Claims
- 1. A compound comprising a composition Ax(M′1-aM″a)y(XD4)z, Ax(M′1-aM″a)y(DXD4)z, or Ax(M′1-aM″a)y(X2D7)z, having a conductivity at 27° C. of at least about 10−8 S/cm, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x is equal to or greater than 0, y and z are greater than 0 and have values such that x, plus y(1-a) times a formal valence or valences of M′, plus ya times a formal valence or valence of M″, is equal to z times a formal valence of the XD4, X2D7, or DXD4 group.
- 2. A compound comprising a composition (A1-aM″a)xM′y(XD4)z, (A1-aM″a)xM′y(DXD4)z, or (A1-aM″a)xM′y(X2D7)z, having a conductivity at 27° C. of at least about 10−8 S/cm, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x, y, and z are greater than zero and have values such that (1-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group.
- 3. A compound comprising a composition (Ab-aM″a)xM′y(XD4)z, (Ab-aM″a)xM′y(DXD4)z, or (Ab-aM″a)xM′y(X2D7)z, having a conductivity at 27° C. of at least about 10−8 S/cm, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, a≦b≦1, and x, y, and z are greater than zero and have values such that (b-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group.
- 4. A compound comprising a composition Ax(M′1-aM″a)y(XD4)z, Ax(M′1-aM″a)y(DXD4)z, or Ax(M′1-aM″a)y(X2D7)z, having a specific surface area of at least 15 m2/g, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x is equal to or greater than 0, y and z are greater than 0 and have values such that x, plus y(1-a) times a formal valence or valences of M′, plus ya times a formal valence or valence of M″, is equal to z times a formal valence of the XD4, X2D7, or DXD4 group.
- 5. A compound comprising a composition (A1-aM″a)xM′y(XD4)z, (A1-aM″a)xM′y(DXD4)z, or (A1-aM″a)xM′y(X2D7)z, having a specific surface area of at least 15 m2/g, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x, y, and z are greater than zero and have values such that (1-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group.
- 6. A compound comprising a composition (Ab-aM″a)xM′y(XD4)z, (Ab-aM″a)xM′y(DXD4)z, or (Ab-aM″a)xM′y(X2D7)z, having a specific surface area of at least 15 m2/g, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, a≦b≦1, and x, y, and z are greater than zero and have values such that (b-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group.
- 7. A compound comprising a composition Ax(M′1-aM″a)y(XD4)z, Ax(M′1-aM″a)y(DXD4)z, or Ax(M′1-aM″a)y(X2D7)z, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x is equal to or greater than 0, y and z are greater than 0 and have values such that x, plus y(1-a) times a formal valence or valences of M′, plus ya times a formal valence or valence of M″, is equal to z times a formal valence of the XD4, X2D7, or DXD4 group, crystallizing in an ordered or partially disordered structure of the olivine (AxMXO4), NASICON (Ax(M′,M″)2(XO4)3), VOPO4, LiFe(P2O7) or Fe4(P2O7)3 structure-types, and additionally having a molar concentration of the metals (M′+M″) relative to the concentration of the elements X that exceeds the ideal stoichiometric ratio y/z of the prototype compounds by at least 0.0001.
- 8. A compound comprising a composition (A1-aM″a)xM′y(XD4)z, (A1-aM″a)xM′y(DXD4)z, or (A1-aM″a)xM′y(X2D7)z, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, and x, y, and z are greater than zero and have values such that (1-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group, crystallizing in an ordered or partially disordered structure of the olivine (AxMXO4), NASICON (Ax(M′,M″)2(XO4)3), VOPO4, LiFe(P2O7) or Fe4(P2O7)3 structure-types, and additionally having a molar concentration of the metals (M′+M″) relative to the concentration of the elements X that exceeds the ideal stoichiometric ratio y/z of the prototype compounds by at least 0.0001.
