Electrode structural body, rechargeable battery provided with said electrode structural body, and rechargeable battery

• US 6,432,585 B1
• Filed: 01/28/1998
• Issued: 08/13/2002
• Est. Priority Date: 01/28/1997
• Status: Expired due to Term

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Asao, Masaya, Kosuzu, Takeshi, Kimura, Hironao, Kawakami, Soichiro, Kobayashi, Naoya
• Primary Examiner(s): Kalafut, Stephen
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/014,408
• Time in Patent Office: 1,658 Days
• Field of Search: 429/233, 429/209, 429/212, 429/218, 429/235
• US Class Current: 429/233
• CPC Class Codes: C23C 18/31 Coating with metals
• CPC Class Codes: C23C 18/50 with alloys based on iron, cobalt or nickel
• CPC Class Codes: C25D 3/32 characterised by the organic bath constituents used
• CPC Class Codes: C25D 3/60 containing more than 50% by weight of tin
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/24 Alkaline accumulators
• CPC Class Codes: H01M 10/32 Silver accumulators H01M10/34 takes precedence
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/244 Zinc electrodes
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/664 Ceramic materials
• CPC Class Codes: H01M 4/80 Porous plates, e.g. sintered carriers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

An electrode structural body comprising a plate-like shaped collector having opposite surfaces and an electrode material layer formed an at least one of said opposite surfaces of said collector, wherein said electrode material layer contains 35% by weight or more of a grained host matrix material of 5 to 60 in average particle size. A rechargeable battery provided with said electrode structural body as an electrode thereof.

Claims

1. An electrode structural body comprising a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector,

wherein said electrode material layer contains 35% by weight or more of a grained host matrix material of 0.5 to 60 μ

m in average particle size,

wherein said electrode material layer has a void ratio of 0.10 to 0.86,

wherein said electrode material layer has a density in a range of 1.00 to 6.56 g/cm³,

wherein the grained host matrix material comprises a grained material composed of one or more elements selected from the group consisting of Si, Ge, Sn, Pb, In, Mg, and Zn, and

wherein said collector is constituted of a metallic material which is inactive in a battery reaction selected from the group consisting of Cu, Ni, Fe, Ti, and alloys of two or more of these metals.

2. An electrode structural body according to claim 1, wherein said electrode structural body is used in a rechargeable battery in which charging and discharging are alternatively operated, and a plurality of pores of 0.10 to 10 μ

m in diameter are formed at a surface of the grained host matrix material layer after discharging.

3. An electrode structural body according to claim 1, wherein the electrode material layer has a thickness in a range of 5 to 500 μ

m.

4. An electrode structural body according to claim 1, wherein said electrode structural body is used in a rechargeable battery in which charging and discharging are alternately operated, and said electrode material layer of said electrode structural body in an unused state prior to operating either charging or discharging has a surface with a surface roughness of 1 to 60 μ

m in peak-to-valley elevation.

5. An electrode structural body according to claim 1, wherein the collector has a surface provided with at least a protruded portion and said protruded portion is covered by a material having a resistivity which is greater than that of a material constituting said collector.

6. An electrode structural body according to claim 5, wherein the material by which the protruded portion of the collector is covered is an oxide of one or more elements selected from the group consisting of Ni, Zn, Sn, and In.

7. An electrode structural body according to claim 1, wherein the average particle size of the grained host matrix material is in a range of 0.5 to 20 μ

m.

8. An electrode structural body according to claim 1, wherein the grained host matrix material comprises a grained material whose resistivity in bulk state is in a range of 1×

10<sup>−

6</sup> to 1×

10⁰ Ω

·

cm.

9. An electrode structural body according to claim 1, wherein the grained host matrix material comprises a grained material whose resistivity in bulk state is in a range of 1×

10<sup>−

5</sup> to 1×

10<sup>−

1</sup> Ω

·

cm.

