Compliant seal structures for protected active metal anodes

• US 20070037058A1
• Filed: 08/08/2006
• Published: 02/15/2007
• Est. Priority Date: 08/09/2005
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Petrov, Alexei, De Jonghe, Lutgard, Nimon, Yevgeniy, Visco, Steven, Katz, Bruce
• Granted Patent: US 7,824,806 B2
• Time in Patent Office: Days
• US Class Current: 429/246
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 12/065 with plate-like electrodes or stacks of plate-like electrodes
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 50/105 Pouches or flexible bags
• CPC Class Codes: H01M 50/184 characterised by their shape or structure
• CPC Class Codes: H01M 50/186 characterised by the disposition of the sealing members
• CPC Class Codes: H01M 50/191 Inorganic material
• CPC Class Codes: H01M 50/193 Organic material
• CPC Class Codes: H01M 50/195 Composite material consisting of a mixture of organic and inorganic materials
• CPC Class Codes: H01M 50/197 having a layered structure
• CPC Class Codes: H01M 50/451 comprising layers of only organic material and layers containing inorganic material
• CPC Class Codes: H01M 50/457 comprising three or more layers
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: H01M 6/34 Immersion cells, e.g. sea-water cells
• CPC Class Codes: H01M 6/42 : Grouping of primary cells into batteries H01M6/40 takes precedence
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y10T 29/4911 : including sealing

Abstract

Protected anode architectures have ionically conductive protective membrane architectures that, in conjunction with compliant seal structures and anode backplanes, effectively enclose an active metal anode inside the interior of an anode compartment. This enclosure prevents the active metal from deleterious reaction with the environment external to the anode compartment, which may include aqueous, ambient moisture, and/or other materials corrosive to the active metal. The compliant seal structures are substantially impervious to anolytes, catholyes, dissolved species in electrolytes, and moisture and compliant to changes in anode volume such that physical continuity between the anode protective architecture and backplane are maintained. The protected anode architectures can be used in arrays of protected anode architectures and battery cells of various configurations incorporating the protected anode architectures or arrays.

Claims

1. A protected anode architecture, comprising:

an active metal anode having a first surface and a second surface;

an ionically conductive protective membrane architecture in physical continuity with the first surface of the anode;

an active metal anode backplane in physical continuity with the second surface of the anode; and

a compliant seal structure interfacing with the protective membrane architecture and the anode backplane to enclose the anode in an anode compartment, the seal structure being compliant to changes in anode thickness such that physical continuity between the anode, protective architecture and backplane are maintained;

wherein the ionically conductive protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the active metal of the anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with an environment exterior to the anode compartment; and

wherein the seal structure interfaces with the protective membrane architecture and the anode backplane such that a substantially impervious barrier between the interior and exterior of the anode compartment is provided.

2. The protected anode architecture of claim 1, wherein the architecture is a stand-alone component.

3. The protected anode architecture of claim 1, wherein the active metal anode is in the solid phase.

4. The protected anode architecture of claim 1, wherein the active metal anode is at least 10 microns thick.

5. The protected anode architecture of claim 1, wherein the active metal anode is at least 50 microns thick.

6. The protected anode architecture of claim 1, wherein the active metal anode is at least 1 mm thick.

7. The protected anode architecture of claim 1, wherein the active metal anode is at least 1 cm thick.

8. The protected anode architecture of claim 1, wherein the active metal anode comprises an alkali metal.

9. The protected anode architecture of claim 8, wherein the alkali metal is Li.

10. The protected anode architecture of claim 8, wherein the alkali metal is Na.

11. The protected anode architecture of claim 1, wherein the active metal anode comprises active metal-ions.

12. The protected anode architecture of claim 1, wherein the active metal anode comprises active metal alloying metal.

13. The protected anode architecture of claim 12, wherein the active metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Bi, Al, Cd, Ga, In and Sb.

14. The protected anode architecture of claim 1, wherein the active metal anode comprises intercalating material.

15. The protected anode architecture of claim 12, wherein the active metal intercalating material comprises carbon.

16. The protected anode architecture of claim 1, wherein the protective membrane architecture comprises an ionically conductive solid state membrane.

17. The protected anode architecture of claim 16, wherein the solid state membrane has an ionic conductivity of at least 10⁻

5 S/cm.

18. The protected anode architecture of claim 16, wherein the solid state membrane has an ionic conductivity of at least 10⁻

3 S/cm.

19. The protected anode architecture of claim 16, wherein the solid state membrane is monolithic.

20. The protected anode architecture of claim 16, wherein the solid state membrane comprises a composite comprising,

a first material component in contact with the anode that is ionically conductive and chemically compatible with the active metal of the anode, and

a second material component in contact with the first material component, the second material being substantially impervious, ionically conductive and chemically compatible with the first material component and the exterior of the anode compartment.

