CA2555637A1 - Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture - Google Patents

Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture Download PDF

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CA2555637A1
CA2555637A1 CA002555637A CA2555637A CA2555637A1 CA 2555637 A1 CA2555637 A1 CA 2555637A1 CA 002555637 A CA002555637 A CA 002555637A CA 2555637 A CA2555637 A CA 2555637A CA 2555637 A1 CA2555637 A1 CA 2555637A1
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cell
active metal
group
anolyte
aqueous
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CA2555637C (en
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Steven J. Visco
Yevgeniy S. Nimon
Bruce D. Katz
Lutgard C. De Jonghe
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Polyplus Battery Co Inc
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Polyplus Battery Company
Steven J. Visco
Yevgeniy S. Nimon
Bruce D. Katz
Lutgard C. De Jonghe
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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    • H01M10/058—Construction or manufacture
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Abstract

Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.

Claims (102)

1. An electrochemical cell structure, comprising:
an anode comprising a material selected from the group consisting of active metal, active metal-ion, active metal alloying metal, and active metal intercalating material; and an ionically conductive protective architecture on a first surface of the anode, the architecture comprising, an active metal ion conducting separator layer comprising a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and a substantially impervious ionically conductive layer chemically compatible with the separator layer and with aqueous environments, and in contact with the separator layer.
2. The structure of claim 1, wherein the separator layer comprises a semi-permeable membrane impregnated with a non-aqueous anolyte.
3. The structure of claim 2, wherein the semi-permeable membrane is a micro-porous polymer.
4. The structure of claim 3, wherein the anolyte is in the liquid phase.
5. The structure of claim 4, wherein the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.
6. The structure of claim 5, wherein the anolyte comprises a solvent selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME or higher glymes, sufolane, methyl formate, methyl acetate, and combinations thereof and a supporting salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiC1O4, LiSO3CF3, LiN(CF3SO2)2 and LiN(SO2C2F5)2.
7. The structure of claim 6, wherein the anolyte further comprises 1,3-dioxolane.
8. The structure of claim 3, wherein the anolyte is in the gel phase.
9. The structure of claim 8, wherein the anolyte comprises a gelling agent selected from the group consisting of PVdF, PVdF-HFP copolymer, PAN, and PEO and mixtures thereof; a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and mixtures thereof; and a Li salt selected from the group consiting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSO3CF3, LiN(CF3SO2)2 and LiN(SO2C2F5)2.
10. The structure of any preceding claim, wherein the substantially impervious sonically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.
11. The structure of any preceding claim, wherein the active metal is lithium.
12. The structure of any preceding claim, wherein substantially impervious sonically conductive layer is an ion conductive glass-ceramic having the following composition:
and containing a predominant crystalline phase composed of Li1+x(M,A1,Ga)x(Ge 1-y Ti y)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 and Li1+x+y Q x Ti2-x Si y P3-y O12 where 0< X<= 0.4 and 0< Y<= 0.6, and where Q is A1 or Ga.
13. The structure of any preceding claim, wherein the substantially impervious sonically conductive layer has an ionic conductivity of at least 10-5S/cm.
14. The structure of any preceding claim, wherein non-aqueous electrolyte separator layer has an ionic conductivity of at least 10-5S/cm.
15. The structure of any preceding claim, wherein the anode comprises active metal.
16. The structure of any preceding claim, wherein the anode comprises active metal-ions.
17. The structure of any preceding claim, wherein the anode comprises active metal alloying metal.
18. The structure of claim 17, wherein the active metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.
19. The structure of any preceding claim, wherein the anode comprises active metal intercalating material.
20. The structure of claim 19, wherein the active metal intercalating material comprises carbon.
21. A battery cell, comprising:
an active metal anode;
a cathode structure; and an ionically conductive protective architecture on a first surface of the anode, the architecture comprising, an active metal ion conducting separator layer comprising a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and a substantially impervious ionically conductive layer chemically compatible with the separator layer and the cathode structure, and in contact with the cathode structure.
22. The cell of claim 21, wherein the separator layer comprises a semi-permeable membrane impregnated with a non-aqueous anolyte.
23. The cell of claim 22, wherein the semi-permeable membrane is a micro-porous polymer.
24. The cell of claim 23, wherein the anolyte is in the liquid phase.
25. The cell of claim 24, wherein the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.
26. The cell of claim 25, wherein the anolyte comprises a solvent selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME or higher glymes, sufolane, methyl formate, methyl acetate, and combinations thereof and a supporting salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSO3CF3, LiN(CF3SO2)2 and LiN(SO2C2F5)2.
27. The cell of claim 26, wherein the anolyte further comprises 1,3-dioxolane.
28. The cell of claim 23, wherein the anolyte is in the gel phase.
29. The cell of claim 28, wherein the anolyte comprises a gelling agent selected from the group consisting of PVdF, PVdF-HFP copolymer, PAN, and PEO and mixtures thereof; a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and mixtures thereof; and a Li salt selected from the group consiting of LiPF6, LiBF4, LiAsF6, LiC1O4, LiSO3CF3, LiN(CF3SO2)2 and LiN(SO2C2F5)2.
30. The cell of claim 21, wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.
31. The cell of claim 30, wherein the active metal is lithium.
32. The cell of claim 31, wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:
Composition ~mol P2O5 ~~26-55 %
SiO2 ~~0-15%
GeO2 + TiO2 ~25-50%
in which GeO2 ~0-50%
TiO2 ~~0-50%
ZrO2 ~~0-10%
M2O3 ~~0 < 10%
A12O3 ~~0-15%
Ga2O3 ~~0-15%