10. An electrode structural body according to claim 1, wherein the electrode material layer contains 50% by weight or more of the grained host matrix material.

11. An electrode structural body according to claim 1, wherein said electrode structural body is used as an electrode of a rechargeable battery in which oxidation-reduction reaction of lithium is used, and the grained host matrix material of the electrode material layer comprises a grained matrix composed of one or more elements selected from the group consisting of Si, Sn, and In.

12. An electrode structural body according to claim 1, wherein said electrode structural body is used as an electrode of a rechargeable battery in which oxidation-reduction reaction of zinc is used, and the granted host matrix material of the electrode material layer comprises a grained material composed of one or more members selected from the group consisting of zinc oxide and zinc alloy.

13. An electrode structural body according to claim 1, wherein the grained host matrix material comprises a grained material whose surfaces are covered by a layer comprising one or more kinds of metallic materials.

14. An electrode structural body according to claim 1, wherein the electrode material layer contains an electrically conductive auxiliary in addition to the grained host matrix material.

15. An electrode structural body according to claim 14, wherein the electrically conductive auxiliary comprises a carbonous material or a metallic material.

16. An electrode structural body according to claim 14, wherein the electrode material layer contains the electrically conductive auxiliary in an amount of 1 to 30% by weight.

17. An electrode structural body according to claim 14, wherein the electrically conductive auxiliary is shaped in a form selected from the group consisting of a spherical form, a flake form, a filament form, a fibrous form, a spike form, and a needle form.

18. An electrode structural body according to claim 1, wherein the electrode material layer contains an organic polymer in addition to the grained host matrix material.

19. An electrode structural body according to claim 18, wherein the electrode material layer contains the organic polymer in an amount of 2 to 20% by weight.

20. An electrode structural body according to claim 1, wherein the electrode material layer contains an electrically conductive auxiliary and an organic polymer in addition to the grained host matrix material.

21. An electrode structural body according to claim 1, wherein the grained host matrix material of the electrode material layer is constituted by a metallic tin material or a tin alloy material.

22. An electrode structural body according to claim 21, wherein the tin alloy material has a tin element content of 50% to less than 100%.

23. An electrode structural body according to claim 21 wherein the tin alloy material is an alloy of Sn with one or more elements selected from the group consisting of Sb, Bi, Pb, Ni, Cu, Ag, and Zn.

24. An electrode structural body according to claim 21, wherein the grained host matrix material constituted by the metallic tin material or the tin alloy material is 10 to 50 nm in crystallite size.

25. An electrode structural body according to claim 21, wherein the electrode material layer has a void ratio in the range of 0.31 to 0.73.

26. An electrode structural body according to claim 21, wherein the electrode material layer has a density in a range of 2.00 to 6.00 g/cm³.

27. An electrode structural body according to claim 21, wherein said electrode structural body is used in a rechargeable battery in which charging and discharging are alternatively operated, and a plurality of pores of 0.10 to 10 μ

m in diameter are formed at a surface of the grained host matrix material layer after discharging.

28. An electrode structural body according to claim 21, wherein the electrode material layer has a thickness in a range of 5 to 500 μ

m.

29. An electrode structural body according to claim 21, wherein said electrode structural body is used in a rechargeable battery in which charging and discharging are alternately operated, and said electrode material layer of said electrode structural body in an unused state prior to operating either charging or discharging has a surface with a surface roughness of 1 to 60 μ

m in peak-to-valley elevation.

30. An electrode structural body according to claim 21, wherein the electrode material layer contains one or more elements selected from the group consisting of C, N, O, F, and S.

31. An electrode structural body according to claim 30, wherein the one or more elements selected from the group consisting of C, N, O, F, and S are contained in a layer region of the electrode material layer on the side opposite the collector at a concentration which is greater than that of said one or more elements contained in a layer region of said electrode material layer which is adjacent to the collector.

