Source: http://www.google.fr/patents/US8652686
Timestamp: 2018-01-22 02:48:28
Document Index: 548342089

Matched Legal Cases: ['Application No. 60', 'art 1', 'application No. 2003301383', 'application No. 2003301383', 'application No. 2004306866', 'application No. 2004306866', 'application No. 2004316638', 'application No. 2006280097', 'art 1', 'application No. 2', 'application No. 2', 'application No. 2', 'application No. 2', 'application No. 2', 'application No. 2003801061464', 'application No. 200480037293', 'application No. 200480037293', 'application No. 200480037293', 'application No. 200480042697', 'application No. 200480042697', 'application No. 200480042697', 'application No. 200910174918', 'application No. 200980131906', 'application No. 03809186', 'application No. 03809186', 'application No. 03809186', 'application No. 04794655', 'application No. 04794699', 'application No. 04794699', 'application No. 04794699', 'application No. 2004', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2006', 'application No. 2011', 'application No. 10', 'application No. 10', 'application No. 10', 'application No. 10', 'application No. 2005', 'application No. 2006', 'application No. 9', 'application No. 9', 'application No. 2010']

Brevet US8652686 - Substantially impervious lithium super ion conducting membranes - Google Brevets
A composite solid electrolyte includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte. In this way a solid electrolyte produced by any process that...http://www.google.fr/patents/US8652686?utm_source=gb-gplus-shareBrevet US8652686 - Substantially impervious lithium super ion conducting membranes
Numéro de publication US8652686 B2
Numéro de demande US 13/673,789
Autre référence de publication US8182943, US8334075, US20070172739, US20120270112, US20130344397, WO2007075867A2, WO2007075867A3
Numéro de publication 13673789, 673789, US 8652686 B2, US 8652686B2, US-B2-8652686, US8652686 B2, US8652686B2
Inventeurs Steven J. Visco, Lutgard C. De Jonghe, Yevgeniy S. Nimon
Cessionnaire d'origine Polyplus Battery Company
Citations de brevets (201), Citations hors brevets (192), Référencé par (13), Classifications (67), Événements juridiques (1)
US 8652686 B2
A composite solid electrolyte includes a monolithic solid electrolyte base component that is a continuous matrix of an inorganic active metal ion conductor and a filler component used to eliminate through porosity in the solid electrolyte. In this way a solid electrolyte produced by any process that yields residual through porosity can be modified by the incorporation of a filler to form a substantially impervious composite solid electrolyte and eliminate through porosity in the base component. Methods of making the composites are also disclosed. The composites are generally useful in electrochemical cell structures such as battery cells and in particular protected active metal anodes, particularly lithium anodes, that are protected with a protective membrane architecture incorporating the composite solid electrolyte. The protective architecture prevents the active metal of the anode from deleterious reaction with the environment on the other (cathode) side of the architecture, which may include aqueous, air and organic liquid electrolytes and/or electrochemically active materials.
1. A composite active metal ion conducting solid electrolyte membrane, comprising:
an inorganic monolithic active metal ion conducting base component comprising a continuous inorganic solid electrolyte matrix having through pores that extend from one major surface of the base component to the opposing major surface, and a filler component contained in the through pores of the base component;
wherein the active metal ion conductivity of the composite is within the same order of magnitude as the active metal ion conductivity of the base component matrix.
2. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conductivity of the composite is not less than half the active metal ion conductivity of the base component.
3. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the density of the active metal ion conducting base component is greater than 75% and less than 95% of the theoretical density of the base component material.
4. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the density of the active metal ion conducting base component is greater than 95% of the theoretical density of the base component material.
5. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the filler component is a conductor of the active metal ion.
6. The composite active metal ion conducting solid electrolyte membrane of claim 5, wherein the conductive filler component is a polymer electrolyte.
7. The composite active metal ion conducting solid electrolyte membrane of claim 6, wherein the polymer electrolyte comprising a polymer and an active metal salt.
8. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises polyethylene oxide (PEO).
9. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises crosslinked PEO.
