STABLE LOW VOLTAGE ELECTROCHEMICAL CELL

• US 20190312269A1
• Filed: 11/22/2017
• Published: 10/10/2019
• Est. Priority Date: 11/22/2016
• Status: Abandoned Application

• Current Assignee: CAMX Power LLC (KES5 LLC)
• Original Assignee: CAMX Power LLC (KES5 LLC)
• Inventors: Treger, Jack, Ofer, David, Sriramulu, Suresh
• Application Number:
  US16/461,053
• Publication Number:
  US 20190312269A1
• Time in Patent Office: Days
• CPC Class Codes: H01M 2220/30 Batteries in portable systems, e.g. mobile phone, laptop
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 4/0435 Rolling or calendering
• CPC Class Codes: H01M 4/044 Activating, forming or electrochemical attack of the supporting material
• CPC Class Codes: H01M 4/06 Electrodes for primary cells
• CPC Class Codes: H01M 4/08 Processes of manufacture
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/382 Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/387 Tin or alloys based on tin
• CPC Class Codes: H01M 4/62 Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/622 being polymers
• CPC Class Codes: H01M 4/625 Carbon or graphite
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• CPC Class Codes: H01M 50/417 Polyolefins
• CPC Class Codes: H01M 50/423 Polyamide resins
• CPC Class Codes: H01M 50/426 : Fluorocarbon polymers
• CPC Class Codes: H01M 50/429 : Natural polymers
• CPC Class Codes: H01M 50/437 : Glass
• CPC Class Codes: H01M 50/44 : Fibrous material
• CPC Class Codes: H01M 6/16 : with organic electrolyte H01M6/18 takes precedence
• CPC Class Codes: H01M 6/164 : by the solvent
• CPC Class Codes: H01M 6/166 : by the solute
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

Provided are primary electrochemical cells having a stable operating voltage of 0.3 V to 2.0 V that include a Li anode coupled to a cathode that is formed of one or more Group 4A, 3A, or 5A elements provided alone or as an alloy with a second, third or other Group 4A, 3A, or 5A element or one or more transition metals. The cells further include a non-aqueous electrolyte optionally with low volatility such as having a vapor pressure of 5 mm Hg or lower at STP, and optionally a lithium-ion conductive and electrically insulating separator inserted between the anode and the cathode. The cells provide stable operating voltage that in some aspects can serve to power ultra-low power devices for 10 or more years without the need for expensive or inefficient circuitry to alter the cell voltage.

Claims

1. A primary electrochemical cell having a stable operating voltage of 0.3 V to 2.0 V and comprising:

an anode comprising Li, optionally metallic lithium, lithiated carbon, lithium-aluminum alloys, lithium-tin alloys, or lithiated silicon;

a cathode comprising a Group 4A, 3A, or 5A element;

a non-aqueous electrolyte; and

optionally a lithium-ion conductive and electrically insulating separator inserted between the anode and the cathode.

2. The electrochemical cell of claim 1 wherein the cathode comprises a Group 4A, element or an alloy of a group 4A element.

3. The electrochemical cell of claim 1 wherein the cathode comprises tin, aluminum, indium, lead, zinc, antimony, cadmium, bronze, brass, tin-bismuth alloy, tin-antimony alloy, tin-copper alloy, tin-nickel alloy, gallium-copper alloy, gallium-indium-copper alloy, or tin-lead alloy.

4. The electrochemical cell of claim 1 wherein the cathode comprises tin, aluminum, gallium, antimony, or an alloy comprising tin, aluminum, gallium, antimony, copper or combinations thereof.

5. The electrochemical cell of any one of claims 1-4 wherein the electrochemical cell has a stable operating voltage of 0.3 V to 1.5 V.

6. The electrochemical cell of any one of claims 1-4 wherein the electrochemical cell has a stable operating voltage from 0.3 V to 1.0 V.

7. The electrochemical cell of any one of claims 1-4 wherein the cathode comprises an alloy of tin and antimony, the antimony present in the alloy at 0.1 to 88 atomic percent, optionally 1 to 3 atomic percent.

