Patent Publication Number: US-2021167421-A1

Title: Solid state electrolyte materials

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a division of U.S. application Ser. No. 16/237,101 filed Dec. 31, 2018, the disclosure of which is hereby incorporated in its entirety by reference herein. 
    
    
     TECHNICAL FIELD 
     The present disclosure relates to a lithium conducting ceramic oxide decontamination method and decontaminated lithium conducting ceramic oxide materials, and in some embodiments, the use of such materials as solid state electrolytes (SSEs) with improved interfacial properties. 
     BACKGROUND 
     Solid state electrolyte (SSE) systems exhibiting Li +  conductivity of greater than 10 mScm −1  at room temperature have shown promise for application with lithium metal anodes in high energy and high power density batteries. This application may offer several advantages over traditional liquid electrolyte system. Non-limiting examples of these benefits include higher gravimetric and volumetric energy density, broader operable voltage, wider temperature range, and enhanced safety. However, many obstacles remain for implementing such SSE systems with lithium metal anodes in such applications. 
     SUMMARY 
     According to one embodiment, a solid state electrolyte material is disclosed. The solid state electrolyte material includes a decontaminated lithium conducting ceramic oxide material including a decontaminated surface thickness. The decontaminated surface thickness is less than or equal to 5 nm. The decontaminated surface thickness may be greater than or equal to 1 nm. The decontaminated lithium conducting ceramic oxide material is selected from the group consisting of Li 7 La 3 Zr 2 O 12  (LLZO), Li 5 La 3 Ta 2 O 12  (LLTO), Li 6 La 2 CaTa 2 O 12  (LLCTO), Li 6 La 2 ANb 2 O 12  (A is Ca or Sr), Li 1+x Al x Ge 2-x (PO 4 ) 3  (LAGP), Li 14 Al 0.4 (Ge 2-x Ti x ) 1.6 (PO 4 ) 3  (LAGTP), perovskite Li 3x La 2/3-x TiO 3  (LLTO), Li 0.8 La 0.6 Zr 2 (PO 4 ) 3  (LLZP), Li 1+x Ti 2-x Al x (PO 4 ) 3  (LTAP), Li 1+x+y Ti 2-x Al x Si y (PO 4 ) 3-y  (LTASP), LiTi x Zr 2-x (PO 4 ) 3  (LTZP), Li 2 Nd 3 TeSbO 12  and mixtures thereof. The decontaminated surface thickness may include one or more contaminants. The one or more contaminants may include one or more carbonates, one or more hydroxides and combinations thereof. The one or more carbonates may include one or more bicarbonates. The decontaminated lithium conducting ceramic oxide material may have a wettability in a range of contact angles of 40° to 100°. The decontaminated lithium conducting ceramic oxide material has an interfacial resistance of 0 to 20 Ohm cm 2 . The decontaminated lithium conducting ceramic oxide material may be formed from a contaminated lithium conducting ceramic oxide material having a contaminated surface thickness of the one or more contaminants. The contaminated surface thickness may be greater than the decontaminated surface thickness. The contaminated surface thickness may be in a range of 50 to 70 nm. The contaminated lithium conducting ceramic oxide material may have a contaminated impedance and the decontaminated lithium conducting ceramic oxide material may have a decontaminated impedance. The decontaminated impedance at room temperature may be less than the contaminated impedance at room temperature. The decontaminated impedance may be less than the contaminated impedance by a factor in a range of 6 to 22 times. 
     According to another embodiment, a solid state electrolyte material is disclosed. The solid state electrolyte material includes a decontaminated lithium conducting ceramic oxide material including a decontaminated surface thickness. The decontaminated surface thickness may be less than or equal to 5 nm. The solid state electrolyte material may have a thickness of less than 100 μm. The solid state electrolyte material may be a planar solid state electrolyte material. The thickness of the solid state electrolyte material may be 10 to 40 μm. 