Li2O ~3-25%

and containing a predominant crystalline phase composed of Li1+x(M,Al,Ga)x(Ge 1-y Ti y)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 and Li1+x+y Q x Ti2-x Si y P3-y O12 where 0< X<= 0.4 and 0< Y<= 0.6, and where Q is A1 or Ga.
33. The cell of claim 21, wherein the substantially impervious ionically conductive layer has an ionic conductivity of at least 10-5S/cm.
34. The cell of claim 21, wherein non-aqueous electrolyte separator layer has an ionic conductivity of at least 10-5S/cm.
35. The cell of claim 21, wherein the anode comprises active metal.
36. The cell of claim 21, wherein the anode comprises active metal-ions.
37. The cell of claim 21, wherein the anode comprises active metal alloying metal.
38 The cell of claim 37, wherein the active metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.
39. The cell of claim 21, wherein the anode comprises active metal intercalating material.
40. The cell of claim 39, wherein the active metal intercalating material comprises carbon.
41. The cell of claim 21, wherein the cathode structure comprises an electronically conductive component, an ionically conductive component, and an electrochemically active component, wherein at least one cathode structure component comprises an aqueous constituent.
42. The cell of claim 41, wherein the cathode structure comprises an aqueous electrochemically active component.
43. The cell of claim 42, wherein the aqueous electrochemically active component is water.
44. The cell of claim 42, wherein the aqueous electrochemically active component comprises a water soluble oxidant selected from the group consisting of gaseous, liquid and solid oxidants and combinations thereof.
45. The cell of claim 44, wherein the water soluble gaseous oxidants are selected from the group consisting of O2, SO2 and NO2, and the water soluble solid oxidants are selected from the group consisting of NaNO2, KNO2, Na2SO3 and K2SO3.
46. The cell of claim 44, wherein the water soluble oxidant is a peroxide.
47. The cell of claim 46, wherein the water soluble oxidant is hydrogen peroxide.
48. The cell of claim 41, wherein the ionically conductive component and the electrochemically active component are comprised of an aqueous electrolyte.
49. The cell of claim 48, wherein the aqueous electrolyte is selected from the group consisting of strong acid solutions, weak acid solutions, basic solutions, neutral solutions, amphoteric solutions, peroxide solutions and combinations thereof.
50. The cell of claim 48, wherein the aqueous electrolyte comprises members selected from the group consisting of aqueous solutions of HCl, H2SO4, H3PO4 acetic acid/Li acetate, LiOH; sea water, LiCl, LiBr, LiI, NH4Cl, NH4Br and hydrogen peroxide, and combinations thereof.
51. The cell of claim 50, wherein the aqueous electrolyte is sea water.
52. The cell of claim 10, wherein the aqueous electrolyte comprises sea water and hydrogen peroxide.
53. The cell of claim 50, wherein the aqueous electrolyte comprises an acidic peroxide solution.
54. The cell of claim 50, wherein hydrogen peroxide dissolved in aqueous electrolyte flowing through the cell.
55. The cell of claim 41, wherein the cathode structure electronically conductive component is a porous catalytic support.
56. The cell of claim 55, wherein the porous catalytic electronically conductive support comprises nickel.
57. The cell of claim 55, wherein the porous catalytic electronically conductive support is treated with an ionomer.
58. The cell of claim 42, wherein the cathode structure electrochemically active material comprises air.
59. The cell of claim 58, wherein the air comprises moisture.~
60. The cell of claim 59, wherein the ionically conductive material comprises an aqueous constituent.
61. The cell of claim 60, wherein the ionically conductive material further comprises an ionomer.
62. The cell of claim 61, wherein the ionically conductive material comprises a neutral or acidic aqueous electrolyte.
63. The cell of claim 62, wherein the aqueous electrolyte comprises LiCl.
64. The cell of claim 62, wherein the aqueous electrolyte comprises one of NH4Cl, and HCI.
65. The cell of claim 41, wherein the cathode structure comprises an air diffusion membrane, a hydrophobic polymer layer, an oxygen reduction catalyst, an electrolyte, and an electronically conductive component/current collector.
66. The cell of claim 65, wherein the electronically conductive component/current collector comprises a porous nickel material.
67. The cell of claim 65, further comprising a separator disposed between the protective membrane and the cathode structure.
68. The cell of claim 41, wherein the cathode structure electrochemically active component comprises a metal hydride alloy.
69. The cell of claim 68, wherein the cathode structure ionically conductive component comprises an aqueous electrolyte.
70. The cell of claim 69, wherein the aqueous electrolyte is acidic.
71. The cell of claim 70, wherein the aqueous electrolyte comprises a halide acid or acidic salt.