8. The electrochemical cell of any one of claims 1-4 wherein the lithium anode comprises lithium metal foil, the electrochemical cell optionally further comprising a tin-antimony alloy cathode.

9. The electrochemical cell of any one of claims 1-4 wherein the lithium anode is a lithium composite comprising lithium powder and a binder coated onto a copper foil substrate.

10. The electrochemical cell of claim 9 wherein the binder is a polymer.

11. The electrochemical cell of claim 9 wherein the binder comprises polybutadiene-styrene, polyisobutylene, polyisoprene or ethylene-propylene diene.

12. The electrochemical cell of any one of claims 1-4 wherein the cathode comprises a cathode metal foil comprising the Group 4A, 3A or 5A element.

13. The electrochemical cell of claim 12 wherein the cathode metal foil comprises aluminum.

14. The electrochemical cell of claim 12 wherein the cathode metal foil comprises tin.

15. The electrochemical cell of claim 12 wherein the cathode metal foil comprises an alloy of tin and antimony, the antimony present in the alloy at 0.1 to 88 atomic percent, optionally 1 to 3 atomic percent.

16. The electrochemical cell of claim 12 wherein the cathode metal foil thickness is greater than 1 micron, optionally greater than 25 microns and less than 1000 microns.

17. The electrochemical cell of claim 12 wherein the metal foil is substantially free of native surface oxide.

18. The electrochemical cell of claim 12 wherein the metal foil is coated with an abrasive powder and a polymer, and then calendered in air.

19. The electrochemical cell of claim 18 wherein the calender pressure is greater than 10 psi, optionally greater than 50 psi, optionally greater than 100 psi.

20. The electrochemical cell of claim 12 wherein the metal foil is coated with an abrasive powder, optionally acetylene black, optionally graphene, and optionally a polymer, and then calendered in air.

21. The electrochemical cell of claim 20 wherein the abrasive powder and the acetylene black are present at 50 to 95 weight percent.

22. The electrochemical cell of claim 20 wherein the abrasive powder comprises submicron boron and the polymer is polyvinylidene fluoride.

23. The electrochemical cell of claim 1 wherein cathode is a composite comprising a Group 4A, 3A, or 5A metal, a polymeric binder and a conductive additive coated onto a copper foil substrate and then calendered in air.

24. The electrochemical cell of claim 23 wherein the calender pressure is greater than 10 psi, optionally greater than 50 psi, optionally greater than 100 psi.

25. The electrochemical cell of claim 12 wherein cathode comprises indium, lead, zinc, antimony, brass, bronze, cadmium, silicon, carbon, germanium, aluminum, tin-bismuth, tin-antimony, tin-copper alloy, tin-nickel, tin-lead, tin silicon-tin, germanium-tin, niobium-tin, tin-silver-copper, or other alloy comprising these elements such as white metal or babbitt alloys, and mixtures thereof.

26. The electrochemical cell of claim 20 wherein the polymeric binder comprises polyvinylidene fluoride, polybutadiene-styrene, polyisobutylene, polyisoprene, ethylene-propylene diene, or polyacrylic acid.

27. The electrochemical cell of claim 23 wherein the conductive additive is acetylene black, graphite, graphene, and mixtures thereof.

28. The electrochemical cell of any one of claims 1-4 wherein the non-aqueous electrolyte has a vapor pressure of less than 5 mm Hg at standard temperature and pressure, optionally less than 0.2 mm Hg at standard temperature and pressure.

29. The electrochemical cell of any one of claims 1-4 wherein the non-aqueous electrolyte comprises a lithium salt and an organic solvent.

30. The electrochemical cell of claim 29 wherein the lithium salt comprises lithium hexafluorophosphate, lithium bistrifluoromethanesulfonimide, lithium triflate, lithium tetrafluoroborate, lithium iodide, and mixtures thereof.