10. The composite active metal ion conducting solid electrolyte membrane of claim 7, wherein the polymer comprises amorphous PEO.
11. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conducting filler component is an active metal ion conducting glass-ceramic.
12. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion conducting filler component is an active metal ion conducting glass.
13. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a glass.
14. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a glass-ceramic.
15. The composite active metal ion conducting solid electrolyte membrane of claim 14, wherein the density of the active metal ion conducting base component is greater than 95% of the theoretical density of the base component material.
16. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a glass-ceramic and the active metal ion conductive filler component is a polymer electrolyte.
17. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the inorganic base component is a ceramic and the active metal ion conductive filler component is a polymer electrolyte.
18. The composite active metal ion conducting solid electrolyte membrane of claim 1, wherein the active metal ion is lithium.
19. A protected anode, comprising:
a protective membrane architecture on at least the first surface of the anode, the architecture having ionic conductivity of the active metal of at least 10−6 S/cm; and
wherein the protective membrane architecture comprises a substantially impervious composite solid electrolyte membrane according to claim 1.
20. A battery cell, comprising:
a protected anode in accordance with claim 19; and
This application is a continuation of prior U.S. application Ser. No. 13/453,964 filed on Apr. 23, 2012, titled SUBSTANTIALLY IMPERVIOUS LITHIUM SUPER ION CONDUCTING MEMBRANES now pending, which is a continuation of U.S. application Ser. No. 11/612,741 filed on Dec. 19, 2006, titled COMPOSITE SOLID ELECTROLYTE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES, now issued as U.S. Pat. No. 8,182,943, which in turn claims priority from U.S. Provisional Application No. 60/752,255 filed Dec. 19, 2005, titled COMPOSITE SOLID ELECTROLYTE MEMBRANES FOR PROTECTION OF ACTIVE METAL ANODES, the disclosures of which are incorporated by reference herein.
Suitable solid electrolyte base component materials include glassy or amorphous metal ion conductors, such as a phosphorus-based glass, oxide-based glass, sulpher-based glass, oxide/sulfide based glass, selenide based glass, gallium based glass, germanium-based glass, Nasiglass or boracite glass (such as are described D. P. Button et al., Solid State Ionics, Vols. 9-10, Part 1, 585-592 (December 1983); ceramic active metal ion conductors, such as lithium beta-alumina, sodium beta-alumina, Na superionic conductor (NASICON), and Li superionic conductor (LISICON) and the like; as well as glass ceramic active metal ion conductors. Specific examples include, Li3PO4.Li2S.SiS2, Li2S.GeS2.Ga2S3, Li2O.11Al2O3, Na2O.11Al2O3, (Na,Li)1+xTi2−xAlx(PO4)3 (0.0≦x≦0.9) and crystallographically related structures, Na3Zr2Si2PO12, Li3Zr2Si2P3O12, Na5ZrP3O12, Na5TiP3O12, Na3Fe2P3O12, Na4NbP3O12, Na-Silicates, Li0.3La0.7TiO3, Na5MSi4O12 (M: rare earth such as Nd, Gd, Dy) Li5ZrP3O12, Li5TiP3O12, Li3Fe2P3O12, Li4NbP3O12, Li5La3Ta2O12, Li5La3Nb2O12 and combinations thereof, optionally sintered or melted. Suitable ceramic ion alkali metal ion conductors are described, for example, in U.S. Pat. No. 4,985,317 to Adachi et al., incorporated by reference herein in its entirety and for all purposes.
and contains a predominant crystalline phase composed of Li1+x(M,Al,G)x(Ge1−yTiy)2−x(PO4)3 where x≦0.8 and 0≦y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or Li1+x+yQxTi2−xSiyP3−yO12 where 0<x≦0.4 and 0<y≦0.6, and where Q is Al or Ga.
In another preferred embodiment, the solid electrolyte base component comprises a ceramic or glass-ceramic solid electrolyte material based on lithium hafnium phosphate. Such solid electrolytes according to current invention include compounds with a general formula of Li1+xM2−xMxHf2−x(PO4)3, where M is Cr, In, Fe, Ta, Sc, Lu or Y, and where 0<x≦0.5.