- 9. A compound comprising a composition (Ab-aM″a)xM′y(XD4)z, (Ab-aM″a)xM′y(DXD4)z, or (Ab-aM″a)xM′y(X2D7)z, wherein A is at least one of an alkali metal or hydrogen, M′ is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M″ any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0001<a≦0.1, a≦b≦1, and x, y, and z are greater than zero and have values such that (b-a)x plus the quantity ax times the formal valence or valences of M″ plus y times the formal valence or valences of M′ is equal to z times the formal valence of the XD4, X2D7 or DXD4 group, crystallizing in an ordered or partially disordered structure of the olivine (AxMXO4), NASICON (Ax(M′,M″)2(XO4)3), VOPO4, LiFe(P2O7) or Fe4(P2O7)3 structure-types, and additionally having a molar concentration of the metals (M′+M″) relative to the concentration of the elements X that exceeds the ideal stoichiometric ratio y/z of the prototype compounds by at least 0.0001.
- 10. The compound of claim 1, wherein the compound can intercalate at least one of an alkali or hydrogen.
- 11. The compound of claim 1, wherein M″ has a formal valence greater than 1+ as an ion in the compound.
- 12. The compound of claim 1, wherein M″ is any of aluminum, titanium, zirconium, niobium, tantalum, tungsten, and magnesium.
- 13. The compound of claim 1, wherein A is lithium.
- 14. The compound of claim 1, wherein X is phosphorus.
- 15. The compound of claim 1, wherein D is oxygen.
- 16. The compound of claim 1, wherein M′ is any of iron, vanadium, chromium, manganese, cobalt or nickel.
- 17. The compound of claim 1, wherein M′ is Fe2+.
- 18. The compound of claim 1, wherein at least one of M′ and M″ has an ionic radius less than the ionic radius of Fe2+.
- 19. The compound of claim 1, wherein the compound is substantially free of silicon.
- 20. The compound of claim 1, wherein the compound has a crystalline structure in which at least one of the M′ or M″ atoms occupy lattice sites coordinated by anion polyhedra, said polyhedra forming a continuous network through the structure by sharing at least one of vertices, corners, edges, or faces.
- 21. The compound of claim 20, wherein the polyhedra of the continuous network are filled with transition-metals.
- 22. The compound of claim 20, wherein the polyhedral units are octahedra or distorted octahedra.
- 23. The compound of claim 20, wherein polyhedral units share corners and edges with other polyhedral units containing M′ or M″.
- 24. The compound of claim 1, wherein the compound is an n-type conductor.
- 25. The compound of claim 1, wherein the compound comprises a mixture of an n-type conductor and a p-type conductor.
- 26. The compound of claim 1, wherein the compound is a p-type conductor.
- 27. The compound of claim 1, wherein A is lithium and during preparation or use the compound is substantially fully delithiated.
- 28. The compound of claim 1, wherein the compound is a p-type conductor when substantially fully lithiated and an n-type conductor when substantially fully delithiated.
- 29. The compound of claim 1, wherein the compound, upon delithiation, undergoes phase-separation into a substantially lithiated compound and a substantially delithiated compound, each of which have an electronic conductivity of at least 10−6 S/cm.
- 30. The compound of claim 1, wherein x has a value between zero and about 1, y is about 1, and z is about 1.
- 31. The compound of claim 1, wherein x has a value between zero and about 1, and y is about 1.
- 32. The compound of claim 1, wherein x has a value between zero and about 5, y is about 2, and z is about 3.
- 33. The compound of claim 1, wherein x has a value between zero and about 2, y is about 1, and z is about 1.
- 34. The compound of claim 1, wherein x has a value between zero and about 4, y is about 4, and z is about 3.
- 35. The compound of claim 1, wherein 0<x/(x+y+z)≦⅔.
- 36. The compound of claim 1, wherein the compound has at least one of an ordered or partially disordered structure of the olivine (AxMXO4), NASICON (Ax(M′,M″)2(XO4)3), VOPO4, LiFe(P2O7) or Fe4(P2O7)3 structure-types.
- 37. The compound of claim 1, wherein the compound is LiFePO4 containing additional metals M″.
- 38. The compound of claim 1, wherein the compound has an olivine structure and contains in crystalline solid solution, amongst the metals M′ and M″, simultaneously metal ions of at least one type that is oxidizable and another that is reducible at 23° C.
- 39. The compound of claim 1, wherein the compound has an olivine structure and contains in crystalline solid solution, amongst the metals M′ and M″, simultaneously the metal ions Fe2+ and Fe3+, Mn2+ and Mn3+, Co2+ and Co3+, Ni2+ and Ni3+, V2+ and V3+, or Cr2+ and Cr3+, with the ion of lesser concentration being at least 10 parts per million of the sum of the two ion concentrations.
