ). The cleaned sulfide glass may then be transferred into surface treating station  850  where it may undergo a second plasma treatment with Nitrogen or a mixture of Nitrogen and Argon, or it may be coated in chamber  850  to form a thin precursor film that is reactive with substantially unpassivated lithium metal to form a conductive solid electrolyte interphase. For instance, in various embodiments it may be coated with a thin layer of iodine or an iodine compound (e.g., condensing the iodine on the glass surface). Once the glass has been cleaned and/or its surface composition modified or coated with a thin precursor film, layers  101  and  201  are brought into laminating station  860  where they are reactive bonded to each other, generally by an application of both heat and pressure (via rollers  812 ) to form a fully solid-state laminate electrode assembly of the present disclosure. 
     A solid-state laminate electrode assembly includes a lithium ion conducting sulfide glass solid electrolyte sheet coated on its first major surface with a lithium metal layer by thermal evaporation without devitrifying the sulfide glass solid electrolyte sheet. The glass sheet is preferably freestandable and typically of thickness in the range of 10 um to 100 um, and more typically in the range of 20 to 50 um thick. The sheet may be positioned in a cooling fixture, such as a ceramic frame, and sealed to the frame via a releasable glue or epoxy, and the sheet is actively cooled during the thermal evaporation, for example by flowing a cryogenic fluid such as cool Argon gas onto the second major surface of the sheet (e.g., the cool Argon gas derived from a cryogenic tank of liquid Argon). The cooling of glass substrate sheet is sufficient to prevent the glass from fully or partially devitrifying and to prevent the heat of the evaporative process from damaging the surface of the glass. For instance, in various embodiments the temperature of the sulfide glass sheet is kept to 100° C. or less during the evaporation process, by application of the cooling gas. By actively cooled it is meant that the sulfide glass sheet is cooled while the evaporation of lithium metal is taking place. For instance, the cooling fluid (e.g., cool Argon gas) contacts the sulfide glass second major surface and it (the gas) is applied to the surface at a temperature that is no greater than 10° C., or no greater than 0° C., or no greater than - 10° C., or no greater than - 20° C. When actively cooling the sulfide glass sheet during evaporation, the sheet is preferably releasably sealed to the ceramic frame in order to prevent the cool Argon gas from releasing into the vacuum chamber of the lithium metal evaporator or from diffusing into the evaporating lithium flux (e.g., the edges of the glass sheet glued to the frame, such as with an epoxy). In other embodiments the sulfide glass sheet may be passively cooled, which is to mean cooled to a temperature below 15° C. prior to evaporating the lithium metal onto the glass first major surface. Typically when passively cooled the sulfide glass sheet is at a temperature that is less than 10° C. prior to evaporation, or less than 0° C., or less than -10° C., or less than -20° C. In some embodiments the substrate is both actively cooled and passively cooled as described above. In other embodiments the substrate is exclusively passively cooled (i.e., passively cooled and not actively cooled), or vice versa exclusively actively cooled. 
     With reference to  FIG.  8 B  there is illustrated another process and apparatus 800B for making fully solid-state laminate electrode assembly 801B wherein thin lithium metal layer 803B is thermally evaporated, under vacuum, onto first major surface z801i of lithium ion conducting sulfide glass substrate Z801. In various embodiments glass substrate Z801 may be solid electrolyte sheet  201  as described above with reference to  FIGS.  2 E-H  or nanofilm encapsulated sulfide glass solid electrolyte structures 200-2I-200-2P, as described with reference to  FIGS.  2 I-P . 
     Continuing with reference to  FIG.  8 B , apparatus 800B includes thermal evaporating device 410H, which includes a crucible for containing the source of molten lithium and a vacuum chamber, both of which are not shown. Glass substrate Z801 is preferably freestandable and substrateless, and typically of thickness in the range of 5 um to 100 um, and more typically in the range of 10 to 50 um thick. 
     In various embodiments lithium metal layer 803B is an ultra-thin layer that is less than 1 um (e.g., about 0.9 um, about 0.8 um, about 0.7 um, about 0.6 um, about 0.5 um, about 0.4 um, about 0.2 um, or about 0.1 um). When ultra-thin, the lithium metal layer may be deposited directly onto first major surface Z801i without actively removing heat away from sub strate Z801. 
     In accordance with the present disclosure, in various embodiments a thermal path for removing heat away from substrate Z801 is provided via a heat transfer fluid, which allows deposition of thicker lithium metal layers without damaging the glass surface or causing it to devitrify (e.g.,  2  -  10  um thick), and has benefit for ultra-thin layers as well, including that it allows for higher deposition rates and improved interface properties. Continuing with reference to  FIG.  8 B , apparatus 800B includes cooling fixture  833  for holding and cooling sub strate Z801 during thermal evaporation. Cooling fixture  833  may be a single substrate fixture, or a multiple substrate fixture as shown in cross sectional view in  FIG.  8 B  and in top down view shown in  FIG.  8 C . Fixture  833  includes material frame  835  with recessed portion  841  for receiving substrate  833  and backplane  837 . The recessed portions of the frame define discrete receptacles into which glass substrate Z801 is mounted, and may be peripherally adhered to the frame via grease or an adhesive. Frame  835  is shaped to include recessed compartment  842  that serves as a volume gap between the glass substrate and backplane  837 , and into which heat transfer fluid  821  (e.g., a cryogenic fluid such as Argon gas) is disposed or caused to flow through during the lithium metal evaporation operation. Volume gap  842  is coupled to heat transfer fluid source  861  (e.g., a tank of cryogenic Argon) via piping system  839  for admitting the Argon gas into fixture  833 , and may be interconnected to the other receptacles via the piping network (as shown). Generally, piping system  839  includes regulation controls and valves for adjusting/controlling the pressure, temperature and flow rate of Argon gas injected into volume gap  842  via piping system  839 . Preferably, volume gap  842  has a very small gap-dimension between the backplane and the second major surface Z801ii of substrate Z801. In various embodiments the gap-dimension is between 10 to 25 um, and in some embodiments the gap may be less than 10 um. Preferably, the second surface of the substrate does not touch backplane. Generally, the gap is less than 50 um, although it is not intended to be limited as such, thicker gaps are contemplated provided they are capable of removing a sufficient amount of heat to prevent glass damage during the evaporation operation. 
     In various embodiments heat transfer fluid  821  (e.g., cold Argon gas), which is admitted into volume gap  842  via piping system  839 , is forced to flow through gap  842  during the evaporation process, and therewith provides a convective cooling effect. In other embodiments, cold Argon gas injected into the gap prior to the lithium evaporation operation provides sufficient cooling to prevent glass damage as a result of the thermal evaporation. When referring to the Argon gas as cold it is meant that it is at a temperature that is less than 20° C., and typically less than 10° C. In various embodiments, the gas supply is cryogenic Argon gas. 
     In various embodiments, the pressure, flow rate and temperature of Argon gas  821  is adjusted and controlled to maintain the temperature of the sulfide glass substrate within a particular temperature range, or below a particular temperature value, such as the glass transition temperature of the sulfide glass solid electrolyte sheet (Tg). In particular embodiments, the thermal path provided by the Argon gas is sufficient to maintain the temperature of the sulfide glass substrate below a temperature value that is at least 10° C. lower than the Tg value, or at least 20° C. lower than the Tg value, or at least 50° C. lower than the Tg value, or at least 100° C. lower than the Tg value. 
     In various embodiments the temperature of glass substrateZ801 is controlled during the evaporation by adjusting/controlling the Argon gas temperature, pressure and flow rate through fixture  833 . In particular embodiments the temperature of sulfide glass substrate Z801 during the lithium evaporation operation is maintained in a range that is less than the glass transition temperature of the sulfide glass solid electrolyte sheet and no less than 40° C., or 60° C. or 80° C. For example, the heat transfer is controlled to maintain the glass substrate temperature within a range between 40° C. to 100° C., and preferably between 60° C. to 80° C. during the evaporation operation. 
     In various embodiments, prior to evaporating the lithium metal layer onto the sulfide glass substrate, first surface z801i is ion etched (e.g., as described herein with an Ar or other suitable plasma). Preferably the ion-etching operation takes place in the same vacuum chamber as the thermal evaporation, or the ion-etching and thermal evaporation tools/units are combined/arranged as a cluster tool, which allows for automatic transfer of the substrate between process chambers. Once the lithium metal layer is deposited onto the surface of the glass, a copper current collector may be applied onto the exposed lithium metal surface (e.g., evaporated or sputter deposited). 
     With reference to  FIG.  8 D  there is illustrated solid-state laminate electrode assembly Z800D composed of nanofilm-encapsulated sulfide glass solid electrolyte structure Z801, as described herein in accordance with various embodiments of the present disclosure, and lithium metal layer Z811 in direct contact with the first major surface of the encapsulating nanofilm. For example, lithium metal layer Z811 evaporated onto the first major surface of the nanofilm. 
     In various embodiments nanofilm encapsulated sulfide glass solid electrolyte structure Z801 has an asymmetric architecture such as those embodied in  FIGS.  2 L,  2 M,  2 N and  2 O . In particular embodiments the first major surface of the nanofilm is defined by a material composition that is devoid of lithium, and reactively transforms in contact with evaporated lithium metal to form a lithiated composition, which, in turn, leads to a low resistance interface between the evaporated lithium metal layer Z811 and the nanofilm. In a specific embodiment the first nanolayer is silicon nitride (e.g., SiN) and it reactively lithiates to form a lithiated compound (e.g., Li2SiN2). In another specific embodiment the first nanolayer is a phosphorous nitride devoid of lithium and oxygen (e.g., P3N5) and it reactively lithiates in contact with evaporated lithium to form a lithiated compound (e.g., LiPN2, Li7PN4, or a combination thereof). Moreover, for the above embodiments, the second nanolayer is generally unchanged as a result of the lithiation reaction (e.g., the second nanolayer may be an inert oxide such as alumina or zirconia), and after lithium metal is evaporated onto the first major surface of the nanofilm, the composition of the second nanolayer does not change (i.e., the evaporation of lithium metal does not lithiate the second nanolayer). 
     In various embodiments the nanofilm has a silicon nitride or a phosphorous nitride nanolayer, and when lithium metal is thermally evaporated onto it, the nanolayer is reactively lithiated. For instance, when the nanolayer is silicon nitride (e.g., SiN) or a phosphorous nitride devoid of oxygen the reaction product formed as a result of lithium metal evaporation is lithiated silicon nitride (e.g., Li2SiN2) and lithiated phosphorous nitride (e.g., LiPN2, Li7PN4, or a combination thereof), respectively. 
