Electrochemical cell with a non-liquid electrolyte

• US 20020122980A1
• Filed: 05/01/2001
• Published: 09/05/2002
• Est. Priority Date: 05/19/1998
• Status: Abandoned Application

• Current Assignee: Eli Rosh Chodesh, Joel Lang, Joost Manssen, Marvid Antelman, Niles A. Fleischer
• Original Assignee: Eli Rosh Chodesh, Joel Lang, Joost Manssen, Marvid Antelman, Niles A. Fleischer
• Inventors: Chodesh, Eli Rosh, Lang, Joel, Manssen, Joost, Antelman, Marvid, Fleischer, Niles A.
• Application Number:
  US09/846,680
• Publication Number:
  US 20020122980A1
• Time in Patent Office: Days
• US Class Current: 429/213
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 2300/0005 Acid electrolytes
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 4/383 Hydrogen absorbing alloys
• CPC Class Codes: H01M 4/48 of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A non-liquid electrolyte containing electrochemical cell which operates efficiently at room temperature. The cell includes: (a) a non-liquid electrolyte (14) in which protons are mobile; (b) an anode (10) including an active material based on the organic compound which is a source of protons during cell discharge; and (c) a solid cathode (12) including a compound which forms an electrochemical couple with the anode. The active materials can be chosen so that the cell has the feature that the electrochemical reactions at the anode and cathode are at least partially reversible. An important feature of the cell is that no thermal activation is required for its operation. Therefore, the cell efficiently operates under ambient temperatures.

Claims

1. An electrochemical cell comprising an anode, a cathode and a non-liquid electrolyte between, and in contact with, the anode and cathode, wherein:

(a) said anode includes an organic compound which is a source of protons during discharge;

(b) said cathode includes a compound which forms an electrochemical couple with the anode; and

(c) said electrolyte includes a non-liquid material in which protons are mobile.

2. An electrochemical cell as in claim 1, wherein at least one of said anode and cathode further includes a proton conducting material.

3. An electrochemical cell as in claim 2, wherein said proton conducting material is in a form selected from the group of forms consisting of a solid, a solution, a gel and a polymer.

4. An electrochemical cell as in claim 3, wherein said solution is an aqueous acid solution.

5. An electrochemical cell as in claim 4, wherein said aqueous acid solution is selected from the group consisting of sulfuric acid, methane sulfonic acid. nitric acid, hydrofluoric acid, hydrochloric acid, phosphoric acid, HBF₄, perchloric acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, sulfurous acid and pyrophosphoric acid.

6. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode is selected from the group of organic compounds consisting of hydroquinone, phloroglucinol, echinochrome, 1,2,5,8-tetrahydroxyanthraquinone, purpogallin, methylenedigallic acid, 2,5-dihydroxy-1,4-benzoquinone, resorcinol, ascorbic acid and its derivatives;

tetrahydroxy napthalene, tetrahydroxy 1,4-naphthaquinone, pentahydroxy 1,4-naphthaquinone, phenolphthalein, indophenol, bromophenol blue, oxindole, o-phenanthroline, phenanthridine, 6(5H)-phenanthridinone, uracil, 2-amino-5-bromopyridine, 5-aminotetrazole monohydrate, 2-aminothiazole, 2-aminopyrimidine, 2-amino-3-hydroxy-pyridine, 2,4,6-triaminopyrimidine, 2,4-diamino-6-hydroxy pyrimidine, 5,6-diamino-1,3-dimethyluracil hydrate, 5,6-diamino-2-thiouracil, cyanuric acid, cyanuric acid compound with melamine, 1,2-diaminoanthraquinone and 3-amino-2-cyclohexen-1-one, methylene blue, hydroxy acetophenone, acetaminophen, hydroxybenzyl alcohol, dopamine, pyrogallol, naphthols, anthranol, hydroxy anthraquinone, anthralin, anthragallol, anthrarufin, anthrobin, purpurin, tetrahydroxybenzophenone, 1,8,9-anthracenetriol, carminic acid, hydroquinone nonomethyl ether, citrazinic acid, hydroxybenzophenone, hydroxy biphenyl, tetrahydro papaveroline, fustin, hydroquinone monobenzylether hydroxymethyl pyridine, squaric acid, tetrahydroxy acetophenone, tetrahydroxy benzoic acid, Rhodizonic acid, croconic acid, hexahydroxy benzene, reductic acid, 5-methyl reductic acid, calix(4)arene, chloranilic acid and tetrahydroxy quinone.

7. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode is selected from the group consisting of the non-hydrated and the hydrated forms of those compounds.

8. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode is selected from the group consisting of tetrahydroxy quinone, hexahydroxybenzene, chloranilic acid, a reduced form of chloranilic acid, chloranil, rhodizonic acid, fluoroanilic acid, a reduced form of fluoroanilic acid, fluoranil and duroquinone.

9. An electrochemical cell as in claim 1. wherein said organic compound contained in said anode is a proton-donating non-aromatic ring compound.

10. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode has both proton-donating and proton-accepting groups.

11. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode is a quinone.

12. An electrochemical cell as in claim 1, wherein said organic compound contained in said anode is a polymer.

13. An electrochemical cell as in claim 1, wherein said anode further includes a catalyst for catalyzing cell anodic reactions.

14. An electrochemical cell as in claim 1, wherein said anode further includes at least one compound which includes a metal whose cation can assume at least two different non-zero oxidation numbers.

15. An electrochemical cell as in claim 14, wherein said metal is selected from the group consisting of Ti, Cu, Sn, Al, Cr, W, Sb, Ir, Mo, Fe, Co and Bi.

16. An electrochemical cell as in claim 1, wherein said non-liquid material in which protons are mobile includes a substance selected from the group consisting of a heteropolyacid in its hydrated form, a heteropolyacid in its non-hydrated form, a polymer-heteropolyacid blend, a single phase substance made of a heteropolyacid and a polymer, a multi-component substance which includes a heteropolyacid and a polymer, an anion exchanger which does not block protons, an anion adsorber which does not block protons, a cation adsorber, cation exchange materials, including their hydrogenated forms, chloro-sulfonated polyethylene, sulfonated polystyrene, sulfonated polysulfones and copolymers based on these materials, a perfluoronated sulfuric acid cation exchanger, cellulose acetate and cellulose triacetate membrane.

17. An electrochemical cell as in claim 1, wherein said non-liquid material in which protons are mobile is selected from the group consisting of sulfonated wax, polyvinylsulfonic acid, polyvinylphosphoric acid, sulfonated polyolefins, sulfonated polystyrenes, sulfonated phthalocyanines, sulfonated porphyrins, poly-2-acrylamido-2-methylpropanesulfonic acid, polyacrylic acid, polyvinyl sulfuric acid and polymethacrylic acid.

18. An electrochemical cell as in claim 1, wherein said non-liquid material in which protons are mobile includes a substance selected from the group consisting of an ion exchange material and an ion adsorber material.

19. An electrochemical cell as in claim 16, wherein said heteropolyacid is selected from the group consisting of molybdophosphoric acid, tungstophosphoric acid, molybdosilicic acid and tungstosilicic acid.

20. An electrochemical cell as in claim 16, wherein said polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone). poly (2-vinylpyridine), poly (4-vinylpyridine), polyvinyl acetate, polyacrylamide. polyethyleneimine, poly(vinyl pyrrolidone), polyvinylidene fluoride, polyhydroxyethylene, polyethyleneimine, polyacrylic acid, poly-2-ethyl-2-oxazoline, phenol formaldehyde resins, polyacrylamide, poly-N-substitued acrylamide, polymethacrylic acid, poly-N-vinylimidazole, poly-2-vinylpyridine, a polymer having a hydrophilic functional moiety, agar and agarose.