In one embodiment the filler component comprises a polymer non-conductive to metal ions. Suitable non-conductive polymeric filler materials include polyisobutylene, epoxy, polyethylene, polypropylene, polytetrafluoroethylene and combinations thereof.
FIG. 1A-B illustrates a top down (A) and cross sectional (B) view of a schematic drawing (not drawn to scale) of a composite solid electrolyte in accordance with the instant invention.
FIG. 3A-C illustrate various alternative configurations of a protected anode and its corresponding protective membrane architecture incorporating a composite solid electrolyte in accordance with the present invention.
The composite solid electrolyte of the instant invention is now described in more detail with reference to FIG. 1A-B and specific embodiments.
Referring to FIG. 1A-B, there is provided a schematic illustration of a composite solid electrolyte in accordance with the present invention. The figures are not drawn to scale in order not to obscure important features. FIG. 1A shows the composite 101 in a top down view and FIG. 1B shows the composite in cross-section. The composite 101 is composed of a highly ionically conductive monolithic solid electrolyte base component 103, filled with a filler component 105 that may or may not be highly ionically conductive. The filler component 105 effectively closes through-pores eliminating through-porosity residual from the manufacturing of the base component 103 to form a composite that is substantially impervious to fluids.
and contains a predominant crystalline phase composed of Li1+x(M,Al,Ga)x(Ge1−yTiy)2−x(PO4)3 where x≦0.8 and 0≦y≦1.0, and where M is an element selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/or Li1+x+yQxTi2−xSiyP3−yO12 where 0<x≦0.4 and 0<y≦0.6, and where Q is Al or Ga.
In one embodiment the composite comprises an organic polymer filler component that is not conductive to metal ions. Suitable non-conductive organic polymer filler material include polyisobutylene, epoxy, polyethylene, polypropylene, polytetrafluoroethylene and combinations thereof.
The separator layer 316 is composed of a semi-permeable membrane impregnated with an organic anolyte. For example, the semi-permeable membrane may be a micro-porous polymer, such as are available from Celgard, Inc. The organic anolyte may be in the liquid or gel phase. For example, the anolyte may include a solvent selected from the group consisting of organic carbonates, ethers, lactones, sulfones, etc, and combinations thereof, such as EC, PC, DEC, DMC, EMC, 1,2-DME or higher glymes, THF, 2MeTHF, sulfolane, and combinations thereof. 1,3-dioxolane may also be used as an anolyte solvent, particularly but not necessarily when used to enhance the safety of a cell incorporating the structure, as described further below. When the anolyte is in the gel phase, gelling agents such as polyvinylidine fluoride (PVdF) compounds, hexafluoropropylene-vinylidene fluoride copolymers (PVdf-HFP), polyacrylonitrile compounds, cross-linked polyether compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and combinations and the like may be added to gel the solvents. Suitable anolytes will also, of course, also include active metal salts, such as, in the case of lithium, for example, LiPF6, LiBF4, LiAsF6, LiSO3CF3 or LiN(SO2C2F5)2. One example of a suitable separator layer is 1 M LiPF6 dissolved in propylene carbonate and impregnated in a Celgard microporous polymer membrane.