     In various embodiments lithium metal layer Z811 is deposited by thermal evaporation (as described throughout this specification), and layer Z811 typically not greater than 10 um and more typically not greater than 5 um thick. In various embodiments, ALD of the nanofilm is immediately followed by lithium evaporation using a combination or cluster tool that includes both an ALD tool and a lithium metal evaporation tool, and optionally an ion etch tool for cleaning the sulfide sheet prior to depositing the nanofilm. The combination of these processes and tools in a cluster provides significant fabrication advantages. Such a combination/cluster tool is illustrated in  FIG.  8 E . In particular embodiments tool 800E is engineered to interface with glove/dry box 896E (e.g., the sulfide solid electrolyte sheet may be fabricated and/or stored in box 896E). In addition to lithium thermal evaporation unit/tool 891E, the combination tool also includes ALD tool 892E, and plasma ion-etch tool 893E. As illustrated, the cluster tool is arranged to interface with glove box 896E for receiving the sulfide glass sheet. In various embodiments cluster tool 800E may further include a sputter deposition tool, for depositing lithium metal directly onto the sulfide sheet or the nanofilm, and/or for sputter depositing a metal current collector onto the exposed surface of the as-evaporated lithium metal layer. In other embodiments lithium metal layer Z811 may be a lithium foil laminated onto the nanofilm. 
     Once the nanofilm is formed, lithium metal may be evaporated directly onto the nanofilm first major surface using a single tool for both ALD deposition and lithium metal evaporation, and thus mitigating exposure to ambient air. Or the solid electrolyte structure may be removed from the ALD chamber for storage and then transferred to a lithium evaporation station. In various embodiments, prior to lithium evaporation, the first major surface of the nanofilm is cleaned by Argon or other suitable plasma etching. In some embodiments, the Argon etching operation may be utilized to remove a substantial thickness portion of the nanofilm, and in certain embodiments thereof it removes the nanofilm entirely in that portion which is adjacent the first major surface of the sulfide glass (i.e., the Argon etching operation removes the nanofilm first major portion, thus exposing the sulfide glass for evaporation of lithium metal directly onto the sulfide glass first major surface. 
     With reference to  FIG.  8 F  there is illustrated a process flow diagram illustrating methods for making solid-state laminate electrode assemblies made by evaporating lithium metal onto a nanofilm-encapsulated sulfide glass solid electrolyte structure. The initial operation is providing a nanofilm-encapsulated sulfide glass solid electrolyte structure in accordance with various embodiments of the present disclosure. In a first process (Process D), the major opposing surfaces of the nanofilm are cleaned by etching the nanofilm surfaces in an Argon or other suitable plasma, and immediately thereafter lithium metal is evaporated onto the first major surface of the nanofilm, and typically the lithium thickness is in the range of 1 um to 10 um (e.g., about 1 um or about 2 um, or about 5 um or about 10 um). In a second process (Process E) the first major portion of the nanofilm is completely removed by etching (e.g., in Argon plasma), and thereafter evaporating the lithium metal layer as described above. In a third process (Process F), the second major surface of the nanofilm is removed by the Argon plasma etch, and followed by the lithium metal evaporation operation. In a fourth process not shown, the Argon plasma etch is configured to remove both the first and the second major portion of the nanofilm. In some embodiments, rather than completely removing the second major portion and/or the first major portion of the nanofilm, those portions are only partially removed to enhance the mobility of Li ions. By incorporating operations to remove the nanofilm portion, entirely or partially, the nanofilm can be configured with a film thickness that is greater than that which would allow facile mobility of Li ions. For instance, in some embodiments, the thickness of the first and/or second major portion of the nanofilm is greater than 10 nm or greater than 20 nm, and therewith provides excellent moisture barrier properties, and during formation of the solid-state laminate the nanofilm thickness is reduced or removed by Argon plasma etching immediately prior to evaporating lithium metal and/or incorporating the solid electrolyte structure into a battery cell. In some embodiments, after removing the nanofilm first major portion a layer of lithium nitride (e.g., Li3N) or lithium phosphide (Li3P), preferably dense, may be deposited (e.g., via ALD) onto the glass sheet first major surface to provide low resistance interface between the sulfide glass sheet and the lithium metal layer. 
     In accordance with various embodiments of a laminate electrode assembly of the present disclosure, the assembly includes a solid electrolyte interphase (SEI) sandwiched between a lithium metal layer and a sulfide solid electrolyte sheet (e.g., a lithium ion conducting sulfide glass sheet). 
     In various embodiments, the SEI layer comprises lithium and one or more of phosphorous and nitrogen. In accordance with the present disclosure, a method of making the assembly, and in particular the SEI, involves injecting phosphorous and/or nitrogen into the sulfide glass sheet surface followed by lithium metal evaporation. In one embodiment the injecting operation involves implanting phosphorous and/or nitrogen into the surface of the glass, thus forming an implanted zone; for example, by ion implantation of nitrogen and/or phosphorous using a nitrogen and/or phosphorous ion gun. During lithium metal evaporation at least a portion of the evaporated lithium reacts with the injected surface (i.e., the implanted zone) of the sulfide glass to form the SEI. The implantation may be performed uniformly over the entire glass surface (i.e., the implanted zone is uniform) such that the SEI formed as a result of Li evaporation is continuous layer disposed between a lithium metal layer of the assembly and the sulfide glass sheet. Uniform may be understood with respect to thickness, so the implanted zone thickness is considered uniform if the variation in implant thickness (depth) is less than about 30%, for example less than 20%. In various embodiments, the uniform SEI may be a continuous layer of lithium nitride, lithium phosphide or a combination thereof. In various embodiments, the process involves nitriding and/or phosphiding the surface of the sulfide glass sheet followed by evaporating a lithium metal layer to form a sandwich structure composed of lithium ion conducting sulfide solid electrolyte sheet, a lithium metal layer, and a continuous SEI of a lithium nitride or lithium phosphide layer compound disposed there between. In various embodiments phosphiding and/or nitriding of the sulfide glass surface may be performed by ion implantation. In other embodiments the surface may be treated with a nitrogen and/or phosphorous plasma followed by Li metal evaporation. The SEI formed as such allows facile electrical migration of lithium ions between the metal layer and the sulfide solid electrolyte (e.g., glass sheet). In various embodiments the nitriding or phosphiding operation is performed by use of a nitrogen and/or phosphorous plasma (e.g., via plasma immersion), or by ion implantation (i.e., with nitrogen and/or phosphorous ions directed into the glass surface using a localized nitrogen or phosphorous ion gun as the source). 
     Li3N is a compound that is highly conductive to lithium ions and completely reduced, and therefore chemically compatible in contact with lithium metal; likewise Li3P. Accordingly, for some embodiments, it is desirable to achieve a lithium nitride layer compound stoichiometry that is close to that of Li3N, and to limit the incorporation of constituent elements from the glass, especially sulfur. To achieve a stoichiometric Li3N layer, the method of nitriding can involve saturating the glass surface with nitrogen ions (i.e., performing the nitriding operation for an amount of time sufficient to achieve saturation) followed by lithium metal evaporation. This method may also be applied for phosphiding the sulfide glass to form a near stoichiometric Li3P layer compound by saturating the glass surface with ion implanted phosphorous. In other phosphiding/nitriding embodiments, it is preferred to allow the incorporation of constituent elements from the glass when forming the lithium phosphorous/nitride SEI layer (e.g., to form lithium phosphorous sulfide compounds) by controlling the concentration and depth of the phosphorous ion and/or nitrogen ion implantation zone. 
     In a particular embodiment the nitriding/phosphiding or nitrogen/phosphorous injection operation and the lithium metal evaporation operation are performed consecutively (i.e., not simultaneously), wherein the nitriding, for example, of the surface is performed first and this is followed by lithium metal evaporation operation. In other embodiments the nitrogen injection (or the nitriding operation, for example) and the lithium evaporation operation are performed simultaneously, or performed partially simultaneously, which is to mean that the injection operation may be started first and then evaporating lithium while the injection operation is taking place, and then the injection operation is stopped while the lithium evaporation operation is allowed to continue. For instance, the method including: i) a first operation of injecting nitrogen/phosphorous into the glass surface prior to lithium evaporation (e.g., via ion implantation); ii) a second operation of simultaneously injecting nitrogen/phosphorous and evaporating lithium metal; and iii) a third operation of evaporating lithium metal in the absence of an injection operation. Accordingly, the process leads to a thin lithium metal layer on the surface of the SEI layer. 
     In a particular embodiment the nitriding/phosphiding operation is performed using a localized nitrogen/phosphorous ion source such as a nitrogen/phosphorous ion gun. In various embodiments the ion-implanted zone as defined by the depth of nitriding/phosphiding, is shallow and not greater than 10 nm. In other embodiments the depth of nitriding is between 10 nm to 100 nm, or between 100 nm to 1000 nm, or between 1 um to 5 um. The nitrogen and/or phosphorous containing SEI layer is formed by the chemical reaction that takes place as a result of the subsequent and/or simultaneous evaporation of lithium metal onto the surface of the ion-implanted glass surface. The lithium nitride/phosphide layer compound so formed may include additional elemental constituents of the sulfide glass substrate, including sulfur and/or boron, silicon and phosphorous when present in the sulfide glass. In various embodiments, the evaporated lithium metal layer on the surface of the glass is thin (e.g., less than 10um thick or less than 5um thick). 
     With reference to  FIG.  9   , laminate electrode assembly  700 , which may be formed as described above, includes second major surface 201ii of the sulfide glass, and which may be highly sensitive to moisture. Accordingly, in various embodiments, after laminate electrode assembly  700  has been formed it may be stored in cartridge  900 , as shown in  FIG.  9   . Cartridge  900  containing a bath of super dry hydrocarbon protective liquid  902  and laminate assembly  700  immersed in the bath, and by this expedient preserving the sulfide glass second major surface. Cartridge  900  is suitable for storing laminate electrode assembly  700  over extended time periods, including hours, days, or even weeks. More generally, the laminate electrode assemblies described herein, and in particular with reference to  FIGS.  8 B-D  may also be stored in cartridge  900 , as described above with reference to  FIG.  9   . 
     Battery Cells 
     With reference to  FIG.  10    there is illustrated battery cell  1000  composed of fully solid-state laminate electrode assembly  700  combined with positive electrode  1030 , such as a lithium ion intercalating material electrode (e.g., intercalating transition metal oxides), and battery electrolyte  1010 , disposed between the second major surface of sulfide glass layer  201  and positive electrode  1010 . In various embodiments it is contemplated that the battery cell is fully solid-state. In some fully solid-state battery embodiments, it is contemplated that the positive electrode is disposed in direct contact with the sulfide glass second major surface, in the absence of battery electrolyte layer  1010 . In other embodiments, battery cell  1000  may be a liquid or gel electrolyte battery wherein electrolyte layer  1010  is a liquid electrolyte impregnated porous polymer membrane and/or a gel electrolyte layer. The method of making the battery cell may include providing the solid-state laminate electrode assembly and disposing it in a battery cell housing adjacent to a liquid electrolyte impregnated in a Celgard-like porous polymer layer, and placing the positive electrode adjacent to it. 
     With reference to  FIG.  11    there is illustrated battery cell  1100  composed of positive electrode  1105  and solid-state lithium laminate electrode assembly 800D as described above in accordance with various embodiments of the present disclosure. 