     In yet another embodiment, a solid state electrolyte material is disclosed. The solid state electrolyte material includes a decontaminated lithium conducting ceramic oxide material including a decontaminated surface thickness. The decontaminated surface thickness may be less than or equal to 5 nm. The solid state electrolyte material is formed in a spherical shape having a diameter. The diameter of the spherical shape may be in the range of 400 to 600 nm. The decontaminated surface thickness may be greater than or equal to 1 nm. The decontaminated lithium conducting ceramic oxide material is selected from the group consisting of Li 7 La 3 Zr 2 O 12  (LLZO), Li 5 La 3 Ta 2 O 12  (LLTO), Li 6 La 2 CaTa 2 O 12  (LLCTO), Li 6 La 2 ANb 2 O 12  (A is Ca or Sr), Li 1+x Al x Ge 2-x (PO 4 ) 3  (LAGP), Li 14 Al 0.4 (Ge 2-x Ti x ) 1.6 (PO 4 ) 3  (LAGTP), perovskite Li 3x La 2/3-x TiO 3  (LLTO), Li 0.8 La 0.6 Zr 2 (PO 4 ) 3  (LLZP), Li 1+x Ti 2-x Al x (PO 4 ) 3  (LTAP), Li 1+x+y Ti 2-x Al x Si y (PO 4 ) 3-y  (LTASP), LiTi x Zr 2-x (PO 4 ) 3  (LTZP), Li 2 Nd 3 TeSbO 12  and mixtures thereof. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a schematic diagram of a solid state battery (SSB) according to one embodiment. 
         FIG. 2  is a schematic diagram of method steps for removing surface contamination from a Li +  conducting ceramic oxide according to one embodiment. 
         FIGS. 3A, 3B, 3C and 3D  show graphs of soft x-ray absorption spectroscopy (XAS) spectrums of LLZO powder under different conditions. 
         FIG. 4  depict representative Nyquist plots for Li/LLZO/Li cells at room temperature before and after a treatment according to an embodiment. 
         FIG. 5  depicts a graph of galvanostic cycling of Li/LLZO/Li cells at room temperature with a current density of 1.4 μAcm −2  before and after a treatment according to an embodiment. 
     
    
    
     DETAILED DESCRIPTION 
     Embodiments of the present disclosure are described herein. It is to be understood, however, that the disclosed embodiments are merely examples and other embodiments can take various and alternative forms. The figures are not necessarily to scale; some features could be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the embodiments. As those of ordinary skill in the art will understand, various features illustrated and described with reference to any one of the figures can be combined with features illustrated in one or more other figures to produce embodiments that are not explicitly illustrated or described. The combinations of features illustrated provide representative embodiments for typical applications. Various combinations and modifications of the features consistent with the teachings of this disclosure, however, could be desired for particular applications or implementations. 
     Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, “parts of,” and ratio values are by weight; the term “polymer” includes “oligomer,” “copolymer,” “terpolymer,” and the like; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; molecular weights provided for any polymers refers to number average molecular weight; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property. 
     This invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way. 
     As used in the specification and the appended claims, the singular form “a,” “an,” and “the” comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components. 
     The term “substantially” or “about” may be used herein to describe disclosed or claimed embodiments. The term “substantially” or “about” may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, “substantially” or “about” may signify that the value or relative characteristic it modifies is within ±0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic. 
     The use of lithium metal anodes in solid state batteries (SSBs) with energy densities exceeding 500 Whkg −1  or 1,000 WhL −1  with costs lower than $100 per kWh −1  is not currently feasible. Advancement of solid state electrolytes (SSEs) to achieve a Li +  conductivity greater than 10 mScm −1  at room temperature is sought so that these performance levels may be met. One material that shows promise to achieve this conductivity is the garnet-type ceramic oxide of Li 7 La 3 Zr 2 O 12  (otherwise referred to as LLZO). LLZO is a prime candidate for this application because it has (1) a property of fast Li-ion conduction, (2) decreased flammability properties, (3) adequate mechanical strength (e.g., an elastic modulus of at least 150 GPa and a fracture toughness of 0.86 to 1.63 MPam), (4) a wide electrochemical window (e.g., 6 volts or higher), and (5) chemical stability with metallic Li. Despite these promising attributes, there has been minimal success in employing ceramic oxides (including LLZO) in high-performance SSBs. One of the major obstacles to such success has been the large interfacial impedance between the ceramic oxide and electrode materials. 