72. The cell of claim 71, wherein the aqueous electrolyte comprises a chloride or bromide acid or acidic salt.
73. The cell of claim 72, wherein the aqueous electrolyte comprises one of HCI, HBr, NH4Cl and NH4Br.
74. The cell of claim 73, wherein the metal hydride alloy comprises one of an and an AB2 alloy.
75. The cell of claim 21, wherein the cell is a primary cell.
76. The cell of claim 21, wherein the cell is a rechargeable cell.
77. The cell of claim 21, wherein the cell has a planar configuration.
78. The cell of claim 21, wherein the cell has a tubular configuration.
79. The cell of claim 41, wherein the active metal is lithium and the cathode structure comprises an aqueous ionically conductive component and a transition metal oxide electrochemically active component.
80. The cell of claim 79, wherein the transition metal oxide is selected from the group consisting of NiOOH, AgO, iron oxide, lead oxide and manganese oxide.
81. The cell of claim 21, wherein the anolyte further comprises a monomer for a polymer that is insoluble or minimally soluble in water and the catholyte comprises a polymerization initiator for the monomer.
82. The cell of claim 81, wherein the monomer is 1,3-dioxolane.
83. The cell of claim 82, wherein the polymerization initiator comprises at least one of the group consisting of protonic acid and water soluble Lewis acids dissolved in the catholyte.
84. The cell of claim 83, wherein the polymerization initiator comprises benbenzoyl cation.
85. A method of providing for the shut down of an electrochemical cell in accordance with claim 21 in the event of structural failure comprising providing in the anolyte a monomer for a polymer that is insoluble or minimally soluble in water and in the catholyte a polymerization initiator for the monomer.
86. The cell of claim 21, wherein the cathode structure comprises an ionically conductive component.
87. The cell of claim 86, wherein the ionically conductive component comprises a non-aqueous catholyte.
88. The cell of claim 87, wherein the catholyte comprises a material selected from the group consisting of organic liquids and ionic liquids.
89. The cell of claim 88, wherein the catholyte is a solution of a Li salt in an aprotic solvent selected from the group consisting of organic carbonates, ethers, lactones, sulfones esters, formats and combinations thereof.
90. The cell of claim 89, wherein the catholyte is selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and higher glymes,1,3 dioxolane, sufolane, methyl formate, methyl acetate, and combinations thereof, and a supporting salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiC1O4, LiSO3CF3, LiN(CF3SO2)2, LiN(SO2C2F5)2 and combinations thereof.
91. The cell of claim 90, further comprising a dissolved a solid, liquid or gaseous oxidant selected from the group consisting of lithium polysulfides, NO2, SO2, SOC1 2.
92. The cell of claim 87, wherein the catholyte comprises an ionic liquid selected from the group consisting of imidazolium derivatives, pyridinium derivatives, phosphonium compounds, and tetralkylammonium compounds, and combinations thereof.
93. The cell of claim 92, wherein the ionic liquid is selected from the group consisting of 1-Ethyl-3-methylimidazolium tosylate (EMIM-Ts), 1-Butyl-3-methylimidazolium octyl sulfate (BMIM-OctSO4), 1-Ethyl-3-methylimidazolium hexafluorophosphate, and 1-Hexyl-3-methylimidazolium tetrafluoroborate.
94. A method of making a battery cell in accordance with claim 21, comprising:
providing the following components, an active metal anode;
a cathode structure; and an sonically conductive protective architecture on a first surface of the anode, the architecture comprising, an active metal ion conducting separator layer comprising a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and a substantially impervious sonically conductive layer chemically compatible with the separator layer and the cathode structure, and in contact with the cathode structure; and assembling the components.
95. The method of claim 94, wherein the substantially impervious sonically conductive layer is tubular.
96. The cell of claim 21, wherein the cell has a discharge capacity of greater than 10 mAh/cm2.
97. The cell of claim 96, wherein the cell has a discharge capacity of greater than 100 mAh/cm2.
98. The cell of claim 97, wherein the cell has a discharge capacity of greater than 500 mAh/cm2.
99. The cell of claim 50, wherein the anode is about 3.35 mm thick Li, the cell is filled with aqueous electrolyte comprising NH4C1 and the cell has a discharge capacity of about 650 mAh/cm2.
100. The cell of claim 58, wherein the cell has a 3.3 mm thick Li anode and an area of 45 cm2 and an unpackaged specific energy of about 3400 Wh/1 (4100 Wh/kg).
101. The cell of claim 100, wherein the cell has a 70% package burden, and a packaged specific energy of about 1000 Wh/1 (1200 Wh/kg).
102. The cell of claim 43, further comprising a PEM H2/O2 fuel cell to capture hydrogen released from the cathode structure in the battery cell redox reaction.
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