     In various embodiments positive electrode  1105  is a lithium ion-intercalating electrode. Particularly suitable lithium ion intercalation compounds include, for example, intercalating transition metal oxides such as lithium cobalt oxides, lithium manganese oxides, lithium nickel oxides, lithium nickel manganese cobalt oxides, lithium nickel cobalt aluminum oxides (e.g., LiCoO2, LiMn2O4,LiNiO, LiNi0.33Mn0.33Co0.33O2, LiNi0.8Co0.15Al0.05O2 and the like) or intercalating transition metal phosphates and sulfates (e.g., LiFePO4, Li3V2(PO4)3, LiCoPO4, LiMnPO4, and LiFeSO4) or others (e.g., LiFeSO4F and LiVPO4F), as well as high voltage intercalating materials capable of achieving operating cell voltages versus lithium metal in excess of 4.5 Volts, including LiNiPO4, LiCoPO4, LiMn1.5Ni0.5O4, and Li 3 V 2 (PO 4 ) 3 . In some embodiments the intercalating material (e.g., an oxide), is unlithiated prior to incorporation in a battery cell, such as vanadium oxides and manganese oxides, including V 2 O 5  and V 6 O 13 . 
     In some embodiments, battery cell  1100  further comprises a non-aqueous electrolyte layer (not shown), which may be a liquid electrolyte layer impregnated in a microporous polymer separator or a gel electrolyte layer or a solid polymer electrolyte layer disposed between laminate electrode assembly  800 D and positive electrode  1105 . In other embodiments, positive electrode  1105  directly contacts laminate electrode assembly 800D, and, in particular, directly contacts the inorganic encapsulating nanofilm, which, in such embodiments, is configured with a material composition having oxidative stability in direct contact with the cathode electroactive material (e.g., the nanofilm surface in contact with the cathode is composed of one or more of aluminum oxide, zirconium oxide or niobium oxide). Accordingly, in various embodiments the nanofilm is chemically compatible in direct contact with cathode electroactive material having an electrochemical potential versus lithium metal that is at least 3 Volts, or at least 3.5 V, and the presence of the nanofilm provides a material barrier that prevents oxidation of the sulfide glass sheet by the cathode electroactive material. 
     In other embodiments it is contemplated that the battery cell is fully solid-state, and thus devoid of liquid electrolyte. For instance, in various solid-state battery embodiments, positive electrode  1105  (e.g., a lithium ion cathode of an intercalation material) directly contacts the encapsulating nanofilm. 
     In accordance with another aspect of the present disclosure, in various embodiments the glass sheet is protected by a protective coating to mitigate adverse reaction with vapor phase Li metal (e.g., Li metal vacuum evaporated at high rate) and/or moisture present in the ambient environment about the glass. 
     With reference to  FIG.  12    there is illustrated a cross sectional depiction of protected sulfide solid electrolyte glass sheet  12 - 100  in accordance with the present disclosure as well as a method of making said protected sulfide glass sheet. The method for making protected sulfide glass  12 - 100  involves a first step of providing sulfide glass solid electrolyte layer  12 - 102  (e.g., a lithium ion conducting sulfide glass sheet as described throughout U.S. Pat. No.: 10,164,289 and U.S. Pat. No.: 10,147,968), followed by a second step of depositing protective metal coating  12 - 104  onto the surface(s) of glass sheet  12 - 102 . In various embodiments, metal coating  12 - 104  is applied onto a first major surface of the glass sheet  12 - 102   i , or on both major opposing surfaces of the sheet  12 - 102   i / 12 - 102   ii , or on all exposed surfaces of the glass sheet, including the first and second principal side surfaces as well as its lengthwise edges  12 - 102   iii  and/or widthwise edges (not shown). As illustrated in  FIG.  12   , protective coating  12 - 104  is applied onto all exposed surfaces of sulfide glass sheet  1202 . Protective metal coating  12 - 104  may be deposited onto sheet  12 - 102  by physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques, such as metal evaporation. 
     In one embodiment protective metal coating  12 - 104  is a metal layer that readily alloys with lithium metal but does not react in contact with the sulfide glass sheet, and preferably does not react with H2S. It should be understood that metal layer  104  is not a Li metal layer. A thin gold layer exemplifies such a coating. Gold is chemically resistant to sulfur compounds and will not react with H2S, sulfide glass surfaces, or inclusions of elemental sulfur. Gold readily forms alloys with lithium. Preferably the gold layer forms a pinhole free and continuous coating on the glass surface, such that it provides a moisture barrier. For example, a continuous metal coating on the first principal side surface of the glass, and/or on the second principal side surface of the glass, and/or on all exposed surfaces of the glass. The gold coating is preferably just thick enough to provide a continuous moisture barrier. The gold coating generally has a thickness ranging from 1 to 3000 nm. Preferably the gold coating is exceptionally thin; for instance, between 1-10 nm (e.g., between 2 - 5 nm). 
     In other embodiments, protective metal coating  12 - 104  is composed of other suitable metals, such as indium, silver or tin, or more than one type of metal other than Li metal, for example, gold and silver, or gold and indium or gold and tin. In certain embodiments metal coating  12 - 104  is a multi-layer of a first metal layer (e.g., an exceptionally thin gold layer) in direct contact with the glass surface(s) and a second metal layer subsequently deposited on top of the first metal layer (e.g., a silver, tin or indium layer). For instance, a first gold metal layer having thickness ≤ 10 nm and a second silver metal layer having thickness ≥ 10 nm. The first gold layer provides a sulfur inert material cap on the surface of the glass, which minimizes sulfur from escaping and reacting with the second layer (e.g., Ag, In, Sn), which serves to provide mass for protectively absorbing vapor phase Li metal via an alloying reaction during electrode assembly when Li metal is evaporated onto the glass sheet, as described in more detail herein below. Additionally, the second layer may also provide a further moisture barrier for enabling protected glass sheet  100  to be transferred to a different chamber or shipped to another facility. 
     In various embodiments, the protective metal coating layer as described above provides the additional benefit of improving thermal management of the sulfide glass during Li deposition process, when making the electrode assembly. This benefit is described in more detail herein below. 
     The thin protective metal coating layer can improve thermal management of the sulfide glass during Li deposition. For instance, in various methods of making an electrode assembly in accordance with the present disclosure, there is an initial stage of Li evaporation that takes place prior to depositing Li metal onto the sulfide glass. During this initial stage, Li metal is deposited onto a shutter to achieve steady state deposition conditions and to improve vacuum in the deposition chamber, since freshly deposited lithium metal serves as a getter for residual gases including O2, H2O and N2. Improving the vacuum prior to Li deposition can improve the quality of the Li metal layer especially at lower rates of deposition, which may be desirable, depending on the thickness of the Li metal layer and the sensitivity of the sulfide glass sheet to thermal damage at high rates. However, the initial stage may itself cause the glass substrate to heat up overtime due to infrared radiation (thermal radiation) from the Li source vessel (Ta, W, Mo crucible wherein the Li metal is melted and from which the evaporative Li is derived). To mitigate sulfide glass heating during the initial stage of evaporation, the metals composing the thin protective metal layer may be selected to reflect the IR radiation, and in particular the surface of the composition of the metal layer. For instance, the composition of the metal layer surface may be selected to be nearly 100% reflective of the IR radiation, and thus preventing overheating, as described above, and preferably maintaining the temperature of the glass surface below the melting point of Li metal (about 180C). 
     With reference to  FIG.  13    there is illustrated in cross sectional depiction an electrode assembly in accordance with the present disclosure as well as a method for making the electrode assembly. Electrode assembly  13 - 200  is made by providing protected sulfide glass solid electrolyte sheet  12 - 100 , as shown in  FIG.  12    and depositing Li metal layer  13 - 210  directly onto the surface of sheet  12 - 100 , and in particular onto the first principal side surface of protective coating  12 - 104 . Thickness of the deposited lithium layer is selected such that protective metal coating  12 - 104  (e.g., a gold layer) is completely consumed by the alloying process with lithium. For example, both the gold protective coating and lithium metal are deposited onto the glass sheet by metal evaporation. The steps of gold coating and lithium evaporation may be performed in the same evaporation unit, or protected sulfide glass sheet  12 - 100 , preferably protectively coated on all exposed surfaces, may be transferred to a different chamber for Li metal evaporation onto the first principal side surface of the glass. Protective coating  12 - 104  alloys with the as-deposited Li metal transforming it (the protective coating) from a metal layer that is initially devoid of Li metal to lithiated layer  13 - 204 , which is a Li metal alloy. Eventually, the Li metal alloy so formed may react with the glass surface (e.g., via inclusions of elemental sulfur); however, the reaction is not as rapid and deep as that in the case of reaction between unprotected glass surface (i.e., no metal coating) and vapor phase Li. 
     In alternative embodiments the protective coating as described above with reference to  FIGS.  12 - 13    is not a metal layer or solely a metal layer, but rather a layer comprising a metal sulfide compound. With reference to  FIG.  14    there is illustrated protected sulfide glass  14 - 300  composed of sulfide glass  14 - 302  and protective metal sulfide coating  14 - 304  which is formed by metal evaporation onto the glass surface. Similar to that described above with reference to the metal layer protective coating, metal sulfide protective coating  14 - 304  may be deposited solely onto the first principal side surface of the glass, or both first and second principal side surfaces, and/or all exposed glass surfaces, including the lengthwise and/or widthwise edges. Suitable metals for forming the metal sulfide protective coating include metals that readily alloy with Li metal such as Ag, Sn, In, Al, Ge, Si and combinations thereof, as well as metals that do not readily alloy with Li metal such as Cu, Ni, Mo, Fe and combinations thereof. To form the metal sulfide protective coating, the metal is deposited to ensure that it reacts with sulfur derived from the sulfide glass sheet, and the metal should itself also be reactive with sulfur containing compounds, in particular H2S. 
     In some embodiments the protective metal sulfide coating is a single layer of metal sulfide. In other embodiments the protective metal sulfide coating is a multi-layer composed of first layer that is a metal sulfide layer and a second layer that is a metal layer. 
     With reference to  FIG.  15   , there is illustrated protected sulfide glass solid electrolyte sheet  15 - 400  having protective coating  15 - 402  that is a single layer of metal sulfide, as well as a method of making the protected sheet in accordance with the present disclosure. The method involves providing sulfide glass sheet  12 - 102  and depositing a metal onto the surface(s) of the glass (e.g., via vacuum evaporation of the metal) in a manner that results in the formation of a metal sulfide layer on the glass surface. Suitable metals for forming the metal sulfide layer include Ag, Sn, In, Al, Ge, Si, Cu, Ni, Mo, Fe and combinations thereof. 