     Unlike many traditional ceramic oxides (e.g., La 2 O 3 , Al 2 O 3  and ZrO 2 ), LLZO and other Li +  conducting ceramic oxides require a high degree of care during processing and storage due to their high reactivity. During wet processing, Li′ conducting ceramic oxides react with solvents and produce adventitious carbon. Similarly, during storage, Li +  conducting ceramic oxides produce thick layers of ionically insulating materials (e.g., carbonates, hydroxides, etc.) on the surface of the Li +  conducting ceramic oxides that act as surface contamination. The formation of these layers is one of the main causes of interfacial resistance between LLZO and Li metal. Moreover, the formation of these layers may cause a dramatic decrease in contact area between the Li metal and the Li +  conducting ceramic oxide. 
     Current proposals exist to clean the surface of Li +  conducting ceramic oxides such as LLZO of surface contamination. Several surface conditioning protocols have been proposed to decontaminate the LLZO surface. One conditioning protocol is dry polishing (DP) and another conditioning protocol is wet polishing (WP). DP can include dry polishing LLZO manually with sand paper at a grit size. The grit size can be any one of the following values or within the range of any two of the following values: 400, 600 and 1200. WP can include wet polishing LLZO with a glycol-based polishing liquid using an automated polisher with diamond polishing abrasives. After this step, the LLZO is washed with alcohol to remove residual polishing fluid from the surface. However, it is not possible to use these WP and DP processes in a relatively thin (e.g., 10 to 40 μm) Li+ conducting ceramic oxides because these processes would damage the oxide material. Post heat treatments (e.g., at a temperature in a range of 400 to 700° C.) may also be used to decompose surface contaminants. However, in many situations, the surface contaminant layer simply reforms during cooling. As another drawback, these treatments are also energy intensive. As another proposal, a surface modification or coating using Au or Al 2 O 3  has been attempted. Another proposal is reacting LLZO with carbon at 700° C. However, these processes are not scalable and add additional processing steps. Additionally, if the coating does not maintain integrity upon cycling, it might compromise the cycle life. 
     Yet, in view of these challenges, much work continues to be conducted in the area of SSE systems exhibiting Li +  conductivity greater than 10 mScm −1  at room temperature to implement lithium metal anodes in high energy and high power density batteries. However, many fundamental issues and significant engineering challenges remain to realize the potential of these applications, especially in the area of electrochemical interfaces. Surface chemistry of a Li +  conducting ceramic oxide of a SSE controls the interfacial resistance and Li wettability. Typically, in SSBs, lower interfacial resistance relative to liquid electrolytes is obtained by a complicated surface modification or using a laborious post sintering process or mechanical grinding. What is needed is a processing method that significantly reduces the interfacial resistance between Li +  conducting ceramic oxide and Li metal by removing surface contaminants. 
     In one or more embodiments, a method is disclosed to reduce interfacial resistance between a Li +  conducting ceramic oxide layer and Li metal. Moreover, a ceramic oxide material having a surface with reduced interfacial resistance is disclosed. These methods and materials may increase the Li wettability and achieve lower interfacial resistance between Li and a ceramic oxide layer such as LLZO. In one aspect, wettability may be measured by a contacting angle of wetting of molten Li on the Li +  conducting ceramic oxide, such as LLZO. An acceptable wettability may be indicated by one of the following contact angles or within a range of any two of the following contact angles: 40°, 50°, 60°, 70°, 80°, 90° and 100°. In one aspect, interfacial resistance may be determined by electrochemical impedance spectroscopy. An acceptable lower interfacial resistance may be any one of the following or in the range of any two of the following: 0, 5, 10, 15 and 20 Ohm cm 2 . 
       FIG. 1  is a schematic diagram of a SSB  10  according to one embodiment. SSB  10  includes cathode  12 , electrolyte  14 , anode  16 , negative current collector  18  and positive current collector  20 . Electrolyte  14  is configured to function as both an ionic conductor and separator. Cathode  12  and anode  16  contact opposing surfaces of electrolyte  14 . Negative current collector  18  contacts the surface of anode  16  opposing the surface of anode  16  contacting electrolyte  14 . Positive current collector  18  contacts the surface of cathode  12  opposing the surface of cathode  12  contacting electrolyte  14 . SSB  10  is connected to electric load  22  through conductors  24  and  26 . Conductor  24  connects negative current collector  18  to electric load  22 . Conductor  26  connects positive current collector  20  to electric load  22 . 