31. The electrochemical cell of claim 29 wherein the organic solvent is a polar aprotic liquid.

32. The electrochemical cell of claim 31 wherein the organic solvent comprises a carbonate, an ether, a fluoro-substituted carbonate, a fluoroalkyl-substituted carbonate, a hydrofluoro ether, or a fluoroalkyl substituted ether and mixtures thereof.

33. The electrochemical cell of claim 32 wherein the carbonate comprises ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl-methyl carbonate, or diethylcarbonate, and mixtures thereof.

34. The electrochemical cell of claim 32 wherein the ether comprises diethylether, dimethoxyethane, bis(2-methoxyethyl) ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1,2-dioxolane, and mixtures thereof.

35. The electrochemical cell of claim 32 wherein the fluoro-substituted carbonate comprises monofluoroethylene carbonate, difluoroethylene carbonate, or mixtures thereof.

36. The electrochemical cell of claim 32 wherein the fluoroalkyl-substituted carbonate comprises methyl 2,2,2 trifluoroethyl carbonate, ethyl 2,2,2 trifluoroethyl carbonate, or mixtures thereof.

37. The electrochemical cell of claim 32 wherein the hydrofluoro ether comprises 2-trifluoromethyl-3-methoxyperfluoropentane, 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane, or mixtures thereof.

38. The electrochemical cell of any one of claims 1-4 wherein the non-aqueous electrolyte comprises an ionic liquid and a lithium salt, the ionic liquid comprising an ionic liquid cation and an ionic liquid anion.

39. The electrochemical cell of claim 38 wherein the ionic liquid cation comprises a imidazolium, alkysubstituted imidazolium, ammonium, pyridinium, pyrrolidinium, phosphonium, sulfonium moiety, or mixtures thereof.

40. The electrochemical cell of claim 38 wherein the ionic liquid anion comprises a hexafluorophosphate, bistrifluoromethanesulfonamide, triflate, tetrafluoroborate, dicyanamide, iodide moiety, or mixtures thereof.

41. The electrochemical cell of claim 38 wherein the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl)imide, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium dicyanamide, 11-methyl-3-octylimidazolium tetrafluoroborate, or mixtures thereof.

42. The electrochemical cell of claim 38 wherein the lithium salt comprises lithium hexafluorophosphate, lithium bistrifluoromethanesulfonamide, lithium triflate, lithium tetrafluoroborate, lithium iodide, or mixtures thereof.

43. The electrochemical cell of claim 38 wherein the lithium salt concentration is 0.1 to 20% by weight.

44. The electrochemical cell of any one of claims 1-4 wherein the non-aqueous electrolyte and lithium-ion conductive and electrically insulating separator/electrolyte combination comprises a solid polymer electrolyte.

45. The electrochemical cell of claim 44 wherein the solid polymer electrolyte comprises poly(ethylene oxide) complexed with a lithium salt.

46. The electrochemical cell of claim 44 wherein the lithium salt comprises lithium hexafluorophosphate, lithium bistrifluoromethanesulfonamide, lithium triflate, lithium tetrafluoroborate, lithium iodide, or mixtures thereof.

47. The electrochemical cell of claim 44 wherein the solid polymer electrolyte comprises a plasticizing additive.

48. The electrochemical cell of claim 47 wherein the plasticizing additive has a 1 bar boiling point greater than 130°

C.

49. The electrochemical cell of claim 47 wherein the plasticizing additive is present at a concentration of 0.1 to 50 percent by weight.

50. The electrochemical cell of claim 47 wherein the plasticizing additive comprises an oligomeric ether.

51. The electrochemical cell of claim 50 wherein the oligomeric ether comprises bis(2-methoxyethyl) ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or mixtures thereof.

52. The electrochemical cell of claim 47 wherein the plasticizing additive comprises an ionic liquid comprising an ionic liquid cation and an ionic liquid anion.

53. The electrochemical cell of claim 52 wherein the ionic liquid cation comprises a imidazolium, alkysubstituted imidazolium, ammonium, pyridinium, pyrrolidinium, phosphonium, sulfonium moiety, or mixtures thereof.