     To form a protective coating that is a single layer of metal sulfide, the evaporation parameters, such as deposition rate, vacuum level, and the amount of metal deposited onto the glass surface (i.e., the effective thickness of the metal) is carefully controlled to ensure that the metal vapor is fully consumed by sulfur. This is particularly important when forming an electrode assembly by evaporation of Li metal onto the protected sulfide glass surface, as any unreacted metal might prevent direct contact between Li metal and the metal sulfide coating when forming an electrode assembly as described in more detail below. 
     With reference to  FIG.  16    there is illustrated electrode assembly  16 - 500  composed of protected sulfide glass solid electrolyte sheet  14 - 300 / 15 - 400  as illustrated in  FIG.  14    and  FIG.  15   , respectively, and Li metal layer  16 - 510 . Evaporation of Li metal reactively lithiates the metal sulfide layer, resulting in a Li-ion conducting metal sulfide protective coating. 
     As described above, in some embodiments the protective metal sulfide coating is a multi-layer coating composed of a first layer that is a metal sulfide layer in direct contact with the glass surface and a second layer that is a metal layer covering the metal sulfide first layer. With reference to  FIG.  17    there is illustrated, in cross sectional depiction, protected sulfide glass solid electrolyte sheet  17 - 600  composed of sulfide glass sheet  12 - 102  having protective coating  17 - 602  on one or more of its surfaces (e.g., solely on the first principal side surface or both first and second principal side surfaces, or on all exposed surfaces, as shown in  FIG.  17   ). In accordance with this embodiment protective coating  17 - 602  is a multi-layer stacking of first layer  17 - 602   a  that is a metal sulfide layer and second layer  17 - 603   b  that is a metal layer. In accordance with methods of making a protected sulfide glass sheet in accordance with this disclosure, multi-layer protective coating  17 - 602  is formed by deposition of metal(s) onto sulfide glass  12 - 102 , and in particular vacuum evaporation of said metal(s). Metal sulfide first layer  17 - 602   a  forming as a result of sulfur derived from the glass sheet reacting with metal vapor during the evaporation step, and second layer  17 - 602   b  formed thereafter, as a result of first layer  17 - 602   a  providing an effective cap on the glass surface that mitigates further reaction of the metal vapor with sulfur derived from the glass. In accordance with this embodiment it is important that the evaporated metal is selected such that it (the metal itself) is capable of readily alloying Li metal during fabrication of an electrode assembly by evaporation of Li metal onto the protective coating, and in particular directly onto the metal second layer  17 - 602   b . Particularly suitable metals for protective coating  17 - 602  include Ag, Sn, In, Al, Ge, Si, and combinations thereof. The interface between layers  17 - 602   a  and  17 - 602   b  occurs naturally during the evaporation step in accordance with the ability of layer  17 - 602   a  to cap the sulfide glass surface. In various embodiments the thickness of protective coating  17 - 602  is in the range of 10 to 3000 nm. 
     With reference to  FIG.  18    there is illustrated electrode assembly  18 - 700  composed of protected sulfide glass solid electrolyte sheet  17 - 600  and Li metal layer  18 - 710 . Evaporation of Li metal transforms metal second layer  17 - 602   b  into a Li metal alloy and this alloying reaction subsequently leads to lithiation of metal sulfide first layer  17 - 17 - 602   a , imparting Li-ion conductivity to protective coating  17 - 600 . 
     With reference to electrode assemblies  13 - 200 ,  16 - 500  and  18 - 700  as shown in  FIG.  13   ,  FIG.  16    and  FIG.  18    respectively, the amount of lithium deposited (e.g., via vacuum evaporation) is sufficient to completely alloy and/or lithiate the underlying protective coating and to provide excess lithium to form Li metal layer  13 - 210 ,  16 - 510 , and  18 - 710 . Thickness of the Li metal layer is generally at least 1 □m and more typically between 2-10 □m thick (e.g., about 2 or about 5 or about 10 □m thick). 
     With reference to  FIG.  19    there is illustrated a cross sectional depiction of battery cell  19 - 800  composed of electrode assembly  19 - 801  of the present disclosure which may be assembly  200 ,  500 ,  700  as described above with reference to various electrode assembly embodiments illustrated in  FIG.  13   ,  FIG.  16    and  FIG.  18    respectively, and positive electrode  19 - 820  (e.g., a Li-ion intercalation electrode), wherein electrode assembly  19 - 801  provides the negative electrode in the form of Li metal layer  19 - 810  and solid electrolyte separator protected sulfide glass solid electrolyte sheet  19 - 802  sandwiched between positive electrode  19 - 820  (e.g., a Li-ion intercalation electrode) and negative electrode  19 - 810  (e.g., Li metal). In accordance with the various electrode assemblies described above, when making battery cell  19 - 800 , prior to making battery cell  800  and placing electrode assembly  19 - 801  adjacent to positive electrode  19 - 820 , the opposing second principal side surface of the protected sulfide glass sheet adjacent to and opposing positive electrode  19 - 820  (if it has a protective coating) is cleaned to remove the protective coating from that surface. For example, the protective coating removed by an ion-etching step. In other embodiments, the protective coating on the second principal side surface of the glass sheet may be removed prior to making the electrode assembly (i.e., prior to depositing Li metal on the first principal side of the glass sheet, and in particular depositing Li metal in direct contact with the protective coating on the first principal side surface of the glass). 
     With reference to  FIG.  20    there is illustrated cross sectional depiction of a protected sulfide solid electrolyte glass sheet  20 - 100  in accordance with the present disclosure. The protected sulfide solid electrolyte glass sheet includes i) a lithium ion conducting sulfide solid electrolyte glass sheet  20 - 102 , as described above with reference to layer  12 - 102  shown in  FIG.  12   , and ii) first and second converted protective compound layers  20 - 104  and  20 - 106 , respectively. Protective compound layers  20 - 104  and  20 - 106  are formed by converting a protective metal coating layer by exposure to a nonmetal element that reacts with the metal coating to form the compound layer. Particularly suitable protective metal layers are Al, Sn, In, Si, Cu, Fe, Mo, W, Ta, Ag and Ti. In particular embodiments the nonmetal is oxygen, and the converted compound layer is an oxide of the metal element. In other embodiments the nonmetal is sulfur and the converted compound is a metal sulfide. In certain embodiments the nonmetal is nitrogen and the converted compound is a metal nitride. And in yet other embodiments the nonmetal is iodine or bromine and the converted compound is a metal iodide or a metal bromide. In a specific embodiment the metal layer is aluminum and the converted compound layer is aluminum oxide. 
     A method of making a converted compound layer  20 - 104  and  20 - 106  according to various embodiments is illustrated in  FIG.  21   . Method  21 - 100  involves operation  21 - 1  of providing sulfide glass sheet  20 - 102  and operation  21 - 2  of forming a protective metal coating on one or both major surfaces  20 - 102   i  and/or  10 - 102   ii ; for example, protective metal layers  20 - 104   a  and  20 - 106   a  on both opposing surfaces. The thickness of metal coating layers  20 - 104   a  and/or  20 - 106   a  is typically less than 100 nm (e.g., the metal coating may be in the range of about 10 nm to 100 nm). In various embodiments the metal layer is coated onto the glass surface by thermal evaporation of the metal. Particularly suitable metals for use as protective metal coating layer  21 - 104   a  and  21 - 106   a  include Al, Sn, In, Si, Cu, Fe, Mo, W, Ta, Ag, and Ti. Notably, when referring to the metal coating it is meant to include metalloids/semi-metals such as Si and the like. One or both of metal coatings  21 - 104   a  and  21 - 106   a  may be converted to a thin protective compound layer  21 - 104  and  21 - 106 , respectively. Preferably, the converted compound layer retains the continuous nature of the metal coating from which it was converted and is free of cracking that would otherwise expose the glass surface to the ambient environment. 
     Various methods may be used for conversion operation  21 - 3  for converting metal coatings  21 - 104   a  and  21 - 106   a  to their respective compound layers  21 - 104  and  21 - 106 . In various embodiments converted compound layers  21 - 104  and  21 - 106  are metal sulfides, and conversion operation  21 - 3  to a metal sulfide compound may include one or more of direct reaction of the metal layer with sulfur from the gas phase (e.g., sublimed sulfur) or reaction with elemental sulfur dissolved in a liquid carrier (in particular, in amines). The excess of sulfur can be removed by rinsing in amines. In various embodiments converted compound layers  21 - 104  and  21 - 106  are metal nitrides, and conversion operation  21 - 3  to a metal nitride compound may include one or more treating thin metal layer  21 - 104   a  and/or  21 - 106   a  in an atmosphere containing nitrogen or by treating in nitrogen plasma. In various embodiments converted compound layers  21 - 104  and  21 - 106  are metal a halogenide (e.g., iodide, bromide), and conversion operation  21 - 3  to a halogenide may include one or more of treating thin metal layers  21 - 104   a  and/or  21 - 106   a  with a nonmetal halogen (e.g., iodine/bromine) from the gas phase or from liquid solutions of halogens (e.g., iodine / bromine) complexes. 
     In various embodiments converted compound layers  21 - 104  and  21 - 106  are metal oxides, and conversion operation  21 - 3  to a metal oxide may include direct oxidation in oxygen-containing atmosphere (at a variety of temperatures and oxygen partial pressures), treatment in oxygen plasma, and treatment with atomic oxygen (in particular, produced by dissociation of ozone). For instance, a metal layer (e.g., aluminum) is deposited onto the glass as a thin layer and then immediately converted to an oxide layer by reacting the aluminum layer with highly reactive oxygen of an oxygen plasma. For example, compounds so formed may be metal oxides such as aluminum oxide, tin oxide, indium oxide, silicon oxide, copper oxide, iron oxide, molybdenum oxide, tungsten oxide, tantalum oxide, titanium oxide and combinations thereof. 
     When referring to the various metals suitable for use herein, the term metal is meant broadly to include metalloids or semi-metals, such as, for example, Si and Ge. 
     With reference to  FIG.  22 A , there is illustrated electrolyte structure  2201  that is composed of material layer  2220  coated on/covering in direct contact first major surface  2211  of solid electrolyte layer  201 . In various embodiments material layer  2220  is a continuous binary phosphorus nitride nanofilm (e.g., the nanofilm a coating of a P3N5 compound). Generally, the binary phosphorus nitride nanofilm compound maybe described as having stoichiometry PxNy, wherein both x andy are greater than zero. Material layer  2220  is devoid of Li ions, and thus not an intrinsic Li ion conductor. In various embodiments thickness of the nanofilm is between 1 nm to 100 nm (e.g., about 5 nm, about 10 nm, about 20 nm, about  3  0 nm, about 40 nm, about 50 nm, about 60 nm, about 70 nm, about 80 nm, about 90 nm, or about 100 nm). In other embodiments, thickness of layer  2220  is greater than 100 nm (e.g., 100 nm, to 200 nm). In various embodiments the binary phosphorus nitride compound is amorphous, and the binary phosphorus nitride material layer may also be amorphous. In various embodiments material layer  2220  is single phase (e.g., a single-phase binary phosphorus nitride compound, such as P3N5). The P 3 N 5  may be crystalline or amorphous (e.g., amorphous as determined by X-ray diffraction). Preferably material layer  2220  is protective such that it prevents water molecules in the ambient environment (e.g., a dry room) reaching surface  2211 . As described herein solid electrolyte layer  201  is a Li ion conducting sulfide glass sheet. However, the present disclosure contemplates other solid electrolyte layers including Li ion conducting garnet or garnet-like materials or other Li ion conducting sulfide materials. 