21. An electrochemical cell as in claim 17, wherein said polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), poly (2-vinylpyridine), poly (4-vinylpyridine), polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), polyvinylidene fluoride, polyhydroxyethylene, polyethyleneimine, polyacrylic acid, poly-2-ethyl-2-oxazoline, phenol formaldehyde resins, polyacrylamide, poly-N-substitued acrylamide, polymethacrylic acid, poly-N-vinylimidazole, poly-2-vinylpyridine, a polymer having a hydrophilic functional moiety, agar and agarose.

22. An electrochemical cell as in claim 20, wherein said polyvinyl alcohol polymer is in a form selected from the group of forms consisting of a fully hydrolyzed form and a partially hydrolyzed form.

23. An electrochemical cell as in claim 20, wherein said polyvinyl alcohol polymer has a molecular weight in the range between substantially 15,000 and substantially 186,000.

24. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is selected from the group consisting of the non-hydrated and the hydrated forms of those compounds.

25. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is selected from the group consisting of transition metal dichalcogenides, NiOOH, naphthalene, polycarbon fluoride, polydicarbon fluoride, Ni(OH)₂, monovalent silver oxide, divalent silver oxide, tantalum oxide, molybdenum trioxide, niobium triselenide, Bi₂Sr₂CaCu₂O_8+y, Bi₂Sr₂Cu₁O_6+y, YBa₂Cu₃O₇, fullerenes and a manganese compound.

26. An electrochemical cell as in claim 25, wherein said manganese compound is selected from the group consisting of manganese sulfate in its hydrated forms, manganese sulfate in its non-hydrated form, manganese dioxide in its chemical form, manganese dioxide in its electrolytic form, manganese dioxide in its natural form, lambda manganese dioxide and a manganese compound which is made by treating a spinel lithium manganese oxide of a nominal formula LiMn₂O₄ to remove the lithium.

27. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is MnSO₄-x.H₂O, where x is an integer in the range of from 0 to 7.

28. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is MnSO₄-x.H₂O, where x is zero or one.

29. An electrochemical cell as in claim 1, wherein said compound contained in said cathode includes a metal whose cation can assume at least two different non-zero oxidation numbers.

30. An electrochemical cell as in claim 29, wherein said metal is selected from the group consisting of Mn, Ce, Fe and Co.

31. An electrochemical cell as in claim 1, wherein said cathode further includes a material selected from the group consisting of a cation exchange material and a cation adsorber material.

32. An electrochemical cell as in claim 1, wherein said compound contained in said cathode can function as a proton-donator and a proton-acceptor.

33. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is a polymer.

34. An electrochemical cell as in claim 1, wherein said cathode further includes a catalyst for catalyzing cell cathodic reactions.

35. An electrochemical cell as in claim 1, wherein said cathode includes manganese sulfate and carbon, and wherein said anode includes chloranilic acid and carbon.

36. An electrochemical cell as in claim 1, wherein said compound contained in said cathode is selected from the group consisting of a non-hydrated form and hydrated forms of manganese sulfate, and wherein said compound contained in said anode is selected from the group consisting of a non-hydrated form and hydrated forms of chloranilic acid.

37. An electrochemical cell as in claim 1, wherein at least one of said anode and cathode further includes an electrically conductive material.

38. An electrochemical cell as in claim 37, wherein said electrically conductive material is selected from the group consisting of graphite, activated carbons and carbon materials.

40. An electrochemical cell as in claim 39, wherein at least one of said anode and cathode further includes a proton conducting material.

41. An electrochemical cell as in claim 40, wherein said proton conducting material is in a form selected from the group of forms consisting of a solid, a solution, a gel and a polymer.

42. An electrochemical cell as in claim 41, wherein said solution is an aqueous acid solution.

43. An electrochemical cell as in claim 42, wherein said aqueous acid solution is selected from the group consisting of sulfuric acid, methane sulfonic acid, nitric acid, hydrofluoric acid, hydrochloric acid, phosphoric acid, HBF₄, perchloric acid and pyrophosphoric acid, polyvinyl sulfonic acid, polyvinyl sulfuric acid, sulfurous acid and pyrophosphoric acid.