     Anode  16  may be formed of an Li metal. Other non-limiting materials that can be used as anode  16  includes carbon, titanates and lithium alloys. Electrolyte  14  may be formed of an Li +  conducting ceramic oxide such as LLZO. Other non-limiting examples of Li +  conducting ceramic oxides include Li 5 La 3 Ta 2 O 12  (LLTO), Li 6 La 2 CaTa 2 O 12  (LLCTO), Li 6 La 2 ANb 2 O 12  (A=Ca, Sr), Li 1+x Al x Ge 2-x (PO 4 ) 3  (LAGP), Li 14 Al 0.4 (Ge 2-x Ti x ) 1.6 (PO 4 ) 3  (LAGTP), perovskite Li 3x La 2/3-x TiO 3  (LLTO), Li 0.8 La 0.6 Zr 2 (PO 4 ) 3  (LLZP), Li 1+x Ti 2-x Al x (PO 4 ) 3  (LTAP), Li 1+x+y Ti 2-x Al x Si y (PO 4 ) 3-y  (LTASP), LiTi x Zr 2-x (PO 4 ) 3  (LTZP), Li 2 Nd 3 TeSbO 12  and mixtures thereof. Cathode  12  may be formed of an Li-based oxide material such as lithium cobalt oxide (LiCoO 2 ) (LCO), lithium manganese oxide (LiMn 2 O 4 ) (LMO), lithium nickel manganese cobalt oxide (LiNiMnCoO 2 ) (NMC), lithium iron phosphate (LiFePO 4 ) (LIP), lithium nickel cobalt aluminum oxide (LiNiCoAlO 2 ) (NCA), lithium titanate (Li 4 Ti 5 O 12 ) (LT), and mixtures thereof. Cathode  12  may have a crystal lattice structure. Negative current collector  18  may be formed of an elemental or alloy metal material, such as copper or copper alloy. Positive current collector  18  may be formed of an elemental or alloy material, such as aluminum of aluminum alloy. 
     During charging of SSB  10 , Li ions de-intercalate from the crystal lattice structure of cathode  12  and transfer to anode  16  via the ionic conductive solid electrolyte  14 , while the electrons transfer to anode  16  via external circuit  28 , which includes conductors  24  and  26  and electric load  22 . During discharging, as shown in  FIG. 1 , Li ions de-intercalate from anode  16  and transfer to cathode  12  via solid electrolyte  14  while electrons are passed through external circuit  28  and drive electric load  22  to work. Several reaction steps are involved at the interface between electrolyte  14  and cathode  12  and electrolyte  14  and anode  16 . First, Li ions diffuse in electrolyte  14 . Second, the Li ions are adsorbed on the surface of either cathode  12  or anode  16 . Third, a charge is transferred. Fourth, intercalation into either cathode  12  or anode  16  occurs. Fifth, Li ions diffuse into either cathode  12  or anode  16 . Also, surface reactions take place between electrolyte  14  and cathode  12  and electrolyte  14  and anode  16 . 
     In one or more embodiments, a method for removing surface contamination from a Li +  conducting ceramic oxide such as LLZO used as an SSE in an SSB is disclosed.  FIG. 2  is a schematic diagram of method steps for removing surface contamination  29  from Li +  conducting ceramic oxide powder material  34  and thin film material  36  according to one embodiment. The Li +  conducting ceramic oxide powder material  34  may be spherical particles having a diameter one of the following values or within a range of any two of the following values: 400, 450, 500, 550 and 600 nm. 
     The thickness of surface contamination materials on the Li +  conducting ceramic oxide powder material  34  before the soaking step  30  may be one of the following values or within a range of any two of the following values: 50, 55, 60, 65 and 70 nm in a surface region of the Li +  conducting ceramic oxide powder material  34 . The thickness of surface contamination materials on the Li +  conducting ceramic oxide thin film material  36  before the soaking step  32  may be one of the following values or within a range of any two of the following values: 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 200 nm and 2 μm nm in a surface region of thin film material  36 . In one embodiment, a planar 40 μm LLZO film would have the following amounts by weight of Li 2 CO 3  surface contamination based on the thickness of Li 2 CO 3  surface contamination: 0.2 wt % (200 nm) and 2 wt % (2 μm). 