- 40. The compound of claim 1, wherein the compound has an olivine structure, M′ includes Fe, and at least one of M′ and M″ has an ionic radius less than the ionic radius of Fe2+.
- 41. The compound of claim 1, wherein the compound has an olivine structure, and M″ includes at least one metal with ionic radius less than the average ionic radius of the M′ ions.
- 42. The compound of claim 1, wherein the compound has an olivine structure with a crystalline solid solution of formula Axvacy(M′1-aM″a)XO4, Ax-a-yM″avacyM′XO4, Ax(M′1-a-yM″avacy)XO4 or Ax-aM″aM′1-yvacyXO4, wherein vac represents a vacancy in any of an M1 and M2 site of the primary crystallites.
- 43. The compound of claim 1, wherein said compound has the ordered olivine structure type and A is lithium and is substituted onto a M2 site of a crystal of the composition at a concentration of at least about 1018 per cubic centimeter.
- 44. The compound of claim 1, wherein said compound has the ordered olivine structure type and A is lithium and x and a are selected such that lithium can substitute into an M2 site of a crystal of the composition as an acceptor defect.
- 45. The compound of claim 1, wherein the composition is any of Lix(M′1-aM″a)PO4, LixM″aM′PO4, Lix(M′1-a-yM″aLiy)PO4, or Lix-aM″aM′1-yLiyPO4.
- 46. The compound of claim 1, wherein the composition is any of Lix(Fe1-aM″a)PO4, LixM″aFePO4, Lix(Fe1-a-yM″aLiy)PO4, or Lix-al M″aFe1-yLiyPO4.
- 47. The compound of claim 1, wherein the composition is Lixvac1-x(M′1-aM″a)PO4, LixM″avac1-a-yM′PO4, Lix(M′1-a-yM″avacy)PO4 or Lix-aM″aM″1-yvacyPO4, wherein vac represents a vacancy in a structure of the compound.
- 48. The compound of claim 1, wherein the composition is Lixvac1-x(Fe1-aM″a)PO4, LixM″avac1-a-yFePO4, Lix(Fe1-a-yM″avacy)PO4 or Lix-aM″aFe1-yvacyPO4, wherein vac represents a vacancy in a structure of the compound.
- 49. The compound of claim 1, wherein the compound has an olivine structure and at least a portion of A occupies a M1 site.
- 50. The compound of claim 1, wherein M″ is substantially in solid solution in a crystal structure of the compound.
- 51. The compound of claim 1, wherein M″ is partially in solid solution in a crystal structure of the compound at a concentration of at least 0.01 atom % relative to the concentration of M′, the balance appearing as an additional phase.
- 52. The compound of claim 1, wherein the concentration is at least 0.02 mole %.
- 53. The compound of claim 1, wherein the concentration is at least 0.05 mole %.
- 54. The compound of claim 1, wherein the concentration is at least 0.1 mole %.
- 55. The compound of claim 1, wherein the compound comprises doped LiFePO4 in an olivine structure.
- 56. The compound of claim 1, wherein the compound forms primary crystallites, at least 50% of which have a smallest dimension less than 500 nm.
- 57. The compound of claim 56, wherein the smallest dimension is less than 200 nm.
- 58. The compound of claim 56, wherein the smallest dimension is less than 100 nm.
- 59. The compound of claim 56, wherein the smallest dimension is less than 50 nm.
- 60. The compound of claim 56, wherein the smallest dimension is less than 20 nm.
- 61. The compounds of claim 56, wherein the smallest dimension is less than 10 nm.
- 62. The compound of claim 56, wherein the primary crystallites form an interconnected porous network
- 63. The compound of claim 56, wherein at least about 25% of the surface area of the primary crystallites is available for contact with an electrolyte.
- 64. The compound of claim 56, wherein at least about 50% of the surface area of the primary crystallites is in contact with an electrolyte.
- 65. The compound of claim 1, wherein the compound has a specific surface area of at least about 10 m2/g.
- 66. The compound of claim 1, wherein the specific surface area is at least about 20 m2/g.