44. An electrochemical cell as in claim 41, wherein said solution is a liquid which includes:

(a) a solvent selected from the group consisting of a protic solvent and a non-aqueous aprotic solvent; and

(b) an acidic compound.

45. An electrochemical cell as in claim 41, wherein said solution includes a substance selected from the group consisting of sugars, starches and their derivatives.

46. An electrochemical cell as in claim 41, wherein said solution includes a salt.

47. An electrochemical cell as in claim 39, wherein said metal is selected from the group consisting of Sn, Ti, Cu, Cr, Al, W, Sb, Ir, Mo, Fe, Co and Bi.

48. An electrochemical cell as in claim 39, wherein said material contained in said anode is selected from the group consisting of the non-hydrated and the hydrated forms of those materials.

49. An electrochemical cell as in claim 39, wherein said material contained in said anode is a polymer.

50. An electrochemical cell as in claim 39, wherein said anode further includes a catalyst for catalyzing cell anodic reactions.

51. An electrochemical cell as in claim 39, wherein said anode further includes a material selected from the group consisting of a cation exchange material and a cation adsorber material.

52. An electrochemical cell as in claim 39, wherein said material contained in said anode is selected from the group consisting of a cation exchange material and a cation adsorber material treated with a solution containing a substance selected from the group consisting of Sn, Cu, Ti, Cr, Al, W, Sb, Ir, Mo, Fe Co and Bi salts and non-salt compounds.

53. An electrochemical cell as in claim 39, wherein said anode further includes a substance selected from the group consisting of chloranilic acid, tetrahydroxy quinone, phenol, catechol, hydroquinone, 3,4,5-trichloro salicylanilide and tetrachloro salicylanilide.

54. An electrochemical cell as in claim 39, wherein said non-liquid material in which protons are mobile includes a substance selected from the group consisting of a heteropolyacid in its hydrated form, a heteropolyacid in its non-hydrated form, a polymer-heteropolyacid blend, a single phase substance made of a heteropolyacid and a polymer, a multi-component substance which includes a heteropolyacid and a polymer, an anion exchanger which does not block protons, an anion adsorber which does not block protons, a cation adsorber, cation exchange materials, including their hydrogenated forms, chloro-sulfonated polyethylene, sulfonated polystyrene, sulfonated polysulfones and copolymers based on these materials, a perfluoronated sulfuric acid cation exchanger, cellulose acetate and cellulose triacetate membrane.

55. An electrochemical cell as in claim 39, wherein said non-liquid material in which protons are mobile is selected from the group consisting of sulfonated wax, polyvinylsulfonic acid, polyvinylphosphoric acid, sulfonated polyolefins, sulfonated polystyrenes, sulfonated phthalocyanines, sulfonated porphyrins, poly-2-acrylamido-2-methylpropanesulfonic acid, polyacrylic acid, polyvinyl sulfuric acid and polymethacrylic acid.

56. An electrochemical cell as in claim 39, wherein said non-liquid material in which protons are mobile includes a substance selected from the group consisting of an ion exchange material and an ion adsorber material.

57. An electrochemical cell as in claim 54, wherein said heteropolyacid is selected from the group consisting of molybdophosphoric acid. tungstophosphoric acid, molybdosilicic acid and tungstosilicic acid.

58. An electrochemical cell as in claim 54, wherein said polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), poly (2-vinylpyridine), poly (4-vinylpyridine), polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), polyvinylidene fluoride, polyhydroxyethylene, polyethyleneimine, polyacrylic acid, poly-2-ethyl-2-oxazoline, phenol formaldehyde resins, polyacrylamide, poly-N-substitued acrylamide, polymethacrylic acid, poly-N-vinylimidazole, poly-2-vinylpyridine, a polymer having a hydrophilic functional moiety, agar and agarose.