21. The protected anode architecture of claim 20, wherein the composite is a laminate.

22. The protected anode architecture of claim 20, wherein composite is graded.

23. The protected anode architecture of claim 20, wherein the first component comprises a material selected from the group consisting of active metal nitrides, active metal phosphides, and active metal halides, and active metal phosphorus oxynitride glass.

24. The protected anode architecture of claim 23, wherein the first component comprises a material selected from the group consisting of Li₃N, Li₃P and LiI, LiBr, LiCl, LiF and LiPON. Li-sulfide, Li-phosphorous sulfide, Li₂S-P₂S₅, Li₂S-P₂S₅-LiI.

25. The protected anode architecture of claim 23, wherein the first component comprises a metal nitride first layer material precursor.

26. The protected anode architecture of claim 25, wherein the first component comprises Cu₃N.

27. The protected anode architecture of claim 20, wherein the second component comprises a material selected from the group consisting of glassy or amorphous metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.

28. The component of claim 27 wherein the second component comprises a material selected from the group consisting of phosphorous based glass, oxide based glass, sulfur based glass, oxide sulfur based glass, selenide based glass, gallium based glass, germanium based glass, glass ceramic active metal ion conductors, sodium beta-alumina and lithium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), LiPON, Li₃PO₄.Li₂S.SiS₂, Li₂S.GeS₂.Ga₂S₃, Li₂O.11Al₂O₃, Na₂O.11Al₂O₃, Nasiglass, Li_0.3La_0.5TiO₃, Na₅MSi₄O₁₂ (M:

rare earth such as Nd, Gd, Dy), (Na, Li)_1+xTi<sub>2−

x</sub>Al_x(PO₄)₃ (0.0≦

x≦

0.9) and crystallographically related structures, Li_1+xHf<sub>2−

x</sub>Al_x(PO₄)₃ (0.0≦

x≦

0.9), Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂, Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂, Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂ and Li₄NbP₃O₁₂.

29. The protected anode architecture of claim 28, wherein the second component is an ion conductive glass-ceramic having the following composition:

30. The protected anode architecture of claim 1, wherein the protective membrane architecture comprises,

an active metal ion conducting separator layer chemically compatible with the active metal of the anode and in contact with the anode, the separator layer comprising a non-aqueous anolyte, and

a substantially impervious, ionically conductive layer in contact with the separator layer, and chemically compatible with the separator layer and with the exterior of the anode compartment.

31. The protected anode architecture of claim 30, wherein the separator layer comprises a semi-permeable membrane impregnated with a non-aqueous anolyte.

32. The protected anode architecture of claim 31, wherein the semi-permeable membrane is a micro-porous polymer.

33. The protected anode architecture of claim 32, wherein the anolyte is in the liquid phase.

34. The protected anode architecture of claim 33, wherein the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.

35. The protected anode architecture of claim 34, wherein the anolyte comprises a solvent selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 1,3-dioxolane, 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, NaClO₄, NaPF_c, NaAsF₆ NaBF₄, NaSO₃CF₃, NaN(CF₃SO₂)₂ and NaN(SO₂C₂F₅)₂,

36. The protected anode architecture of claim 35, wherein the anolyte is in the gel phase.

37. The protected anode architecture of claim 36, 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, 1,3-dioxolane 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, NaClO₄, NaPF_c, NaAsF₆ NaBF₄, NaSO₃CF₃, NaN(CF₃SO₂)₂ and NaN(SO₂C₂F₅)₂,

38. The protected anode architecture of claim 30, 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.

39. The component of claim 30 wherein the second component comprises a material selected from the group consisting of phosphorous based glass, oxide based glass, sulfur based glass, oxide sulfur based glass, selenide based glass, gallium based glass, germanium based glass, glass ceramic active metal ion conductors, sodium beta-alumina and lithium beta-alumina, Li superionic conductor (LISICON), Na superionic conductor (NASICON), LiPON, Li₃PO₄.Li₂S.SiS₂, Li₂S.GeS₂.Ga₂S₃, Li₂O.11Al₂O₃, Na₂O11Al₂O₃, Nasiglass, Li_0.3La_0.5TiO₃, Na₅MSi₄O₁₂ (M:

rare earth such as Nd, Gd, Dy), (Na, Li)_1+xTi<sub>2−

x</sub>Al_x(PO₄)₃ (0.0≦

x≦

0.9) and crystallographically related structures, Li_1+xHf<sub>2−

x</sub>Al_x(PO₄)₃ (0.0≦

x≦

0.9) Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂, Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂, Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂ and Li₄NbP₃O₁₂.