- 67. The compound of claim 1, wherein the specific surface area is at least about 30 m2/g.
- 68. The compound of claim 1, wherein the specific surface area is at least about 40 m2/g.
- 69. The compound of claim 1, wherein the specific surface area is at least about 50 m2/g.
- 70. The compound of claim 1, wherein the conductivity is at least about 10−7 S/cm.
- 71. The compound of claim 1, wherein the conductivity is at least about 10−6 S/cm.
- 72. The compound of claim 1, wherein the conductivity is at least about 10−5 S/cm.
- 73. The compound of claim 1, wherein the conductivity is at least about 10−4 S/cm.
- 74. The compound of claim 1, wherein the conductivity is at least about 10−3 S/cm.
- 75. The compound of claim 1, wherein the conductivity is at least about 10−2 S/cm.
- 76. The compound of claim 1, further comprising less than about 15 weight percent of a conductivity-enhancing additive based on the weight of the composition.
- 77. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 10 weight percent.
- 78. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 7 weight percent.
- 79. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 5 weight percent.
- 80. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 3 weight percent.
- 81. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 2 weight percent.
- 82. The compound of claim 76, wherein the conductivity-enhancing additive is present in an amount of less than about 1 weight percent.
- 83. The compound of claim 76, wherein the conductivity-enhancing additive comprises carbon.
- 84. The compound of claim 1, wherein the compound forms at least part of an electrode in an electrochemical device.
- 85. The compound of claim 84, wherein the electrochemical device is a fuel cell.
- 86. The compound of claim 1, wherein the compound is a mixed proton conducting and electronically conducting material.
- 87. The compound of claim 1, wherein the compound is a gas separation membrane comprising a mixed proton conducting and electronically conducting material.
- 88. The compound of claim 1, wherein the compound is a gas separation membrane comprising a mixed proton conducting and electronically conducting material comprising LiFePO4.
- 89. The compound of claim 1 formed by mixing an alkali metal or hydrogen salt, a first-row transition metal compound, a salt of at least one of phosphorus, sulfur, arsenic, molybdenum and tungsten, and an ethoxide or methoxide of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal; milling the mixture; and heat treating the mixture at a first temperature sufficient to form at least one of an olivine, NASICON, VOPO4, LiFe(P2O7) or Fe4(P2O7)3 structure.
- 90. A method of forming a compound, comprising:
mixing an alkali metal or hydrogen salt, a first-row transition metal salt, a salt of at least one of phosphorus, sulfur, arsenic, silicon, aluminum, boron, vanadium, molybdenum and tungsten, and a salt of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal; milling the mixture; and heat treating the mixture at a temperature between 300-900° C.
- 91. The method of claim 90, wherein the alkali metal salt is a metal carbonate.
- 92. The method of claim 90, wherein the alkali metal salt is lithium carbonate.
- 93. The method of claim 90, wherein the alkali metal salt is LiPO3.
- 94. The method of claim 90, wherein the salt of the first-row transition metal is a metal oxalate.
- 95. The method of claim 90, wherein the salt of the first-row transition metal is a metal acetate.
- 96. The method of claim 90, wherein the salt of the first-row transition metal is a metal oxide.
- 97. The method of claim 90, wherein the salt of the first-row transition metal is iron oxalate.
- 98. The method of claim 90, wherein the salt of the first-row transition metal is iron acetate.
- 99. The method of claim 90, wherein the salt of the first-row transition metal is iron oxide.
- 100. The method of claim 90, wherein the salt of at least one of phosphorus, sulfur, arsenic, silicon, aluminum, boron, vanadium, molybdenum and tungsten, is ammonium phosphate.
- 101. The method of claim 90, wherein the salt of at least one of phosphorus, sulfur, arsenic, silicon, aluminum, boron, vanadium, molybdenum and tungsten, is LiPO3.
- 102. The method of claim 90, wherein the salt of at least one of phosphorus, sulfur, arsenic, silicon, aluminum, boron, vanadium, molybdenum and tungsten, is P2O5.
- 103. The method of claim 90, wherein the salt of at least one of phosphorus, sulfur, arsenic, silicon, aluminum, boron, vanadium, molybdenum and tungsten, is phosphoric acid.