54. The electrochemical cell of claim 52 wherein the ionic liquid anion comprises hexafluorophosphate, bistrifluoromethanesulfonamide, triflate, tetrafluoroborate, dicyanamide, iodide moiety, or mixtures thereof.

55. The electrochemical cell of claim 52 wherein the ionic liquid concentration is from 0.1 to 30 weight percent.

56. The electrochemical cell of any one of claims 1-4 wherein the lithium-ion conductive and electrically insulating separator is a microporous or non-woven polymer or glass fiber separator.

57. The electrochemical cell of claim 56 wherein the polymer comprises polyolefin, cellulose, mixed cellulose ester, nylon, cellophane, polyvinylidene fluoride, or glass fiber.

58. An electrochemical battery comprising two or more bipolar cells electrically connected in series wherein each bipolar cell comprises the electrochemical cell of any one of claims 1-4.

59. The battery of claim 58 wherein the non-aqueous electrolyte is a gelled electrolyte.

60. The battery of claim 58 wherein the non-aqueous electrolyte is a solid polymer electrolyte.

61. The battery of claim 58 wherein the gelled electrolyte comprises a lithium salt, an organic solvent and a polymer that is soluble in the solvent.

62. The battery of claim 58 wherein the gelled electrolyte has a yield stress of at least 5 Pa.

63. The battery of claim 60 wherein the concentration of polymer is 0.1 to 50% by weight.

64. The battery of claim 60 wherein the polymer is an organic solid.

65. The battery of claim 60 wherein the polymer is polar.

66. The battery of claim 60 wherein the polymer comprises poly(ethylene oxide), polyacrylate, polyvinylidene fluoride, poly(vinylidene fluoride-co-hexafluoropropylene) polyacrylonitrile, polystyrene-co-acrylonitrile, polyacrylamide, polyvinylacetate, polyurethane or mixtures thereof.

67. The battery of claim 59 wherein the gelled electrolyte comprises an ionic liquid, a lithium salt and a polymer that is soluble in the ionic liquid.

68. The battery of claim 67 wherein the concentration of polymer is 0.1 to 30% by weight.

69. The battery of claim 67 wherein the ionic liquid comprises a cation of a imidazolium, alkysubstituted imidazolium, ammonium, pyridinium, pyrrolidinium, phosphonium, sulfonium moiety, or mixtures thereof.

70. The gelled electrolyte of claim 67 wherein the ionic liquid comprises an anion comprising hexafluorophosphate, bistrifluoromethanesulfonamide, triflate, tetrafluoroborate, dicyanamide, iodide, or mixtures thereof.

71. The battery of claim 60 wherein the yield stress point of the solid polymer is greater than 5 Pa.

72. The battery of claim 60 wherein the polymer is an organic polar solid.

73. The battery of claim 60 wherein the solid polymer electrolyte comprises poly(ethylene oxide) complexed with a lithium salt.

74. The battery of claim 73 wherein the lithium salt comprises lithium hexafluorophosphate, lithium bistrifluoromethanesulfonamide, lithium triflate, lithium tetrafluoroborate, lithium iodide, or mixtures thereof.

75. The battery of claim 60 wherein the electrolyte is a solid polymer electrolyte comprising a plasticizing additive.

76. The battery of claim 75 wherein the plasticizing additive is present at a concentration of 0.1 to 50 weight percent.

77. The battery of claim 75 wherein the plasticizing additive has a 1 bar boiling point greater than 130°

C.

78. The battery of claim 75 wherein the plasticizing additive comprises an oligomeric ether.

79. The battery of claim 78 the oligomeric ether comprises bis(2-methoxyethyl) ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or mixtures thereof.

80. The battery of claim 75 wherein the plasticizing additive comprises an ionic liquid comprising a cation and an anion.