32. An electrode structural body according to claim 21, wherein the grained host matrix material constituted by the metallic tin material or the tin alloy material comprises particles of the metallic tin material or the tin alloy material containing tin oxide among the particles or on surfaces of the particles.

33. An electrode structural body according to claim 21, wherein the electrode material layer contains an organic polymer, a carbonous material, or both an organic polymer and a carbonous material in addition to the grained metallic tin host matrix material or the grained tin alloy host matrix material.

34. An electrode structural body according to claim 21, wherein said electrode structural body is used as an anode of a rechargeable battery in which oxidation-reduction reaction of lithium is used.

35. A electrode structural body according to any of claim 1, 2-10, 11-24, 25 and 26-34 which has an additional layer comprising 80 to 98% by weight of an inorganic material and 2 to 20% by weight of an organic polymer on the electrode material layer comprising the grained matrix material formed on the collector.

36. An electrode structural body according to claim 35, wherein the grained host matrix material in bulk state at 20°

C. has a resistivity which is greater than that of the material constituting the collector, and the inorganic material in bulk state at 20°

C. has a specific resistance which is greater than said resistivity of the grained host matrix material.

37. An electrode structural body according to claim 36, wherein the resistivity of the inorganic material is in a range of 1×

10<sup>−

4</sup> to 1×

10² Ω

·

cm.

38. An electrode structural body according to claim 36, wherein the resistivity of the inorganic material is in a range of 1×

10<sup>−

4</sup> to 1×

10¹ Ω

·

cm.

39. An electrode structural body according to claim 35, wherein the additional layer has a thickness in a range of 1 to 30 μ

m.

80. An electrode structural body according to claim 1, wherein the electrode material layer comprises a mixture of said grained host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

81. An electrode structural body according to claim 1, wherein said grained host matrix material comprises a Si powder with a purity of less than 99% which contains an impurity comprising one or more elements selected from the group consisting of Al, Ca, Cr, Fe, Mg, Mn, and Ni.

82. An electrode structural body according to claim 81, wherein said Si powder comprises particles whose surfaces are partially covered by one or more materials selected from the group consisting of Cu, Ni, Ag and Sn.

83. An electrode structural body according to claim 81 to 82, wherein the electrode material layer comprises a mixture of said grained host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

40. A rechargeable battery comprising at least an anode, a cathode, and an electrolyte in which charging and discharging are alternately operated using oxidation-reduction reaction of an active material of said anode, characterized in that said anode comprises a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector,

wherein said electrode material layer contains 35% by weight or more of a grained host matrix material of 0.5 to 60 μ

m in average particle size,

wherein said electrode material layer has a void ratio of 0.10 to 0.86,

wherein said electrode material layer has a density in a range of 1.00 to 6.65 g/cm³,

wherein the graned host matrix material comprises a grained material composed of one or more elements selected from the group consisting of Si, Ge, Sn, Pb, In, Mg, and Zn, and

wherein said collector is constituted of a metallic material which is inactive in a battery reaction selected from the group consisting of Cu, Ni, Fe, Ti, and alloys of two or more of these metals.

41. A rechargeable battery according to claim 40, wherein a plurality of pores of 0.10 to 10 μ

m in diameter are formed at a surface of the grained host matrix material layer after discharging.

42. A rechargeable battery according to claim 40, wherein the electrode material layer has a thickness in a range of 5 to 500 μ

m.

43. A rechargeable battery according to claim 40, wherein the electrode material layer of the anode in an unused state prior to operating either charging or discharging has a surface with a surface roughness of 1 to 60 μ

m in peak-to-valley evaluation.

44. A rechargeable battery according to claim 40, wherein the collector has a surface provided with at least a protruded portion and said protruded portion is covered by a material having a resistivity which is greater than that of a material constituting said collector.

45. A rechargeable battery according to claim 40, wherein the material by which the protruded portion of the collector is covered is an oxide of one or more elements selected from the group consisting of Ni, Zn, Sn, and In.