59. An electrochemical cell as in claim 55, wherein said polymer is selected from the group consisting of polyvinyl alcohol, polyethylene oxide, polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), poly (2-vinylpyridine), poly (4-vinylpyridine), polyvinyl acetate, polyacrylamide, polyethyleneimine, poly(vinyl pyrrolidone), polyvinylidene fluoride, polyhydroxyethylene, polyethyleneimine, polyacrylic acid, poly-2-ethyl-2-oxazoline, phenol formaldehyde resins, polyacrylamide, poly-N-substitued acrylamide, polymethacrylic acid, poly-N-vinylimidazole, poly-2-vinylpyridine, a polymer having a hydrophilic functional moiety, agar and agarose.

60. An electrochemical cell as in claim 58, wherein said polyvinyl alcohol polymer is in a form selected from the group of forms consisting of a fully hydrolyzed form and a partially hydrolyzed form.

61. An electrochemical cell as in claim 58, wherein said polyvinyl alcohol polymer has a molecular weight in the range between substantially 15,000 and substantially 186,000.

62. An electrochemical cell as in claim 39, wherein said non-liquid electrolyte further includes an electronically insulating metal oxide compound.

63. An electrochemical cell as in claim 62, wherein said metal oxide includes a metal selected from the group consisting of Al, Si, Ce, Ti, Mg and Fe.

64. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is selected from the group consisting of transition metal dichalcogenides, NiOOH, naphthalene, polycarbon fluoride, polydicarbon fluoride, Ni(OH)₂, monovalent silver oxide, divalent silver oxide, tantalum oxide molybdenum trioxide, niobium triselenide, Bi₂Sr₂CaCu₂O_8+y, Bi₂Sr₂Cu₁O_6+Y, YBa₂Cu₃O₇, fullerenes and a manganese compound.

65. An electrochemical cell as in claim 64, wherein said manganese compound is selected from the group consisting of manganese sulfate in its hydrated forms, manganese sulfate in its non-hydrated form, manganese dioxide in its chemical form, manganese dioxide in its electrolytic form. manganese dioxide in its natural form, lambda manganese dioxide and a manganese compound which is made by treating a spinel lithium manganese oxide of a nominal formula LiMn₂O₄ to remove the lithium.

66. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is selected from the group consisting of the non-hydrated and the hydrated forms of those compounds.

67. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is MnSO₄-x.H₂O, where x is an integer in the range of from 0 to 7.

68. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is MnSO₄-x.H₂O, where x is zero or one.

69. An electrochemical cell as in claim 39, wherein said compound contained in said cathode includes a metal whose cation can assume at least two different non-zero oxidation numbers.

70. An electrochemical cell as in claim 69, wherein said metal is selected from the group consisting of Mn, Ce, Fe and Co.

71. An electrochemical cell as in claim 39, wherein said cathode further includes a material selected from the group consisting of a cation exchange material and a cation adsorber material.

72. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is selected from the group consisting of a cation exchange material and a cation adsorber material treated with a solution containing a substance selected from the group consisting of Mn, Ce, Fe and Co salts and non-salt compounds.

73. An electrochemical cell as in claim 39, wherein said compound contained in said cathode can function as a proton-donator and a proton-acceptor.

74. An electrochemical cell as in claim 39, wherein said compound contained in said cathode is a polymer.

75. An electrochemical cell as in claim 39, wherein said cathode further includes a catalyst for catalyzing cell cathodic reactions.

76. An electrochemical cell as in claim 39, wherein at least one of said anode and cathode further include an electrically conductive material.

77. An electrochemical cell as in claim 76, wherein said electrically conductive material is selected from the group consisting of graphite, activated carbons and carbon materials.

39. An electrochemical cell comprising an anode, a cathode and a non-liquid electrolyte between, and in contact with, the anode and cathode, the cell operating under ambient conditions, wherein:

(a) said anode includes at least one material which includes a metal whose cation can assume at least two different non-zero oxidation numbers;

(b) said cathode includes a compound which forms an electrochemical couple with the above anode; and

(c) said electrolyte includes a non-liquid material in which protons are mobile.