- 104. The method of claim 90, wherein the salt of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal is a metal alkoxide.
- 105. The method of claim 90, wherein the salt of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal is a metal oxide.
- 106. The method of claim 90, wherein the salt of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal is a metal acetate.
- 107. The method of claim 90, wherein the salt of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal is a metal nitrate.
- 108. The method of claim 90, wherein the salts comprise lithium carbonate, iron oxalate, ammonium phosphate, and an alkoxide of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal.
- 109. The method of claim 90, wherein the salts comprise lithium carbonate, iron oxalate, ammonium phosphate, and an alkoxide of any of magnesium, aluminum, iron, manganese, titanium, zirconium, niobium, tantalum, or tungsten.
- 110. The method of claim 90, wherein the salts comprise lithium carbonate, iron oxalate, ammonium phosphate, and an oxide of any of magnesium, aluminum, iron, titanium, zirconium, niobium, tantalum, or tungsten.
- 111. The method of claim 90, wherein the salts comprise LiPO3, FeO, and an alkoxide of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal.
- 112. The method of claim 90, wherein-the salts comprise LiPO3, FeO, and an oxide of any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal.
- 113. The method of claim 90, wherein the salts comprise LiPO3, FeO, and an alkoxide of any of magnesium, aluminum, iron, manganese, titanium, zirconium, niobium, tantalum, or tungsten.
- 114. The method of claim 90, wherein mixing is performed while the mixture is under a nonreactive atmosphere.
- 115. The method of claim 90, wherein heat-treating is performed while the mixture is under a gaseous atmosphere with an oxygen partial pressure of less than about 10−4 atmospheres.
- 116. The method of claim 90, wherein heat-treating is performed while the mixture is under a gaseous atmosphere with an oxygen partial pressure of less than about 10−5 atmospheres.
- 117. The method of claim 90, wherein heat-treating is performed while the mixture is under a gaseous atmosphere with an oxygen partial pressure of less than about 10−6 atmospheres.
- 118. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially nitrogen gas.
- 119. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially argon gas.
- 120. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially hydrogen gas.
- 121. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially a mixture of nitrogen and hydrogen gas.
- 122. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially a mixture of carbon monoxide and carbon dioxide gas.
- 123. The method of claim 90, wherein heat-treating is performed in a gaseous atmosphere that is substantially nitrogen gas.
- 124. The method of claim 90, further comprising heat treatment at two temperatures, the second heat treatment being at a temperature higher the first temperature.
- 125. The method of claim 90, further comprising heat treatment at two temperatures, the first temperature being from 300-400° C. and the second temperature being from 500-900° C.
- 126. A method of doping a material to form a lithium or hydrogen storage compound, comprising:
selecting a starting material to be doped, in conjunction with selection of milling equipment comprising a dopant for doping the starting material at a predetermined level of dopant; milling the starting material in the milling equipment; and recovering from the milling step a material suitable for forming a lithium or hydrogen storage compound comprising the starting material doped with the dopant at the predetermined level.
- 127. The method of claim 126, wherein the lithium or hydrogen storage compound is any one of the compounds of claims 1-3.
- 128. The method of claim 126, wherein the dopant added from the milling equipment is at least one of zirconium, aluminum, iron, carbon, or fluorine.
- 129. The method of claim 126, wherein the dopant comprises at least zirconium and the milling equipment comprises zirconia milling media or containers.
- 130. The method of claim 126, wherein the dopant comprises at least aluminum and the milling equipment comprises aluminum oxide milling media or containers.
- 131. The method of claim 126, wherein the dopant comprises at least iron and the milling equipment comprises iron or steel milling media or containers.
- 132. The method of claim 126, wherein the dopant comprises at least carbon and the milling equipment comprises polymer milling media or containers.
- 133. The method of claim 126, wherein said milling equipment includes at least one of polypropylene-bearing, polystyrene-bearing, or polytetrafluoroethylene-bearing milling media or milling containers.
- 134. The method of claim 126, wherein the dopant comprises at least fluorine and the milling equipment comprises fluoropolymer milling media or containers.