     In various embodiments electrolyte structure  2201  is an intermediary solid electrolyte structure that is formed and then transformed under a continuous flow process that is commensurate with, in various embodiments, continuous manufacturing an electrode assembly. In other embodiments structure  2201  is an intermediate product that may be used for batchwise manufacture of the electrode assembly, wherein material layer  2220  protects one or more surfaces of solid electrolyte layer  201  against degradation from contact with moisture or oxygen from the ambient environment during handling and/or storage; for instance, handling/storage in a dry room (e.g., having a dew point ≤ -20° C., such as -30° C. or -40° C.) or other low moisture containing environment (e.g., dry box having a moisture content below 100 ppm). 
     As illustrated in  FIG. ,  22 B , in accordance with the present disclosure, in various embodiments material layer  2220  may be applied as a coating onto surface  2211  by physical vapor deposition (PVD), using a sputtering or pulsed laser deposition apparatus  2250  in a manner that covers major surface  2211 . In other embodiments the material layer may be deposited by chemical vapor deposition (CVD). In various embodiments the method of making intermediary glass solid electrolyte product  2201  includes providing physical vapor deposition target  2252  of phosphorous nitride (e.g., a sputtering or pulse laser deposition target of P3N5). In various embodiments the phosphorous nitride target may be made by sintering powders (e.g., sintering powders of P3N5) or reactively forming the target from phosphorous and nitrogen precursor materials. As deposited, material layer  2220  may have a thickness in the range of 5 nm to 1um.. In various embodiments, the thickness may be in the range of 5 nm to 100 nm, or 100 nm to 1um. The thickness of the conversion layer  2220  may be about 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm. In some embodiments, the thickness of layer  2220  may be from 10 to 100 nm. In other embodiments the material layer coating may be applied to cover both first and second major opposing surfaces of solid electrolyte layer  201 , and in some embodiments, material layer coating  2220  covers all exposed surfaces of Li ion conducting glass sheet  201 . 
     In various embodiments a method for making binary phosphorus nitride material layer  2220  on solid electrolyte layer  201  is provided. The method includes providing a source of phosphorus and nitrogen and providing solid electrolyte substrate (or more generally layer  201 ). In various embodiments a single source of phosphorus and nitrogen may be used (e.g., a P 3 N 5  source). In other embodiments two or more sources may be employed (e.g., a first source for phosphorus and a second source for nitrogen). In various embodiments substrate  201  is a Li ion conducting sulfide glass sheet (or it may be a different solid electrolyte material, such as garnet). Thereafter, a binary phosphorus nitride film may be deposited onto a first major surface of the solid electrolyte layer by energizing the source(s). In various embodiments the source of phosphorus and nitrogen is a binary phosphorus nitride solid material (e.g., solid a P3N5 source). In various embodiments the deposition is physical vapor deposition that involves sputtering and/or pulsed laser deposition processes. In other embodiments the deposition process is chemical vapor deposition processing. In various embodiments the source is a solid target of composition of P3N5 (e.g., crystalline) and the material layer formed as a result of the deposition is amorphous. 
     In various embodiments powder processing may be used, and a dense sputtering target may be made by sintering phosphorous nitride particles (e.g., sintering P3N5 powders), for instance, by hot isostatically pressing phosphorous nitride particles into a solid article using a hot isostatic press (HIP). In other embodiments, cold isostatic pressing (CIP) may be used to make the target. Pressure may be applied using a gas, typically inert (e.g., argon). For instance, in some suitable implementations of embodiments a powder of a P3N5 or a compact thereofmay be sealed inside a container (e.g., a metal enclosure) and then processed at the requisite temperature and pressure to produce the dense target material. Cold isostatic pressing (CIP) is also contemplated herein. In various embodiments the PVD target is a solid of a first composition (e.g., a P3N5) and the thin phosphorus nitride layer is also a solid of the same composition as the target (e.g., P3N5). In yet another embodiment, a deposition target (e.g., a sputtering target) of phosphorus nitride (e.g., P3N5) may be fabricated by melting a starting material of phosphorus nitride (e.g., P3N5), and cooling the melt to a solid block, preferably the as-melted block having the desired shape and size for use as a target (e.g., sputtering target). In a particular embodiment, the P3N5 material may be melted inside a vacuum or controlled atmosphere furnace (e.g., under a partial pressure of nitrogen gas). In various embodiments, the P3N5 may be melted in a mold to form a target of desired shape and size (e.g., a disc), such as an Inconel™ mold or other mold material suitable for processing the material at its melt temperature. 
     In various embodiments the thin phosphorus nitride layer may be deposited as a phosphorus rich layer using a sputtering or pulse laser deposition target that includes elemental P (e.g., black phosphorus), which may be used as a binder therein to improve processability of the P3N5 target. For instance, a suitable sputter target may be composed of at least 50 vol% of P3N5 (e.g., about 95% P3N5 and 5% elemental phosphorus, or about 90% P3N5 and 10% elemental phosphorus, or about 80% P3N5 and 20% elemental phosphorus, or about 70% P3N5 and 30% elemental phosphorus, or about 60% P3N5 and 40% elemental phosphorus, or about 50% P3N5 and 50% elemental phosphorus). In other embodiments it is contemplated that the combination target of P3N5 and elemental phosphorus has less than 50 vol% of P3N5. It is also contemplated that elemental phosphorus may be deposited as a layer on the sulfide glass from a target of elemental phosphorus (e.g., black phosphorus). In various embodiments the target of P3N5 may be made by incorporating lithium phosphide, for example, as a binder material (e.g., Li3P). For instance, a suitable sputter target may be composed of at least 50 vol% ofP3N5 (e.g., about 95% P3N5 and 5% Li3P, or about 90% P3N5 and 10% Li3P, or about 80% P3N5 and 20% Li3P, or about 70% P3N5 and 30% Li3P, or about 60% P3N5 and 40% Li3P, or about 50% P3N5 and 50% Li3P). In yet other embodiments it is contemplated that both elemental P (e.g., black phosphorus) and Li3P may be used as binders for a P3N5 target. For instance, a suitable sputter target may be composed of at least 50 vol% ofP3N5 (e.g., about 95% P3N5 and 5% (Li3P + P), or about 90% P3N5 and 10% (Li3P + P), or about 80% P3N5 and 20% (Li3P + P), or about 70% P3N5 and 30% (Li3P + P), or about 60% P3N5 and 40% (Li3P + P), or about 50% P3N5 and 50% (Li3P + P)). 
     In yet another embodiment, a target of P3N5 may be made by incorporating lithium nitride as a binder material (e.g., Li3N). In various embodiments the target is made by mixing lithium nitride, which melts at about 813° C., with P3N5 and heated above 813° C. (e.g., heated to 850° C.) which leads to molten Li3N wetting and binding to P3N5 particles to form a solid target mixture. While this disclosure is not limited by any particular theory of operation, in various embodiments it is contemplated that the lithium nitride reacts with the phosphorus nitride particles to form a lithiated phosphorus nitride compound (e.g., 4 Li3N + P3N5 ® Li4PN3). In various embodiments the target is made by heating the mixture to a temperature that melts the lithium nitride component but does not melt the phosphorus nitride component (i.e., the processing temperature is above the melt temperature of Li3N and below the melt temperature of P3N5). In other embodiments, it is contemplated that the lithium nitride and the phosphorus nitride components are heated to a temperature that melts both components. For instance, a suitable sputter target may be composed of at least 50 vol% of P3N5 (e.g., about 95% P3N5 and 5% Li3N, or about 90% P3N5 and 10% Li3N, or about 80% P3N5 and 20% Li3N, or about 70% P3N5 and 30% Li3N, or about 60% P3N5 and 40% Li3N, or about 50% P3N5 and 50% Li3N). 
     Material layer  2220  may be converted from a non-lithium ion conducting to lithium ion conducting by the application of active lithium onto its surface. In accordance with the present disclosure the phosphorous nitride coating may be converted to a lithiated layer be applying active lithium onto the phosphorous nitride surface. In various embodiments the active lithium applied onto the phosphorous nitride surface may be lithium metal. In particular embodiments, lithium metal is deposited onto the surface of the phosphorous nitride coating by physical vapor deposition such as sputtering, evaporation or pulsed laser deposition. In various embodiments the lithiated phosphorous nitride coating is fully lithiated. For example, fully lithiated P3N5 converted by application of lithium metal to a ternary lithium phosphorous-nitride compound, such as Li4PN3, Li7PN4, LiPN2, Li12P3N9 or Li10P4N10. 
     With reference to  FIG.  22 C , the present disclosure provides an electrode assembly  2290  that is formed by reacting material layer  2220  with Li metal leading to a lithiated layer  2225 . As illustrated the lithiation may be effectuated by depositing Li metal onto the surface of the material layer to form lithiated layer  2225 . In various embodiments, the conversion layer is fully lithiated by the process. For instance, a conversion layer of stoichiometry P 3 N 5  may be fully or partially lithiated by the lithium deposition process to P 3 N 5  film fully reacted to a layer of a ternary lithium phosphorous-nitride compound, such as Li 4 PN 3 , Li 7 PN 4 , LiPN 2 , Li 12 P 3 N 9  and Li 10 P4N 10 . The lithiation process is a reaction that transforms the conversion coating to an electrochemically operable coating that allows the through transmission of lithium ions and is stable against lithium metal or other electroactive materials with electrochemical potentials within  1  volt of lithium metal. In specific embodiments the conductivity of lithiated layer  2225  is at least 10 -7  S/cm, or at least 10 -6  S/cm or at least 10 -5  S/cm. Lithiated layer  2225  may be a continuous layer. 