40. The protected anode architecture of claim 30, wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:

41. The protected anode architecture of claim 1, wherein the backplane is a substantially impervious structure chemically compatible with the active metal anode and the environment exterior to the anode compartment.

42. The protected anode architecture of claim 41, wherein the backplane comprises an anode current collector.

43. The protected anode architecture of claim 42, wherein the backplane further comprises a terminal connector.

44. The protected anode architecture of claim 43, wherein the backplane further comprises an electronic insulator.

45. The protected anode architecture of claim 41, wherein the backplane is contiguous with the seal structure.

46. The protected anode architecture of claim 41, wherein the anode backplane is a second protective membrane architecture.

47. The protected anode architecture of claim 46, wherein the anode backplane is a second protective membrane architecture, forming a symmetric double-sided protected anode architecture.

48. The protected anode architecture of claim 46, wherein the anode backplane is a second protective membrane architecture, forming an asymmetric double-sided protected anode architecture.

49. The protected anode architecture of claim 1, wherein the compliant seal structure is under tension.

50. The protected anode architecture of claim 1, wherein the compliant seal structure comprises a metal.

51. The protected anode architecture of claim 1, wherein the compliant seal structure comprises a polymer.

52. The protected anode architecture of claim 1, wherein the compliant seal structure is a multi-layer laminate having a plurality of at least two material layers.

53. The protected anode architecture of claim 52, wherein the multi-layer laminate has at least 3 layers whereby a top layer is that is chemically resistant to the environment external to the anode compartment, a bottom layer is a polymer that is chemically resistant to the environment inside the anode compartment, and a middle layer is a metal barrier layer.

54. The multi-layer laminate of claim 53 comprising a polyethylene terephthalate (PET) top layer, a polyethylene bottom layer, and an aluminum foil middle layer.

55. The protected anode architecture of claim 1, wherein the compliant seal structure is a multi-layer laminate and comprises an integrated sealant.

56. The protected anode architecture of claim 55, wherein the integrated sealant comprises a heat-sealable thermoplastic layer.

57. The protected anode architecture of claim 51, wherein the integrated sealant comprises a heat-sealable thermoplastic consisting of PE, PP, and ionomer resins.

58. The protected anode architecture of claim 55, wherein the integrated sealant comprises an adhesive coating layer.

59. The protected anode architecture of claim 58, wherein the integrated sealant comprises an adhesive coating layer comprising a poly isobutylene of average molecular weight from 60,000 to 5,000,000.

60. The protected anode architecture of claim 1, wherein the compliant seal structure is bound to the protective membrane architecture via the integrated sealant by thermal compression.

61. The protected anode architecture of claim 1, wherein the compliant seal structure is bound to the anode backplane via the integrated sealant by thermal compression.

62. The protected anode architecture of claim 1, wherein the compliant seal structure is bound to the protective membrane architecture via a discrete sealant.

63. The protected anode architecture of claim 61, wherein the compliant seal structure to protective membrane architecture bond further comprises a discrete sealant.

64. The protected anode architecture of claim 62, wherein the discrete sealant comprises epoxy.

65. The protected anode architecture of claim 64, wherein the discrete epoxy sealant comprises a polyamide.

66. The protected anode architecture of claim 62, wherein the discrete sealant comprises a poly isobutylene of average molecular weight from 60,000 to 5,000,000.

67. The protected anode architecture of claim 4, wherein the compliant seal member can deform such that physical continuity between the anode, backplane and protective architecture is maintained upon discharge and charge.

68. The protected anode architecture of claim 1, wherein the seal structure is configured to fully accommodate thickness changes of the anode during discharge and charge.

69. The protected anode architecture of claim 1, comprising a plurality of the protected anode architectures arranged in an array interconnected via one or more of a common backplane and shared seal structures.

70. The protected anode architecture of claim 69, wherein a plurality of the anodes of the array are electrically connected.

71. The protected anode architecture of claim 69, wherein the anodes of the array are electrically connected.

72. The protected anode architecture of claim 69, wherein the array has a planar configuration.

73. The protected anode architecture of claim 69, wherein the array has a tubular configuration.

74. The protected anode architecture of claim 69, wherein the array has a spiral configuration.

75. The protected anode architecture of claim 69, wherein the array has a spoke and hub configuration.

76. The protected anode architecture of claim 1 wherein a primer is coated onto the solid electrolyte layer to improve adhesion of the bond interface with the compliant seal structure.

77. The protected anode architecture of claim 76 whereby the primer is a metal nitride.

78. The protected anode architecture of claim 76 whereby the primer is a metal oxide.

94. The protected anode architecture of claim 1 wherein the surface of the solid electrolyte layer is chemically etched to improve adhesion of the bond interface with the compliant seal structure.