- 135. An electrode comprising the compound of claim 1 and having a material energy density that while:
charging or discharging at a rate ≧30 mA per g of storage compound, is greater than 350 Wh/kg, or charging or discharging at a rate ≧150 mA per g of storage compound, is greater than 280 Wh/kg, or charging or discharging at a rate ≧300 mA per g of storage compound, is greater than 270 Wh/kg, or charging or discharging at a rate ≧750 mA per g of storage compound, is greater than 250 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 180 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 40 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 10 Wh/kg.
- 136. The electrode composition of claim 135, having a material energy density that while:
charging or discharging at a rate ≧30 mA per g of storage compound, is greater than 420 Wh/kg, or charging or discharging at a rate ≧150 mA per g of storage compound, is greater than 400 Wh/kg, or charging or discharging at a rate ≧300 mA per g of storage compound, is greater than 370 Wh/kg, or charging or discharging at a rate ≧750 mA per g of storage compound, is greater than 350 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 270 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 150 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 80 Wh/kg, or charging or discharging at a rate ≧6 A per g of storage compound, is greater than 35 Wh/kg, or charging or discharging at a rate ≧7.5 A per g of storage compound, is greater than 50 Wh/kg, or charging or discharging at a rate ≧15 A per g of storage compound, is greater than 10 Wh/kg,
- 137. The electrode composition of claim 135, having a material energy density that while:
charging or discharging at a rate ≧30 mA per g of storage compound, is greater than 475 Wh/kg, or charging or discharging at a rate ≧150 mA per g of storage compound, is greater than 450 Wh/kg, or charging or discharging at a rate ≧300 mA per g of storage compound, is greater than 430 Wh/kg, or charging or discharging at a rate ≧750 mA per g of storage compound, is greater than 390 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 350 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 300 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 250 Wh/kg, or charging or discharging at a rate ≧7.5 A per g of storage compound, is greater than 150 Wh/kg, or charging or discharging at a rate ≧11 A per g of storage compound, is greater than 50 Wh/kg, or charging or discharging at a rate ≧15 A per g of storage compound, is greater than 30 Wh/kg.
- 138. An electrode comprising a lithium storage compound other than one of ordered or partially ordered rocksalt crystal structure type, or spinel crystal structure type, or vanadium oxide or manganese oxide, the electrode having a material energy density that while:
charging or discharging at a rate ≧800 mA per g of storage compound, is greater than 250 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 180 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 40 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 10 Wh/kg.
- 139. The electrode of claim 138, having a material energy density that while:
charging or discharging at a rate ≧800 mA per g of storage compound, is greater than 350 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 270 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 150 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 80 Wh/kg, or charging or discharging at a rate ≧6 A per g of storage compound, is greater than 35 Wh/kg, or charging or discharging at a rate ≧7.5 A per g of storage compound, is greater than 50 Wh/kg, or charging or discharging at a rate ≧15 A per g of storage compound, is greater than 10 Wh/kg,
- 140. The electrode of claim 138, having a material energy density that while:
charging or discharging at a rate ≧800 mA per g of storage compound, is greater than 390 Wh/kg, or charging or discharging at a rate ≧1.5 A per g of storage compound, is greater than 350 Wh/kg, or charging or discharging at a rate ≧3 A per g of storage compound, is greater than 300 Wh/kg, or charging or discharging at a rate ≧4.5 A per g of storage compound, is greater than 250 Wh/kg, or charging or discharging at a rate ≧7.5 A per g of storage compound, is greater than 150 Wh/kg, or charging or discharging at a rate ≧11 A per g of storage compound, is greater than 50 Wh/kg, or charging or discharging at a rate ≧15 A per g of storage compound, is greater than 30 Wh/kg.
- 141. An electrode comprising the lithium storage compound of claim 1.
- 142. The electrode of claim 141, wherein the electrode comprises a sheet or a mesh coated or impregnated with the storage compound.
- 143. The electrode of claim 141, wherein the electrode comprises a metal foil coated one or both sides with the storage compound.
- 144. The electrode of claim 141, wherein the electrode is a sheet or mesh of electronically conductive material coated with a loading of at least 4 mg of said storage compound per square centimeter of projected area of the sheet or mesh.
- 145. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with a loading of at least 8 mg of said storage compound per square centimeter of projected area of the sheet or mesh.
- 146. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with a loading of at least 10 mg of said storage compound per square centimeter of projected area of the sheet or mesh.