Generally, the solid state protective membrane architectures (described with reference to FIG. 3C) are a laminate composed of at least two layers having different chemical compatibility requirements, one chemically compatible with the anode and the other chemically compatible with the cathode environment; generally ambient air, and/or battery cathoytes. Referring to the protected anode embodiment and its corresponding protective membrane architecture depicted in FIG. 3C the protective membrane architecture is laminate having a first and second material layer. The first material layer (or first layer material) of the architecture is ionically conductive, and chemically compatible with an alkali metal anode. Chemical compatibility in this aspect of the invention refers both to a material that is chemically stable and therefore substantially unreactive when contacted with an alkali metal anode. It may also refer to a material that is chemically stable with air, to facilitate storage and handling, and reactive when contacted with an alkali metal anode to produce a product that is chemically stable against the alkali metal anode and has the desirable ionic conductivity (i.e., a first layer material). Such a reactive material is sometimes referred to as a “precursor” material. The second material layer of the composite is substantially impervious, ionically conductive and chemically compatible with the first material. Additional layers are possible to achieve these aims, or otherwise enhance electrode stability or performance. All layers of the composite have high ionic conductivity, at least 10−7S/cm, generally at least 10−6 S/cm, for example at least 10−5S/cm to 10−4 S/cm, and as high as 10−3 S/cm or higher so that the overall ionic conductivity of the multi-layer protective structure is at least 10−7S/cm and as high as 10−3 S/cm or higher.
Alternatively, referring to FIG. 5, a second method 500 for forming a protected anode having fully solid-state protective membrane architecture in accordance with the present invention is shown. The ionically conductive active metal anode compatible interlayer material 540 is formed in situ following formation of a precursor layer 520 on the inventive composite solid electrolyte 502. In the particular example illustrated in the figure, a surface of the composite solid electrolyte 502 is coated 510 with red phosphorus 520, a precursor for an active metal (in this case lithium) phosphide interlayer. Then a layer of lithium metal 550 is deposited onto the phosphorus. The reaction of lithium and phosphorus forms Li3P 540 according to the following reaction: 3Li+P═Li3P. Li3P is an ionically conductive material that is chemically compatible with both the lithium anode and the composite solid electrolyte. In this way, the composite solid electrolyte is not in direct contact with the lithium electrode. Of course, other active metal, interlayer precursor materials, as described herein, may be used as well. Alternative precursor examples include CuN3, which may be formed as a thin layer on the composite solid electrolyte and contacted with a Li anode in a similar manner according to the following reaction: 3Li+CuN3═Li3N+3Cu; or lead iodide which may be formed as a thin layer on a polymer electrolyte and contacted with a Li anode in a similar manner according to the following reaction: 2Li+PbI2═2LiI+Pb.
Alternatively, high concentrations (e.g., 50 to 100 g/liter of iodine can be dissolved in an organic solvent, such as acetonitrile and n-heptane. Dissolved iodine can be coated on a composite solid electrolyte surface by such methods as dip coating, spraying or brushing, among others. In this case, treatment conditions can be easily changed by varying the length of coating treatment and iodine concentrations. Examples of iodine sources for this technique include metal iodides are AgI and PbI2, which are known to be used as the cathode materials in solid-state batteries with Li anode and LH-based solid electrolyte.
Then, lithium (or other active metal) is contacted with the polymer-iodine complex on the conductive glass (or other second layer material), for example by evaporation or pressing onto the composite solid electrolyte layer with this complex. The result is a LH-containing protective membrane architecture on the Li anode.
Li+H2O═LiOH+½H2.
Anode:Li═Li+ +e −
Cathode:e −+H2O═OH−+½H2
Li+½H2O+¼O2═LiOH
Li½O=½Li2O2
Li+½O2+NH4Cl═LiCl+NH3
Suitable aprotic solvents include nitriles (e.g., acetonitrile (AN), higher nitriles, propionitrile, succinonitrile, butyronitrile, benzonitrile), amides (e.g., formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide (DMAC), N,N-diethylacetamide, N,N,N′N′ tetraethylsulfamide, tetramethylurea (TMU), 2-pyrrolidone, N-methylpyrrolidone, N-methylpyrrolidinone), amines (e.g., butylamine, ethylenediamine, triethylamine, pyridine, 1,1,3,3-tetramethylguanidine (TMG), tetraethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine, organosulfur solvents (e.g., dimethylsulfoxide (DMSO), sulfolane, other sulfones, dimethylsulfite, ethylene sulfite, organophosphorous solvent (e.g., tributylphosphate, trimethylphosphate, hexamethylphosphoramide (HMPA)).