46. A rechargeable battery according to claim 40, wherein the average particle size of the grained host matrix material is in a range of 0.5 to 20 μ

m.

47. A rechargeable battery according to claim 40, wherein the grained host matrix material comprises a grained material whose resistivity in bulk state is in a range of 1×

10<sup>−

6</sup> to 1×

10⁰ Ω

·

cm.

48. A rechargeable battery according to claim 40, wherein the grained host matrix material comprises a grained material whose resistivity in bulk state is in a range of 1×

10<sup>−

5</sup> to 1×

10<sup>−

1</sup> Ω

·

cm.

49. A rechargeable battery according to claim 40, wherein the electrode material layer contains 50% by weight or more of the grained host matrix material.

50. A rechargeable battery according to claim 40, wherein said rechargeable batter is a rechargeable battery in which oxidation-reduction reaction of lithium is used, and the grained host matrix material of electrode material layer comprises a grained material composed of one or more elements selected from the group consisting of Si, Sn, and In.

51. A rechargeable battery according to claim 40, wherein said rechargeable batter is a rechargeable battery in which oxidation-reduction reaction of zinc is used, and the grained host matrix material of the electrode material layer comprises a grained material composed of one or more members selected from the group consisting of zinc oxide and zinc alloy.

52. A rechargeable battery according to claim 40, wherein the grained host matrix material comprises a grained material whose surfaces are covered by a layer comprising one or more kinds of metallic materials.

53. A rechargeable battery according to claim 40, wherein the electrode material layer contains an electrically conductive auxiliary in addition to the grained host matrix material.

54. A rechargeable battery according to claim 53, wherein the electrically conductive auxiliary comprises a carbonous material or a metallic material.

55. A rechargeable battery according to claim 54, wherein the electrode material layer contains the electrically conductive auxiliary in an amount of 1 to 30% by weight.

56. A rechargeable battery according to claim 53, wherein the electrically conductive auxiliary is shaped in a form selected from the group consisting of a spherical form, a flake form, a filament form, a fibrous form, a spike form, and a needle form.

57. A rechargeable battery according to claim 40, wherein the electrode material layer contains an organic polymer in addition to the grained host matrix material.

58. A rechargeable battery according to claim 57, wherein the electrode material layer contains the organic polymer in an amount of 2 to 20% by weight.

59. A rechargeable battery according to claim 40, wherein the electrode material layer contains an electrically conductive auxiliary and an organic polymer in addition to the grained best matrix material.

60. A rechargeable batter according to claim 40, wherein the grained host matrix material of the electrode material layer is constituted by a metallic tin material or a tin alloy material.

61. A rechargeable battery according to claim 60, wherein the tin alloy material has a tin element content of 50% to less than 100%.

62. A rechargeable battery according to claim 60, wherein the tin alloy material is an alloy of Sn with one or more elements selected from the group consisting of Sb, Bi, Pb, Ni, Cu, Ag, and Zn.

63. A rechargeable battery according to claim 60, wherein the grained host matrix material constituted by the metallic tin material or the tin alloy material is 10 to 50 nm in crystallite size.

64. A rechargeable battery according to claim 60, wherein the electrode material layer has a void ratio in the range of 0.31 to 0.73.

65. A rechargeable battery according to claim 60, wherein the electrode material layer has a density in a range of 2.00 to 6.00 g/cm³.

66. A rechargeable battery according to claim 60, wherein a plurality of pores of 0.10 to 10 μ

m, diameter are formed at a surface of the grained host matrix material layer after discharging.

67. A rechargeable battery according to claim 60, wherein the electrode material layer has a thickness in a range of 5 to 500 μ

m.

68. A rechargeable battery according to claim 60, wherein the electrode material layer of the anode in an unused state prior to operating either charging or discharging has a surface with a surface roughness of 1 to 60 μ

m in peak-to-valley elevation.