     In one embodiment, the method includes a first step of soaking the Li +  conducting ceramic oxide material in an organic solvent with a salt for a pre-determined amount of time at a pre-determined temperature, as shown by arrow  30  and  32  on  FIG. 2 . The Li +  conducting ceramic oxide material may be soaked in different forms, including, but not limited to, powder form  34  or thin film form  36 , where the thin film is shaped as used in an SSB. The thickness of the thin film may be any one of the following values or within a range of any two of the following values: 20, 30, 40, 50 and 60 μm. Non-limiting examples of organic solvents that can be used in one or more embodiments include tetrahydrofuran (THF) or 1,3-dioxolane (DOL), dimethoxy ethane (DME), tetra(ethylene glycol)dimethyl ether (TEGDME), Ethylene carbonate (EC), Propylene carbonate (PC), Dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), ethyl propyl ether (EPE), Diethyl carbonate (DEC), fluorinated cyclic carbonate (F-AEC), fluorinated linear carbonate (F-EMC), fluorinated ether (F-EPE), THF, glymes and mixtures thereof. Non-limiting examples of salts that can be used in one or more embodiments include LiBF 4 , LiPF 6 , LiBC 4 O 8  (LiBOB), LiPF 3 (CF 2 CF 3 ) 3  (LiFAP), LiBr, LiCl, LiI, LiClO 4 , LiFSI, LiNO 3 , LiPO 2 F 2 , Li(CF 3 SO 2 ) 2 N (LiTFSI), LiCF 3 SO 3 , LiC(CF 3 SO 2 ) 3 , LiAsF 6 , LiN(SO 2 CF 2 CF 3 ) 2  (LiBETI) and mixtures thereof. The concentration of salt in the organic solvent may be any one of the following values or within a range of any two of the following values: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1 and 1.2 M. The pre-determined amount of time may be any one of the following values or within a range of any two of the following values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 hours. The pre-determined temperature may be any one of the following values or within a range of any two of the following values: 20, 30, 40, 50 and 60° C. 
     In one embodiment, the method includes a second step of rinsing the Li +  conducting ceramic oxide material in the same organic solvent as the first step or a different organic solvent for a pre-determined amount of time. Non-limiting examples of organic solvents that can be used in one or more embodiments include tetrahydrofuran (THF), 1,3-dioxolane (DOL), dimethoxy ethane (DME), tetra(ethylene glycol)dimethyl ether (TEGDME), Ethylene carbonate (EC), Propylene carbonate (PC), Dimethyl carbonate (DMC), Ethyl methyl carbonate (EMC), ethyl propyl ether (EPE), Diethyl carbonate (DEC), fluorinated cyclic carbonate (F-AEC), fluorinated linear carbonate (F-EMC), fluorinated ether (F-EPE), THF, glymes and a mixture thereof. The pre-determined amount of time may be any one of the following values or within a range of any two of the following values: 5, 10, 15, 20, 25 and 30 minutes. Li +  conducting ceramic oxide powder material  34  and thin film material  36  may be placed in compartment  38  and  40 , respectively, for the rinsing step. 
     In one embodiment, the method includes a third step of drying the Li +  conducting ceramic oxide material after the soaking and rinsing steps. For example, the Li +  conducting ceramic oxide material may be dried in vacuum conditions for a pre-determined amount of time. The pre-determined amount of time may be any one of the following values or within a range of any two of the following values: 60, 70, 80, 90, 100, 110 and 120 minutes. Li +  conducting ceramic oxide powder material  34  and thin film material  36  may be placed in compartment  38  or  40 , respectively, for the drying step. Compartments  38  and  40  may be held under vacuum conditions. 