81. The battery of claim 80 wherein the ionic liquid concentration ranges from 1 to 30 weight percent.

82. The battery of claim 80 wherein the cation comprises a imidazolium, alkysubstituted imidazolium, ammonium, pyridinium, pyrrolidinium, phosphonium, sulfonium moiety, and mixtures thereof.

83. The battery of claim 80 wherein the anion comprises hexafluorophosphate, bistrifluoromethanesulfonamide, triflate, tetrafluoroborate, dicyanamide, iodide moiety, or mixtures thereof.

84. A wireless communication device comprising the electrochemical cell of any one of claims 1-4.

85. A wireless communication device comprising the electrochemical battery of claim 58.

86. A remote sensor containing the electrochemical cell of any one of claims 1-4.

87. A remote sensor containing the battery of claim 58.

88. An IoT device containing the electrochemical cell of any one of claims 1-4 or the battery of claim 58.

89. The electrochemical cell of any one of claims 1-4 for use in an electrical device requiring a stable voltage of 2 V or lower, optionally 1 V or lower, for 10 years or more.

90. The electrochemical cell of claim 89 wherein the non-aqueous electrolyte has a vapor pressure of less than 5 mm Hg at standard temperature and pressure, optionally less than 0.2 mm Hg at standard temperature and pressure.

91. The electrochemical cell of claim 89 wherein the cathode comprises an alloy of tin and antimony, the antimony present in the alloy at 0.1 to 88 atomic percent, optionally 1 to 5 atomic percent.

92. The electrochemical cell of claim 89 wherein the lithium anode comprises lithium metal foil.

93. The electrochemical cell of claim 92 wherein the metal foil is substantially free of native surface oxide.

94. The electrochemical cell of claim 92 wherein the metal foil is coated with an abrasive powder and a polymer.

95. The electrochemical cell of claim 94 wherein the metal foil is formed by calendaring in air at a calender pressure greater than 10 psi, optionally greater than 50 psi, optionally greater than 100 psi.

96. The electrochemical cell of claim 92 wherein the metal foil is coated with an abrasive powder, optionally acetylene black, optionally graphene, and optionally a polymer, and then calendered in air.

97. The electrochemical cell of claim 96 wherein the weight ratio of abrasive powder, acetylene black, graphene and polymer are about 60/5/15/20 respectively.

98. The electrochemical cell of claim 96 wherein the abrasive powder comprises submicron boron and the polymer is polyvinylidene fluoride.

99. A process of powering an electrical device requiring a stable voltage of 1 V or lower for 10 years or more comprising electrically connecting the electrochemical cell of any one of claims 1-4 with an electrochemical device.

100. The process of claim 99 wherein the non-aqueous electrolyte has a vapor pressure of less than 5 mm Hg at standard temperature and pressure, optionally less than 0.2 mm Hg at standard temperature and pressure.

101. The process of claim 99 wherein the cathode comprises an alloy of tin and antimony, the antimony present in the alloy at 0.1 to 88 atomic percent, optionally 1 to 5 atomic percent.

102. The process of claim 99 wherein the lithium anode comprises lithium metal foil.

103. The process of claim 102 further comprising abrading the metal foil under oxygen free atmosphere prior to the step of electrically contacting.

104. The process of claim 102 further comprising coating the metal foil with an abrasive powder and a polymer, and then calendering the metal foil in air using a calendar pressure.

105. The process of claim 104 wherein the calender pressure is greater than 10 psi, optionally greater than 50 psi, optionally greater than 100 psi.

106. The process of claim 102 further comprising coating the metal foil with an abrasive powder, acetylene black, graphene, and a polymer and then calendaring the metal foil in air.

107. The process of claim 106 wherein the weight ratio of abrasive powder, acetylene black, graphene and polymer are about 60/5/15/20 respectively.

108. The process of claim 106 wherein the abrasive powder comprises submicron boron and the polymer is polyvinylidene fluoride.

109. The cell, battery, process or device of any proceeding claim wherein the Li anode comprises metallic lithium, lithiated carbon, lithium-aluminum alloys, lithium-tin alloys, or lithiated silicon.