     In various embodiments multiple layering steps are involved in the process of making lithiated layer  2225 . For instance, in various embodiments the method may involve making a first coating of a first material layer of a binary phosphorous nitride film followed by depositing lithium metal (e.g., by evaporation) onto the first binary phosphorus nitride film to convert it to a first lithiated layer, and this is followed by depositing a second binary phosphorus nitride material layer film onto the first lithiated layer, and then evaporating lithium metal onto the second layer, thus reactively lithiating that layer. The process may be continued as such multiple times. In various embodiments each of the coatings is of a thickness that can be fully reacted by the lithium metal evaporation. For instance, each sputter deposited coating may be of thickness of about 1 to 10 nm, or about 10 to 20 nm or about 20 - 30 nm or about 30 - 40 nm or about 40 -50 nm. In a particular embodiment, a first binary phosphorus nitride film is deposited onto a Li ion conducting sulfide glass sheet by sputter depositing from a P3N5 target (or other Li ion conducting solid electrolyte, including as an inorganic oxide-based or phosphate-based Li ion conductor a garnet-type or LATP-type, for example), the first film having a thickness that is suitable for complete conversion. In various embodiments the first film thickness may be about 5 to 20 nm (e.g., about 5 nm or about 10 nm or about 15 nm or about 20 nm). The deposition of the first film may be followed by a lithiation/conversion step that may be brought about by evaporating lithium metal onto the first film (such as by PVD). Once the first film is lithiated or converted to a lithiated compound(s), a second film of phosphorus nitride may be deposited onto the first lithiated layer. In various embodiments the second film can have a thickness of about 5 to 20 nm (e.g., about 5 nm or about 10 nm or about 15 nm or about 20 nm). Thereafter, the second film may belithiated by evaporation of lithium metal. The process may be continued by depositing and lithiating a plurality of layers (e.g., two, three, four or five layers). 
     Referring to  FIG.  22 D  an electrode assembly is illustrated in a manner that could be used when incorporated in a battery cell of the present disclosure. The assembly includes lithiated conversion coating layer  2225  and lithium metal layer on the opposing surface of layer  2225 . Solid electrolyte sheet  2210  may be used as the solid electrolyte separator in a fully solid-state battery including opposing positive electrode  2280 . In embodiments, additional material layers may be incorporated between positive electrode  2280  and sheet  2210 . 
     In alternative embodiments, the use of phosphorous nitride conversion coatings may be used in a similar manner as described above and applied to other types of solid electrolyte material layers, including lithium ion conducting polycrystalline ceramics. For instance, the phosphorous nitride conversion coating and lithiation processes may be applied to polycrystalline ceramics such as lithium metal phosphate ceramics and garnet ceramics as are known in the field of solid-state lithium batteries (e.g., layer  2210  may be a garnet ceramic layer, such as a tape cast sintered layer of Li-ion conductive garnet material) and to sulfide solid electrolytes generally, including crystalline, glass and glass ceramic sulfide solid electrolytes. Some examples of suitable such garnet materials are described in US Pat. 8,658,317, 8,092,941, the J. Am. Ceram. Soc. 86, 437-440, 2003, the disclosures of which in this regard are incorporated by reference herein. 
     In yet another aspect of the present disclosure, cathode materials, especially cathode particles, are provided having a phosphorous nitride film covering their surfaces (e.g., P 3 N 5 ). In some examples the phosphorous nitride film may be devoid of oxygen. Surface coated cathode particles may be made by providing cathode particles and coating the particles with a thin phosphorous nitride (e.g., P 3 N 5 ) surface layer. The particles may be coated by physical or chemical methods, including vapor deposition, sputtering, atomic layer deposition and solution methods such as sol gel. The particles may be granular or powder particles. Non-limiting examples of cathode material particles that are suitable herein for coating with a P3N5 surface film (or phosphorous nitride film more generally) include those that are known in the Li-ion battery field, such as lithium metal oxides and phosphates (e.g., nickel rich cathode compositions such as, LiNixMnyCo1-x-yO2 (NMC), and others such as LCO, NCA and LFP (lithium iron phosphate). 
     In yet another aspect, present disclosure provides a high-quality nitrogen rich thin film having a chemical makeup that - in its as-deposited state - is composed of constituent elements lithium (Li), phosphorus (P) and nitrogen (N). In various embodiments the nitrogen rich Li-P-N film, in its as-deposited state, is amorphous. In various embodiments the nitrogen rich Li-P-N film is substantially devoid of oxygen as a constituent element, and in such instances the film is sometimes referred to herein as oxygen-free. In various embodiments the film is moisture resistant in its as-deposited state. In various embodiments the nitrogen rich Li-P-N film is a single-phase material. In other embodiments the film is multi-phase, composed of two or more phases. For example, multi-phase and amorphous. In accordance with the present disclosure the nitrogen rich Li-P-N film is formed on a substrate surface or a particle surface. For example, in various embodiments, the as-deposited film is formed on the surface of a Li ion conducting solid electrolyte layer serving as substrate. In other embodiments, the film may cover surfaces of a cathode or anode electroactive material layer or powder particle. 
     In various embodiments thickness of the as-deposited nitrogen rich Li-P-N film is not greater than 1000 nm. In embodiments thickness of the as-deposited film ranges from about 1000 nm - 900 nm, or about 900 - 800 nm, or about 800 - 700 nm, or about 700 - 600 nm, or about 600 - 500 nm, or about 500 - 400 nm, or about 400 - 300 nm, or about 300 - 200 nm, or about 200- 100 nm, or about 100- 50 nm, or about 50 - 20 nm, or about 20 - 10 nm, or about 10-5 nm, or about 5 - 1 nm. 
     In various embodiments, for example, the nitrogen rich Li-P-N film has a N/P ratio that ranges from about 1.65 to 3.00. In embodiments, for example, the as-deposited film has a N/P ratio of about 1.65 - 1.70. In embodiments, for example, the as-deposited film has a N/P ratio of about 1.70 - 1.75. In embodiments, for example, the as-deposited film has a N/P ratio of about 1.80 - 1.90. In embodiments, for example, the as-deposited film has a N/P ratio of about 1.90 - 2.00. In embodiments, for example, the as-deposited film has a N/P ratio of about 1.90. In embodiments, for example, the as-deposited film has a N/P ratio of about 2.00 - 2.15. In embodiments, for example, the as-deposited film has a N/P ratio of about 2.15 - 2.30. In embodiments, for example, the as-deposited film has a N/P ratio of about 2.30 - 2.50. In embodiments, for example, the as-deposited film has a N/P ratio of about 2.50 - 2.75. In embodiments, for example, the as-deposited film has a N/P ratio of about 2.75 - 3.00, or from about 3.00- 5.00. In various embodiments the N/Li ratio ranges from about 0.75 to 32. In embodiments, for example, the as-deposited film has a N/Li ratio of about 0.75 to 1.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 1.00 to 1.50. In embodiments, for example, the as-deposited film has a N/Li ratio of about 1.50 to 2.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 2.00 - 2.50. In embodiments, for example, the as-deposited film has a N/Li ratio of about 2.50 - 3.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 3.00 - 4.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 4.00 - 5.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 5.00 - 6.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 6.00 - 7.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 7.00 - 10.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 10.00 - 15.00. In embodiments, for example, the as-deposited film has a N/Li ratio of about 15.00 - 30.00. 
     In various embodiments the nitrogen rich as-deposited Li-P-N film is substantially devoid of oxygen. 
     In embodiments the mole percent of Li is in the range of 0.4 to 1.9% and the mole percent of P is in the range of 37.5% to 36.5% and the mole percent of N is in the range of 62.5% to 61.5%. In embodiments the mole percent of Liis in the range of 1.9% to 4% and the mole percent of P is in the range of 36.5% to 35.5% and the mole percent of N is in the range of 61.5% to 60.5%. In embodiments the mole percent of Li is in the range of 4% to 8.3% and the mole percent of Pis in the range of 35.5% to 33.3% and the mole percent of N is in the range of 60.5% to 58.3%. In embodiments the mole percent of Li is in the range of 8.3% to 13.2% and the mole percent of P is in the range of 33.3% to 30.9% and the mole percent of N is in the range of 58.3% to 55.9%. In embodiments the mole percent of Li is in the range of 13.2% to 18.8% and the mole percent of P is in the range of 30.9% to 28.1% and the mole percent of Nis in the range of 55.9% to 53.1%. In embodiments the mole percent of Li is in the range of 18.8% to 25% and the mole percent of P is in the range of 28.1% to 25.0% and the mole percent of N is in the range of 53.15% to 50.0%. In embodiments the mole percent of Li is in the range of 25% to 32.1% and the mole percent of P is in the range of 25.0% to 21.4% and the mole percent of N is in the range of 50.0% to 46.4%. In embodiments the mole percent of Li is in the range of 32.1% to 40.4% and the mole percent of P is in the range of 21.4% to 17.3% and the mole percent of N is in the range of 24.4% to 42.3%. In embodiments the mole percent of Li is in the range of 40.4% to 50% and the mole percent of P is in the range of 17.3% to 12.5% and the mole percent ofN is in the range of 42.3% to 37.5%. In embodiments the mole percent of Li is in the range of 50% to 58.3% and the mole percent of P is in the range of 12.5% to 8.3% and the mole percent of N is in the range of 37.5% to 33.3%. In embodiments the mole percent of Li is in the range of 58.3% to 61.4% and the mole percent of P is in the range of 8.3% to 6.8% and the mole percent of N is in the range of 33.3% to 31.8%. 
     In various embodiments the nitrogen rich as-deposited Li-P-N film is substantially devoid of oxygen. 
     In accordance with various embodiments of the present disclosure, the as-deposited film is amorphous and substantially devoid of oxygen as a constituent element of the film, and such a film is sometimes referred to herein as a non-oxygen containing Li-P-N film/layer, or more simply as an oxygen-free Li-P-N film. Embodiments with one or more additional non-oxygen constituent elements are also contemplated (e.g., one or more of a halogen). In a particular embodiment the as-deposited film is a simple tri-constituent oxygen-free Li-P-N film that consists only of Li, P and N as elemental constituents. The Li-P-N films described herein may be usefully employed as a material layer or film covering the surface of a battery material or battery material component. In particular embodiments the nitrogen rich Li-P-N films and/or oxygen free Li-P-N films and/or nitrogen rich and oxygen free films of the present disclosure cover the surface of a solid electrolyte (e.g., a solid electrolyte powder or layer) and/or the surface of a solid electroactive material (e.g., a cathode active material powder or layer). 
     In various embodiments the Li-P-N film (e.g., oxygen-free and/or nitrogen rich) may be used as a material layer on the surface of a solid electrolyte, and thereon serve as a moisture-resistant protective film or as an artificial solid electrolyte interphase (SEI) or interlayer in contact with a cathode active material (CAM) or anode active material (AAM), such as lithium metal. In various embodiments the oxygen-free/nitrogen-rich LiP-N film of the present disclosure has a chemical makeup that is moisture-resistant, which is surprising for a lithiated material. For instance, such a moisture-resistant Li-P-N film may be used as a protective layer covering the surface(s) of a water sensitive solid electrolyte, such as those composed of Li ion conducting sulfide materials (e.g., Li ion conducting sulfide glasses) or Li ion conducting oxide materials (e.g., garnet and perovskite type Li ion conductors). 