Cathode:HCl+M+e −=MH+Cl−
Anode reaction:Li═Li+ +e −
Cell reaction:Li+NiOOH+H2O═Ni(OH)2+LiOH
The use of protective architecture on active metal electrodes in accordance with the present invention allows the construction of active metal/water batteries that have negligible corrosion currents, described above. The Li/water battery has a very high theoretical energy density of 8450 Wh/kg. The cell reaction is Li+H2O═LiOH+½ H2. Although the hydrogen produced by the cell reaction is typically lost, in this embodiment of the present invention it is used to provide fuel for an ambient temperature fuel cell. The hydrogen produced can be either fed directly into the fuel cell or it can be used to recharge a metal hydride alloy for later use in a fuel cell. At least one company, Millenium Cell makes use of the reaction of sodium borohydride with water to produce hydrogen. However, this reaction requires the use of a catalyst, and the energy produced from the chemical reaction of NaBH4 and water is lost as heat.
Li+H2O═LiOH+½H2
To find out if the process of impregnating the ceramic membrane (base component layer) with EEM filler to form the solid electrolyte composite adversely affects its ionic conductivity, impedance of the “as received” ceramic membrane (base component), before filling the through pores, and of a solid electrolyte composite (ceramic membrane impregnated with EEM and ground from both sides) fabricated as described in Example 1, was determined. For impedance measurements, the two major surfaces of the composite and the base component were sputtered with gold films of about 1 gm in thickness. Ionic conductivity values for both the base component and the composite were calculated from the high intercepts in the complex impedance plots shown in FIGS. 7A-B, respectively. The determined value of ionic conductivity of 2.4×10−4 S/cm was the same for both the composite and the base component. Therefore, impregnation of a ceramic membrane base component with the EEM to form a composite solid electrolyte does not lead to a reduction in the conductivity of the base component layer.
Low viscosity epoxy Duralco 4460 was used for vacuum impregnation of Li-ion conductive ceramic membranes with NASICON-type structure received from OHARA Corporation and described in Example 1. An EE 4460-25 kit containing 1 jar of Duralco 4460 resin and 1 syringe of Duralco 4460 hardener was purchased from Contronics Corporation. 5 ml of the hardener and 6.4 ml of the resin were mixed using a Thinky AR-250 mixer from Thinky Corporation, Japan for 5 minutes in the mixing mode followed by 0.5 minutes in the defoaming mode. Then the membrane was impregnated with this mixture using the procedure described in Example 2. The polymer residue was removed from the membrane surfaces by grinding them with CarbiMet abrasive discs (grits 400, 800 and 1200) purchased from Buehler Ltd. Then the membrane surfaces were polished with 1 μm alumina powder (Micropolish II from Buehler Ltd.). 20-25 gm were ground off from each side of the membrane. The final thickness of the composite membrane was 250 μm.
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Classification aux États-Unis 429/231.95, 429/529, 429/465, 429/145, 429/304, 429/104, 429/249, 429/475, 429/245, 429/218.1, 429/306, 429/236
Classification internationale H01M4/133, H01M10/0561, H01M10/36, H01M4/13, H01M4/139, H01M10/0566, H01M4/131, H01M4/04, H01M4/02, H01M4/134, H01M10/052, H01M10/056
Classification coopérative Y02E60/128, H01M4/387, H01M4/38, H01M4/133, H01M6/185, H01M4/32, H01M6/04, H01M4/383, H01M2300/0068, H01M4/08, H01M6/188, H01M6/24, H01M4/86, H01M6/16, H01M12/08, H01M4/04, H01M10/0566, H01M2300/0005, H01M4/242, H01B1/122, H01M2/1673, H01M2300/0085, H01M4/13, H01M6/34, H01M4/0416, H01M6/181, H01M10/052, H01M4/131, H01M2300/0017, H01M2300/0091, H01M4/139, H01M2300/0071, H01M4/134, H01M4/62, H01M2004/027, H01M12/04, H01M10/056, H01M2300/0082, H01M2300/0065, H01M4/385, H01M12/06, H01M10/0561, H01M8/08