     After the rinsing and drying steps  42  and  44  for Li +  conducting ceramic oxide powder material  34  and thin film material  36 , respectively, these materials are decontaminated from surface contamination. The thickness of surface contamination materials on the Li +  conducting ceramic oxide powder material  34  after drying step  42  may be one of the following values or within a range of any two of the following values: 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 3.0, 4.0, 5.0 and 20.0 nm in a surface region of the Li +  conducting ceramic oxide powder material  34 . The thickness of surface contamination materials on the Li +  conducting ceramic oxide thin film material  36  after drying step  42  may be one of the following values or within a range of any two of the following values: 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 3.0, 4.0, 5.0 and 20.0 nm in a surface region of thin film material  36 . In one embodiment, a planar 40 μm LLZO film would have the following amount by weight of Li 2 CO 3  surface contamination based on the thickness of Li 2 CO 3  surface contamination: 2.1×10 −3  wt % (2 nm) and 0.02 wt % (20 nm). In one embodiment, a spherical 500 nm diameter LLZO particle would have the following amount by weight of Li 2 CO 3  surface contamination based on the thickness of Li 2 CO 3  surface contamination: 0.47 wt % (2 nm) and 5.16 wt % (20 nm). 
       FIGS. 3A, 3B, 3C and 3D  show graphs  50 ,  100 ,  150  and  200  of soft x-ray absorption spectroscopy (XAS) spectrums of LLZO powder under different conditions. As described below, these soft XAS spectral graphs demonstrate that LLZO powder treated with process disclosed in one or more embodiments significantly reduces the presence of surface contaminants (e.g., Li 2 CO 3 ). 
     Graph  50  depicts O K-edge (5 nm) spectra by plotting intensity (a.u) as a function of energy (eV) for LLZO powder under different conditions. Plot  52  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in a dry room for six (6) months. Plot  54  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in ambient air for three (3) days. Plot  56  depicts intensity (a.u) as a function of energy (eV) for LLZO powder that was treated using a treatment process of one embodiment in which the LLZO powder is soaked in a solution of ethylene carbonate and dimethyl carbonate with a LiBF 4  salt for 16 hours after air exposure for three (3) days. Plot  58  depicts intensity (a.u) as a function of energy (eV) for pure Li 2 CO 3  for comparison to plots  52 ,  54  and  56 . A decrease in intensity (a.u) as a function of energy (eV) is a result of carbonate removal from the LLZO powder. In region  60  of graph  50  at about 539 eV, the pure Li 2 CO 3  plot  58  has the highest intensity peak  64 , which is similar to the peak of the LLZO stored in air for three days, plot  54 . The treated LLZO powder plot  56  has the lowest intensity peak  66  (in terms of the height of the peak compared to a baseline). In region  62  of graph  50  at about 543 eV, the pure Li 2 CO 3  plot  58  has the highest intensity peak  68  while the treated LLZO powder plot  56  has a relatively lower intensity peak. These decreases in relative intensity support that carbonate contamination on the treated LLZO powder is significantly reduced by the treatment method, as opposed to the carbonate layer formed on the surface of the LLZO powder according to plots  52  and  54 . 
     Graph  100  depicts O K-edge (50 nm) spectra by plotting intensity (a.u) as a function of energy (eV) for LLZO powder under different conditions. Plot  102  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in a dry room for six (6) months. Plot  104  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in ambient air for three (3) days. Plot  106  depicts intensity (a.u) as a function of energy (eV) for LLZO powder that was treated using the treatment process identified in connection with the example shown in  FIG. 3A  after air exposure for three (3) days. Plot  108  depicts intensity (a.u) as a function of energy (eV) for pure Li 2 CO 3  for comparison to plots  102 ,  104  and  106 . The peaks marked with arrows pointing downward decrease when the sample is treated according to one or more embodiments. These peaks are associated with Li 2 CO 3 , as shown by the reference measurement with Li 2 CO 3  only. Accordingly, the treatment according to one or more embodiments removes Li 2 CO 3 . 
     Graph  150  depicts La M-edge (5 nm) spectra by plotting intensity (a.u) as a function of energy (eV) for LLZO powder under different conditions. Plot  152  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in a dry room for six (6) months. Plot  154  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in ambient air for three (3) days. Plot  156  depicts intensity (a.u) as a function of energy (eV) for LLZO powder that was treated using a treatment process identified in connection with the example shown in  FIG. 3A  after air exposure for three (3) days. In region  158  of graph  150  at about 851 eV, peak  160  of the LLZO powder stored in air for three (3) days plot  154  and peak  162  of the LLZO powder stored in a dry room plot  152  each have a different peak than peak  164  of the treated LLZO powder plot  156  by at least 0.7 a.u. This change supports that carbonate formation on the treated LLZO powder is significantly decreased by the treatment method of one or more embodiments. 