- 147. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with a loading of at least 14 mg of said storage compound per square centimeter of projected area of the sheet or mesh.
- 148. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with a loading of at least 20 mg of said storage compound per square centimeter of projected area of the sheet or mesh.
- 149. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 20 micrometers.
- 150. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 40 micrometers.
- 151. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 60 micrometers.
- 152. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 80 micrometers.
- 153. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 100 micrometers.
- 154. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 150 micrometers.
- 155. The electrode of claim 141, wherein said electrode is a sheet or mesh of electronically conductive material coated with said storage material and has a total thickness of at least 200 micrometers.
- 156. A storage battery cell comprising:
a positive electrode; a negative electrode; and a separator positioned between the positive electrode and the negative electrode. wherein at least one of the positive electrode or negative electrode comprises the compound of claim 1.
- 157. The storage battery cell of claim 156 wherein the cell is a disposable battery cell.
- 158. The storage battery cell of claim 156 wherein the cell is a rechargeable battery cell.
- 159. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 0.25 Wh.
- 160. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 1 Wh.
- 161. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 5 Wh.
- 162. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 10 Wh.
- 163. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 20 Wh.
- 164. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 30 Wh.
- 165. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 40 Wh.
- 166. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 50 Wh.
- 167. The storage battery cell of claim 156 wherein the cell exhibits upon discharge an energy of at least 100 Wh.
- 168. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least 30 Wh/kg or a volumetric energy density of at least 100 Wh/liter.
- 169. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least 50 Wh/kg or a volumetric energy density of at least 200 Wh/liter.
- 170. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least 90 Wh/kg or a volumetric energy density of at least 300 Wh/liter.
- 171. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric power density of at least 100 W/kg or a volumetric power density of at least 350 W/liter.
- 172. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric power density of at least 500 W/kg or a volumetric power density of at least 500 W/liter.
- 173. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric power density of at least 1000 W/kg or a volumetric power density of at least 1000 W/liter.
- 174. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric power density of at least 2000 W/kg or a volumetric power density of at least 2000 Wh/liter.
- 175. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least:
30 Wh/kg at a power density of at least 500 W/kg, or 20 Wh/kg at a power density of at least 1000 W/kg, or 10 Wh/kg at a power density of at least 1500 W/kg, or 5 Wh/kg at a power density of at least 2000 W/kg, or 2 Wh/kg at a power density of at least 2500 W/kg, or 1 Wh/kg at a power density of at least 3000 W/kg.
- 176. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least:
50 Wh/kg at a power density of at least 500 W/kg, or 40 Wh/kg at a power density of at least 1000 W/kg, or 20 Wh/kg at a power density of at least 2000 W/kg, or 10 Wh/kg at a power density of at least 3000 W/kg, or 4 Wh/kg at a power density of at least 4000 W/kg, or 1 Wh/kg at a power density of at least 5000 W/kg.
- 177. The storage battery cell of claim 156 wherein the cell exhibits upon discharge a gravimetric energy density of at least:
80 Wh/kg at a power density of at least 1000 W/kg, or 70 Wh/kg at a power density of at least 2000 W/kg, or 60 Wh/kg at a power density of at least 3000 W/kg, or 55 Wh/kg at a power density of at least 4000 W/kg, or 50 Wh/kg at a power density of at least 5000 W/kg, or 30 Wh/kg at a power density of at least 6000 W/kg, or 10 Wh/kg at a power density of at least 8000 W/kg.
- 178. The cell of claims 156, wherein the lithium storage compound is any other than a compound with an ordered or partially disordered rocksalt or spinel structure type, or vanadium oxide, or manganese oxide.
RELATED APPLICATIONS
[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Serial No. 60/343,060, filed on Dec. 21, 2001, U.S. Provisional Application Serial No. 60/388,721, filed on Jun. 14, 2002, and U.S. Provisional Application Serial No. 60/412,656, filed on Sep. 20, 2002, the disclosures of which are herein incorporated by reference.
Provisional Applications (3)
|
Number |
Date |
Country |
|
60343060 |
Dec 2001 |
US |
|
60388721 |
Jun 2002 |
US |
|
60412656 |
Sep 2002 |
US |