     In various embodiments the as-deposited film, which is composed of constituent elements lithium, phosphorus, and nitrogen, has a chemical makeup that is moisture-resistant. In various embodiments the moisture-resistant as-deposited film is amorphous or substantially amorphous. In various embodiments the stoichiometric range of the constituent elements that form the moisture-resistant as-deposited film (e.g., amorphous) is about Li 0.15 P 2.85 N 4.8 , or about Li 0.23 P 2.78 N 4.7 , or about Li 0.3 P 2.7 N 4.6 , or about Li 0.45 P 2.55 N 4.4 , or about Li 0.6 P 2.4 N 4.2 , or about Li 0.75 P 2.3 N 4 , or about Li 0.9 P 2.1 N 3   .8 , or about Li 1.05 P 1.95 N 3   .6 , or about Li 1   .   2 P 1.8 N 3   .4 , or about Li 1.35 P 1.65 N 3   .2  or about Li 1.5 P 1.5 N 3 , or about Li 1.65 P 1.35 N 2   .8 , or about Li 1.95 P 1.05 N 2   .4 , or about Li 2.1 P 0.9 N 2   .2 , or about Li 2.25 P 0.75 N 2   .0 , or about Li 2.4 P 0.6 N 1   .8.   
     In one aspect the present disclosure provides a physical vapor deposition (PVD) target formed of a mechanically robust ceramic body having a chemical makeup comprising constituent elements lithium, phosphorus, and nitrogen. In various embodiments the ceramic body is uncontaminated by refractory or transition materials (e.g., tungsten metal). In various embodiments the chemical makeup of the ceramic body is substantially devoid of oxygen. In various embodiments the chemical makeup of the ceramic body is substantially devoid of constituent elements other than lithium, phosphorus, and nitrogen, and preferably devoid of refractory material contaminants. In various embodiments the PVD target is a sputtering target, and the ceramic body is the sputtering target material. In various embodiments the sputtering target is substantially single phase and preferably has a phase purity greater than 95%. In other embodiments the ceramic body is multi-phase (e.g., two or more phases). For instance, each phase of the ceramic body comprising constituent elements lithium, phosphorus, and nitrogen. In other embodiments, one or more phases may be absent lithium as a constituent element. For example, a first phase comprising constituent elements lithium, phosphorus, and nitrogen, and a second phase comprising phosphorus and nitrogen and devoid of lithium. In various embodiments the ceramic body of the sputtering target comprises a first phase that is solely composed of lithium, phosphorus, and nitrogen. In some embodiments the ceramic body of the sputtering target is single phase or substantially single phase (e.g., having a phase purity greater than 95%), and solely composed of constituent elements lithium, phosphorus, and nitrogen. In some embodiments the ceramic body of the sputtering target is multi-phase (e.g., composed of two phases), composed of a first phase that is solely composed of constituent elements lithium, phosphorus, and nitrogen, and a second phase that is solely composed of nitrogen and phosphorus. In various of the aforesaid embodiments, the ceramic body of the sputtering target (e.g., single phase or multi-phase) is resistant to moisture, and preferably impervious to moisture. 
     In various embodiments the PVD target is moisture resistant. In particular, the moisture resistant sputtering target does not decompose in direct contact with ambient air. For instance, the moisture resistant character of the ceramic body allows for the vacuum deposition chamber to be opened to ambient air when positioning or removing a substrate into/out of the chamber. In some instances, the ambient air may be the atmosphere of a dry room having a dew point no greater than -20° C., or no greater than -40° C., and/or the ambient air may have a relative humidity in the range of about 10 to 60% (e.g., 20 -50%). Preferably, the target material in accordance with the present disclosure is so chemically resistant to water and mechanically robust that it is substantially unaffected upon immersion of the target in a water bath at 23° C., and in particular no evolution of ammonia is observed and the target retains its mechanical integrity and geometric shape after 1 hour in the bath. Preferably the ceramic body of the sputtering target is impervious to moisture. 
     In various embodiments the sputtering target has a ceramic body, which is composed of constituent elements lithium, phosphorus, and nitrogen, and a chemical makeup that is moisture resistant. In various embodiments the stoichiometric range of the constituent elements that form the moisture-resistant ceramic body of the sputtering target is Li 0.15 P 2.85 N 4.8 , or about Li 0.23 P 2.78 N 4.7 , or about Li 0.3 P 2.7 N 4.6 , or about Li 0.45 P 2.55 N 4.4 , or about Li 0.6 P 2.4 N 4.2 , or about Li 0.75 P 2.3 N 4 , or about Li 0.9 P 2.1 N 3   .8 , or about Li 1.05 P 1.95 N 3   .6 , or about Li 1.2 P 1.8 N 3   .4 , or about Li 1.35 P 1.65 N 3   .2  or about Li 1.5 P 1.5 N 3 , or about Li 1.65 P 1.35 N 2   .8 , or about Li 1.95 P 1.05 N 2   .4 , or about Li 2.1 P 0.9 N 2   .2 , or about Li 2.25 P 0.75 N 2   .0 , or about Li 2.4 P 0.6 N 1   .8 . 
     In various embodiments the mole percent of the constituent elements that form the moisture-resistant ceramic body of the sputtering target is as follows: the mole percent of Li is in the range of 0.4 to 1.9% and the mole percent of Pis in the range of 37.5% to 36.5% and the mole percent of N is in the range of 62.5% to 61.5%. In embodiments the mole percent of Li is in the range of 1.9% to 4% and the mole percent of P is in the range of 36.5% to 35.5% and the mole percent of N is in the range of 61.5% to 60.5%. In embodiments the mole percent of Li is in the range of 4% to 8.3% and the mole percent of P is in the range of 35.5% to 33.3% and the mole percent of N is in the range of 60.5% to 58.3%. In embodiments the mole percent of Li is in the range of 8.3% to 13.2% and the mole percent of P is in the range of 33.3% to 30.9% and the mole percent of N is in the range of 58.3% to 55.9%. In embodiments the mole percent of Li is in the range of 13.2% to 18.8% and the mole percent of P is in the range of 30.9% to 28.1% and the mole percent of N is in the range of 55.9% to 53.1%. In embodiments the mole percent of Li is in the range of 18.8% to 25% and the mole percent of P is in the range of 28.1% to 25.0% and the mole percent of N is in the range of 53.15% to 50.0%. In embodiments the mole percent of Li is in the range of 25% to 32.1% and the mole percent of P is in the range of 25.0% to 21.4% and the mole percent of N is in the range of 50.0% to 46.4%. In embodiments the mole percent of Li is in the range of 32.1% to 40.4% and the mole percent of P is in the range of 21.4% to 17.3% and the mole percent of N is in the range of 24.4% to 42.3%. In embodiments the mole percent of Li is in the range of 40.4% to 50% and the mole percent of P is in the range of 17.3% to 12.5% and the mole percent of N is in the range of 42.3% to 37.5%. In embodiments the mole percent of Li is in the range of 50% to 58.3% and the mole percent of P is in the range of 12.5% to 8.3% and the mole percent of N is in the range of 37.5% to 33.3%. In embodiments the mole percent of Li is in the range of 58.3% to 61.4% and the mole percent of P is in the range of 8.3% to 6.8% and the mole percent of N is in the range of 33.3% to 31.8%. 
     In various of these aforesaid embodiments the ceramic body of the sputtering target is substantially single phase. In other of these aforesaid embodiments the ceramic body of the sputtering target is composed of two or more phases. For instance, a first phase having a first stoichiometric range and second phase having a different stoichiometric range. In other embodiments the first phase has a stoichiometric range as described above (e.g., between Li 2.25 P 0.75 N 2   .0  to Li 2.4 P 0.6 N 1   .8  or between Li 2.1 P 0.9 N 2   .2  to Li 2.25 P 0.75 N 2   .0 , or between Li 1.8 P 1.2 N 2   .6  to Li 2.1 P 0.9 N 2   .2 , or between Li 1   .   5 P 1   .   5 N 3  to Li 1.8 P 1.2 N 2   .6  or between Li 1.2 P 1.8 N 3   .4  to Li 1.5 P 1.5 N 3   
     In another aspect the present disclosure provides methods of making the afore described Li-P-N based PVD targets (e.g., an Li-P-N sputtering target). In various embodiments the method involves making Li-P-N ceramic material and molding/pressing or otherwise shaping the Li-P-N ceramic into the desired target material shape and dimension. Preferably, the Li-P-N ceramic material is of exceptional purity, and, in particular, devoid of refractory or transition metal materials or other unwanted metal that may contaminate the ceramic, especially during processing. In various embodiments the Li-P-N ceramic material is processed by reacting two or material precursor materials (e.g., by heating the precursor materials). In various embodiments oxygen-free Li-P-N ceramic material is processed by reacting a first precursor of a phosphorus nitride compound (e.g., P 3 N 5 ) with a second precursor that is an oxygen-free lithium compound such as lithium nitride (Li 3 N) or lithium phosphide (Li 3 P) or both. Lithium nitride (Li 3 N) is a moisture sensitive material that decomposes in air evolving ammonia, and therefore handling and reacting with Li 3 N is performed in a substantially moisture free environment. Fully reduced lithium nitride (Li 3 N) melts at a temperature near the decomposition temperature of P 3 N 5 . In various embodiments the oxygen-free Li-P-N ceramic material is prepared by heating the first and second precursor materials to a temperature that is above that of the Li 3 N melt temperature and preferably below that of the P 3 N 5  decomposition temperature. As it pertains to contamination, selecting the proper vessel to perform the reaction is important. Tungsten metal for example is a well-known high temperature substantially inert and may be used as such. It has been contemplated those reacting precursors in a tungsten crucible is stabilized by forming a tungsten nitride surface skin on the surface of the crucible, and certainly sufficient for such processing. However, when fabricating a sputtering target material for deposition of a thin film battery functional material layer, exceptional metals purity is needed for achieving a high-quality film that is not disadvantaged by a metallic or refractory contaminate which can lead to shorts or film cracking after extended use in a battery cell. Accordingly, in various embodiments processing of the ceramic Li-P-N material is performed in a nitride vessel that is inert to the forming reactions of the precursors. In particular embodiments the vessel is coated with an inert metal nitride (e.g., a boron nitride layer). In various embodiments the reaction is carried out in a metal nitride vessel, and, for example, in particular embodiments the metal nitride vessel is a silicon nitride vessel or a boron nitride vessel. As such, the as-fabricated ceramic Li-P-N target material is substantially devoid of vessel contaminants. For example, the Li-P-N target material is substantially devoid of tungsten. In addition to the happenstance of tungsten nitride skin particles flaking into the Li-P-N ceramic material, another disadvantage of a tungsten metal vessel is that the formation of the nitride skin leads to complications achieving the desired stoichiometry of the final Li-P-N product material. 
     Having a high-quality target, as described herein, is important for achieving the most desirable as-deposited film characteristics with the highest level of reproducibility, thickness optimization, deposition speed, and low cost. The Li-P-N sputtering target material may be shaped for the desired deposition processing conditions. In various embodiments the Li-P-N sputtering target is disc shaped. In other embodiments the Li-P-N sputtering target is cylindrically shaped. In yet other embodiments, substantially rectangularly shaped target materials are contemplated, including an array of substantially square tile shaped Li-P-N targets arranged onto a sputtering backing plate as an array of tile-like targets. 