79. A battery cell, comprising:

protected anode architecture, comprising,

an active metal anode having a first surface and a second surface,

an ionically conductive protective membrane architecture on the first surface of the anode,

an active metal anode backplane on the second surface of the anode; and

a seal structure interfacing with the protective membrane architecture and the anode backplane to enclose the anode in an anode compartment, the seal structure being compliant to changes in anode thickness such that physical continuity between the anode, protective architecture and backplane are maintained;

a cathode compartment in contact with the ionically conductive protective membrane architecture, the cathode compartment comprising a cathode structure and a catholyte, wherein the cathode structure comprises an electronically conductive component, and at least one of the cathode structure and the catholyte comprises at least one of an ionically conductive component and an electrochemically active component, wherein at least one of the cathode structure and the catholyte component comprises an active metal corrosive constituent;

wherein the ionically conductive protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the active metal of the anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with the cathode compartment and

wherein the seal structure is bound to the protective membrane and the anode backplane such that a substantially impervious barrier between the interior and exterior of the anode compartment is provided.

80. The cell of claim 79, wherein the cathode compartment comprises catholyte.

81. The cell of claim 80, wherein the catholyte comprises a liquid

82. The cell of claim 81, wherein the catholyte comprises aqueous.

83. The cell of claim 81, wherein the catholyte comprises non-aqueous solvent.

84. The cell of claim 81, wherein the catholyte comprises seawater.

85. The cell of claim 80, wherein the catholyte comprises electrochemically active oxidants.

86. The cell of claim 79, wherein the electrochemically active component of the cathode structure comprises oxygen.

87. The cell of claim 79, wherein the electrochemically active component of the cathode structure comprises an intercalation material.

88. The cell of claim 87, wherein the intercalation material comprises a transition metal oxide.

89. The cell of claim 87, wherein the intercalation material comprises a transition metal phosphate.

90. The cell of claim 79, wherein the cell further comprises a cell container wherein the cell container encloses the protected anode architecture and cathode compartment.

91. The cell of claim 90, wherein the cell container is open to ambient air such that the electrochemically active component of the cathode structure comprises ambient air.

92. The cell of claim 90, wherein the cell container comprises the anode backplane.

93. The cell of claim 92, wherein the compliant seal structure is bound to the anode backplane by a crimp seal.

95. The cell of claim 79, wherein the compliant seal structure is configured to fully compensate for contraction of the anode and expansion of the cathode on cell discharge so as to maximize cell energy density.

96. The cell of claim 79, comprising a plurality of the protected anode architectures arranged in an array interconnected via one or more of a common backplane and shared seal structures.

97. The cell of claim 96, wherein the anodes of the array have a common cathode structure.

98. The cell of claim 96, wherein the anodes of the array have distinct cathode structures.

99. A method of making a protected anode structure, comprising:

providing,

an active metal anode having a first surface and a second surface;

an ionically conductive protective membrane architecture in physical continuity with the first surface of the anode;

an active metal anode backplane in physical continuity with the second surface of the anode; and

interfacing the protective membrane architecture with the anode backplane and a compliant seal structure to enclose the anode in an anode compartment, the seal structure being compliant to changes in anode thickness such that physical continuity between the anode, protective architecture and backplane are maintained;

wherein the ionically conductive protective membrane architecture comprises one or more materials configured to provide a first membrane surface chemically compatible with the active metal of the anode in contact with the anode, and a second membrane surface substantially impervious to and chemically compatible with an environment exterior to the anode compartment; and

wherein the compliant seal structure interfaces with the protective membrane architecture and the anode backplane such that a substantially impervious barrier between the interior and exterior of the anode compartment is provided.

100. The method of claim 99, wherein the compliant seal structure comprises a plurality of discrete elements.

101. The method of claim 99, wherein the compliant seal structure is a unified article.

102. The method of claim 99, wherein the compliant seal structure is joined to the protective membrane architecture via an integrated sealant by thermal compression.

103. The method of claim 99, wherein the compliant seal structure is joined to the anode backplane via the integrated sealant by thermal compression.

104. The method of claim 99, wherein the compliant seal structure is joined to the protective membrane architecture by a discrete sealant.

105. The method of claim 103, wherein the seal structure to protective membrane architecture bond further comprises a discrete sealant.

106. The method of claim 99, further comprising combining the protected anode architecture with a cathode to form an electrochemical cell.

107. The method of claim 106, wherein the cell is a battery cell.

108. The method of claim 107, wherein the cell is a metal/air battery cell.

109. The method of claim 108, wherein the cell is a Li-metal/air battery cell.

110. The method of claim 107, wherein the cell is a metal/water battery cell.

111. The method of claim 110, wherein the cell is a metal/seawater battery cell.

112. The method of claim 111, wherein the cell is a Li-metal/seawater battery cell.