     Graph  200  depicts C K-edge (5 nm) spectra by plotting intensity (a.u) as a function of energy (eV) for LLZO powder under different conditions. Plot  202  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in a dry room for six (6) months. Plot  204  depicts intensity (a.u) as a function of energy (eV) for LLZO powder stored in ambient air for three (3) days. Plot  206  depicts intensity (a.u) as a function of energy (eV) for LLZO powder that was treated using a treatment process identified in connection with the example shown in  FIG. 3A  after air exposure for three (3) days. Plot  208  depicts intensity (a.u) as a function of energy (eV) for pure Li 2 CO 3  for comparison to plots  202 ,  204  and  206 . The peaks decrease when the sample is treated according to one or more embodiments. These peaks are associated with Li 2 CO 3 , as shown by the reference measurement with Li 2 CO 3  only. Accordingly, the treatment according to one or more embodiments removes Li 2 CO 3 . 
     In further examples, the electrochemical cycling stability and interfacial resistance of an LLZO pellet with and without the treatment process of the examples in connection with  FIGS. 3A to 3D  was tested using a lithium plating and stripping process and electrochemical impedance spectroscopy (EIS). In one example, an LLZO pellet was a cylindrical pellet with a thickness of 0.2 cm with an electrode area of 11.3 cm 2 . An EIS testing method was used to measure the contribution to impedance of a washed and unwashed pellet of LLZO at room temperature. The results of this test are shown in  FIG. 4 .  FIG. 4  depict representative Nyquist plots for Li/LLZO/Li cells at room temperature before and after treatment. Graph  250  of  FIG. 4  plots −lm (Z) Ohm as a function of Re (Z) (Ohm) for a dry room plot  252  and a treated plot  254 . As shown in  FIG. 4 , treated pellets showed 6.5 times lower impedance in interfacial and bulk regions as compared to the untreated samples. The reduction of impendence may be one of the following values or within a range of any two of the following values: 6, 8, 10, 12, 14, 16, 18, 20 and 22 times. The reduction in total impedance is at least partially attributed to the removal of surface contaminants (e.g., Li 2 CO 3 ) during the treatment. 
     As a benefit of the treatment process of one or more embodiments, the conformal contact of Li metal on the LLZO surface increases, thereby increasing the effective ionic transfer area and transport of ions between LLZO and Li. Direct current lithium plating and stripping experiments were carried out to assess the impendence and Li ion transport capability across the LLZO and Li metal interface.  FIG. 5  depicts a graph of galvanostic cycling of Li/LLZO/Li cells at room temperature with a current density of 1.4 μAcm −2  before and after treatment. At a current density of 1.4 μAcm −2  for 75 hours, the treated pellets stabilized at about 0.03 volts as shown in region  302 , whereas the untreated samples exhibited a noisy potential response with large voltage polarization as shown in regions  304  and  306 , which demonstrates uneven ion transport through the interface. The treatment process of one or more embodiments drastically reduces contamination to minimize or eliminate large interfacial impedance between LLZO (and other lithium conducting ceramic oxides) and Li in SSBs. 
     While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms encompassed by the claims. The words used in the specification are words of description rather than limitation, and it is understood that various changes can be made without departing from the spirit and scope of the disclosure. As previously described, the features of various embodiments can be combined to form further embodiments of the invention that may not be explicitly described or illustrated. While various embodiments could have been described as providing advantages or being preferred over other embodiments or prior art implementations with respect to one or more desired characteristics, those of ordinary skill in the art recognize that one or more features or characteristics can be compromised to achieve desired overall system attributes, which depend on the specific application and implementation. These attributes can include, but are not limited to cost, strength, durability, life cycle cost, marketability, appearance, packaging, size, serviceability, weight, manufacturability, ease of assembly, etc. As such, to the extent any embodiments are described as less desirable than other embodiments or prior art implementations with respect to one or more characteristics, these embodiments are not outside the scope of the disclosure and can be desirable for particular applications.