     In another aspect the present disclosure provides an intermediate solid electrolyte structure (e.g., a sheet of Li-conducting solid electrolyte) having a solid electrolyte first surface that is covered by a Li-P-N surface film of the present disclosure. In various embodiments the solid electrolyte is a Li-conducting sulfide-based material (e.g., a Li-ion conducting sulfide glass sheet). In other embodiments the solid electrolyte is an oxide Li-ion conducting, including garnet and perovskite type Li-ion conductors. In various embodiments the Li-P-N film is deposited onto the surface of the solid electrolyte using physical vapor deposition (PVD). In a particular embodiment, the Li-P-N film is deposited by sputtering, especially RF sputtering, including RF magnetron sputtering. In other embodiments the Li-P-N film may be deposited by chemical vapor deposition (CVD). In various embodiments, for example, the solid electrolyte of the present disclosure has a surface(s) that is covered by an amorphous oxygen-free LPN film having a chemical makeup - in its as-deposited state - that is composed of lithium, phosphorus, and nitrogen constituent elements. Preferably the amorphous oxygen-free Li-P-N film, in its as-deposited state, is of exceptional quality, continuous and pinhole free. Even more preferably, the amorphous oxygen-free Li-P-N film - in its as-deposited state - is moisture-resistant, and thus imparts moisture-resistance to an otherwise moisture sensitive solid electrolyte surface. Preferably, the moisture-resistant solid electrolyte of the present disclosure is sufficiently resistant to attack by moisture in the air that the LPN film protected surface of the solid electrolyte is resistant to chemical degradation in air with liquid phase water on its protected surface. In particular embodiments, for example, batteries utilizing an otherwise moisture sensitive solid electrolyte (e.g., a garnet solid electrolyte) may be manufactured, or partially manufactured, in an environment with a lower requirement on environmental moisture content compared to that for manufacturing the battery with a garnet solid electrolyte surface that is not protected by an Li-P-N film of the present disclosure. Accordingly, as described in more detail hereinbelow, the present disclosure also provides batteries and methods for making batteries having a solid electrolyte with one or more major surfaces protected by a moisture-resistant Li-P-N film of the present disclosure. 
     To serve as an optimal protective film the Li-P-N film is preferably of exceptional quality, pinhole, and continuous. To achieve such a film, the deposition process may be advanced as described herein, and, in particular, by the fabrication of a high quality mechanically robust PVD target material composed of lithium, phosphorus, and nitrogen as constituent elements, for example an oxygen-free Li-P-N ceramic body shaped as a target material for physically vapor depositing Li-P-N as a thin pinhole film (e.g., amorphous). In various embodiments the Li-P-N shaped target material has a chemical makeup that is moisture-resistant, and preferably sufficiently moisture resistant that it can be immersed in a water bath with minimal or no chemical degradation or decomposition. In various embodiments the deposition process for making the Li-P-N film is sputtering, and in particular RF sputtering, including RF magnetron sputtering. In various embodiments the target (e.g., sputtering target). 
     In yet another aspect, the present disclosure provides a composite solid electrolyte PVD target. In various embodiments the composite solid electrolyte PVD target has a layered architecture composed of a primary target material layer composed of phosphorus and/or nitrogen as constituent elements of the target (e.g., P 3 N 5 ) and a secondary target material disposed between the primary target material and a backing plate of the sputtering target. In various embodiments the primary target material is phosphorus nitride (e.g., composed of a primary (e.g.,P 3 N 5 )ceramic body as the target material) and a second ceramic body, serving as the secondary target material, disposed between the primary (e.g., P 3 N 5 )target material body (e.g., in the form of a sputtering target, such as disc shaped) and the backing plate (e.g., a copper backing plate as is known in the sputtering arts). In various embodiments the second ceramic body is similar in shape and size to the ceramic body of the primary (e.g., P 3  N 5 )targetbody (e.g., disc shaped). In various embodiments the second ceramic body is a dense layer, typically disc shaped, of lithium phosphate (e.g., Li 3 PO 4  or LiPO 3 ). In various embodiments the first ceramic body, serving as the primary target material layer, is formed as a disc, with a ceramic body density in the range of 40% to 90% dense (e.g., about 40%, or about 50%, or about 60% or about 70%, or about 805 or about 90% dense). In such instances, during sputtering the secondary target material layer (e.g., Li 3 PO 4 ) undergoes sputtering simultaneous with that of the primary target (e.g., the P 3 N 5  target material), and in so doing offers protection against unwanted sputtering from the copper backing plate. 
     In some specific embodiments, a suitable composite solid electrolyte PVD target is composed of a mixture of a first component material of P 3 N 5  or a lithiated phosphorus nitride and a second component material such as LiPO 3 , which serves as a sintering or densifying aid for forming a dense composite target. In various embodiments, the mole ratio of P 3 N 5  to LiPO 3  can be between 50% to 95% P 3  N 5  or 60% to 95%, or 70% to 95%, or 80% to 95%, or 90% to 95%. In various embodiments the mixed composite target has a weight percent of P 3  N 5  that is between 50% to 95% P 3  N 5 , or 60% to 95%, or 70% to 95%, or 80% to 95%, or 90% to 95%. 
     In yet still another aspect the present disclosure relates to improvements of the Li / solid electrolyte interface electrical properties (e.g., sulfide glass solid electrolyte or other solid electrolyte such as Li ion conducting garnets or Li ion conducting phosphates such as lithium titanium phosphates). In various embodiments, improved performance may be achieved by deposition (e.g., physical vapor deposition (PVD)) of a composite film containing phosphorus nitride (e.g., P 3 N 5 ) onto the solid electrolyte surface (e.g., glass surface). In one embodiment, physical vapor deposition of P 3 N 5  and LiPON onto the glass electrolyte surface followed by thermal deposition of Li metal that reacts with the composite film forms a stable interface with low resistance. Suitable physical vapor deposition techniques may include RF sputtering, E-beam, and pulse laser deposition. 
     In various embodiments, a P 3 N 5  compacted powder or solid fragments may be used to make a mosaic target by placing P 3 N 5  into a cup made of a different material. Since this material would be co-sputtered with P 3 N 5 , in one embodiment the cup may be made from a Li 3 PO 4  target, which is readily available and used to prepare LiPON films with reactive sputtering in nitrogen-containing plasma. An example is illustrated in  FIG.  23   . In this way, the glass electrolyte surface can be coated with a composite film consisting of P 3 N 5  and LiPON. In various embodiments, deposition of 50-100 nm thick pore-free films composed of P 3 N 5  and LiPON appear featureless under a confocal microscope with high magnification (&gt; 1000 X). 
     LiPON films are known to be kinetically stable to Li metal. Also, the reaction between Li and LiPON leads to a minimal change in volume from reagents to products, therefore LiPON films can be made dense and pore-free. 
     In addition, in some embodiments the ratio of the available surface areas of P 3 N 5  and Li 3 PO 4  on the mosaic target may be adjusted or optimized in order to mitigate the volume change that may occur during the reaction of Li and P 3 N 5  and formation of multiple reaction products, since if the molar volumes of reagents and reaction products are significantly different during the initial stage of Li deposition, the deposited film could have through porosity, leading to direct contact between Li and glass during later stages of Li deposition. 
     In one embodiment, P 3 N 5  solid fragments can be fabricated in the form of pressed pellets or cut pieces of known geometry and placed onto the Li 3 PO 4  cup. In this way, the ratio of the exposed Li 3 PO 4  surface to the P 3 N 5  surface can be well-determined and controlled. 
     As an alternative to co-sputtering P 3 N 5  and LiPON from a single target containing P 3 N 5  and Li 3 PO 4 , a dense or substantially dense P 3 N 5  target may be used in combination with a second target, such as a Li 3 PO 4  target, for sputtering deposition and, in particular embodiments, reactive sputtering in N 2  or N 2 -Ar plasma. In various embodiments, the sputtering rates of P 3 N 5  and Li 3 PO 4  may be independently varied thereby permitting control of the composition of deposited films accordingly. An additional benefit of using N 2  or N 2 -Ar plasma is to mitigate N loss from P 3 N 5  during sputter deposition. Generally, the higher the deposition rate, the larger the fraction of N 2  has to be used in the N 2 -Ar mixture. Both targets could be planar or one or both could be a hollow cylindrical target, or other suitable shape. 
     As an alternative to parallel co-sputtering using two targets simultaneously, in another embodiment two materials may be sputter deposited onto glass sequentially, forming a dual protective layer. In this case, a thin pore-free layer of LiPON, or another solid electrolyte compatible with Li, may be deposited onto the solid electrolyte layer (e.g., a sulfide glass solid electrolyte surface) initially as a first layer. Then a thin layer of P 3 N 5  or P 3 N 5  + LiPON may be deposited on top of the first layer. In this case, even if the reaction products of P 3 N 5  and Li do not form a fully dense pinhole-free film, the glass electrolyte surface is protected from reacting with Li by the initial solid electrolyte layer compatible with Li. In one embodiment, this thin solid electrolyte layer is LiPON deposited with one of the aforementioned PVD techniques. In another embodiment, the thin LiPON layer may be deposited with an atomic layer deposition (ALD) technique, or other suitable chemical vapor deposition (CVD) technique. 
     In one embodiment, the formed layer of P 3 N 5  + Li reaction products has low through porosity, while the LiPON film has a low surface density of pinholes, which are not aligned with the pores in the P 3 N 5  + Li reaction product layer. In this case, the required LiPON layer thickness is lower than that in conventional solid-state cells with a LiPON electrolyte. Accordingly, the resistance of the LiPON layer can be reduced significantly. The range of LiPON layer thicknesses is generally greater than 1 nm and &lt;100 nm, or &lt;50 nm, or &lt;20 nm. 
     In one embodiment, the first solid electrolyte layer is a thin layer of sulfide glass stable to Li, such as Li 2 S·P 2 S 5  In one embodiment, a sheet of Li 2 S·B 2 S 3  glass is coated with a thin layer of Li 2 S·P 2 S 5  and then with a thin layer of P 3 N 5 , providing double protection of the Li 2 S·B 2 S 3  glass. 
     In various embodiments, the surface film is formed on a solid electrolyte layer, such as a Li ion conductive sulfide sheet (e.g., a sulfide glass sheet or pressed powder compact of sulfide solid electrolyte material, including both amorphous/glassy and crystalline sulfide powders, such as argyrodite (e.g., Li 6 PS 5 Cl), or a Li ion conductive oxide material, such as those commonly referred to in the Li ion battery field as a garnet Li ion conductor or a garnet like lithium ion conductor (e.g., Li 7 La 3 Zr 2 O 12  (LLZO)), or a Li ion conductive perovskite, or a Li ion conductive phosphate material, such as a lithium titanium phosphate commonly referred to in the battery field as LATP (e.g., Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ). 
     Conclusion 
     It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art. Although various details have been omitted for clarity’s sake, various design alternatives may be implemented. Therefore, the present examples are to be considered as illustrative and not restrictive, and the disclosure is not to be limited to the details in specific examples herein.