69. A rechargeable battery according to claim 60, wherein the electrode material layer contains one or more elements selected from the group consisting of C, N, O, F, and S.

70. A rechargeable battery according to claim 69, wherein the one or more elements selected from the group consisting of C, N, O, F, and S are contained in a layer region of the electrode material layer on the side opposite the collector at a concentration which is greater than that of said one or more elements contained in a layer region of said electrode material layer which is adjacent to the collector.

71. A rechargeable battery according to claim 60, wherein the grained host matrix material constituted by the metallic tin material or the tin alloy material comprises particles of the metallic tin material or the tin alloy material containing tin oxide among the particles or on surfaces of the particles.

72. A rechargeable battery according to claim 60, wherein the electrode material layer contains an organic polymer, a carbonous material, or both an organic polymer and a carbonous material in addition to the grained metallic tin host matrix material or the grained tin alloy host matrix material.

73. A rechargeable battery according to claim 60, wherein said rechargeable battery is a rechargeable battery in which oxidation-reduction reaction of lithium is used.

74. A rechargeable battery according to claim 60, wherein said rechargeable battery is a rechargeable battery in which oxidation-reduction reaction of lithium is used, and wherein the anode comprising the electrode material layer in a charged state has an elemental ratio of lithium element contained therein to the tin element contained therein in a range of 0.1 to 3.52.

75. A rechargeable battery according to claim 40, wherein an additional layer comprising 80 to 98% by weight of an inorganic material and 2 to 20% by weight of an organic polymer is provided on the electrode material layer comprising the grained matrix material formed on the collector.

76. A rechargeable battery according to claim 75, wherein the grained host matrix material in bulk state at 20°

C. has a resistivity which is greater than that of the material constituting the collector, and the inorganic material in bulk state at 20°

C. has a resistivity which is greater than said specific resistance of the grained host matrix material in bulk state.

77. A rechargeable battery according to claim 76, wherein the resistivity of the inorganic material is in a range of 1×

10^-4 to 1×

10¹ Ω

·

cm.

78. A rechargeable battery according to claim 76, wherein the resistivity of the inorganic material is in a range of 1×

10^-4 to 1×

10¹ Ω

·

cm.

79. A rechargeable battery according to claim 75, wherein the additional layer has a thickness in a range of 1 to 30 μ

m.

87. A rechargeable battery according to claim 40, wherein the electrode material layer comprises a mixture of said grained host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

88. A rechargeable battery according to claim 40, wherein said grained host matrix material comprises a Si powder with a purity of less than 99% which contains an impurity comprising one or more elements selected from the group consisting of Al, Ca, Cr, Fe, Mg, Mn, and Ni.

89. A rechargeable battery according to claim 88, wherein said Si powder comprises particles whose surfaces are partially covered by one or more materials selected from the group consisting of Cu, Ni, Ag and Sn.

90. A rechargeable battery according to claim 88 or 89, wherein the electrode material layer comprises a mixture of said grained host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

84. An electrode structural body comprising a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector, wherein said electrode material layer contains 35% by weight or more of a grained host matrix material of 0.5 to 60 μ

m in average particle size, said grained host matrix material comprising a Si powder with a purity of less than 99% which contains an impurity comprising one or more elements selected from the group consisting of Al, Ca, Cr, Fe, Mg, Mn, and Ni.

85. An electrode structural body according to claim 84, wherein said Si powder comprises particles whose surfaces are partially covered by one or more materials selected from group consisting of Cu, Ni, Ag and Sn.

86. An electrode structural body according to claim 84 or 85, wherein the electrode material layer comprises a mixture of said grained host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

91. A rechargeable battery comprising at least an anode, a cathode, and an electrolyte in which charging and discharging are alternately operated using oxidation-reduction reaction of an active material of said anode, characterized in that said anode comprises a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector, said electrode material layer containing 35% by weight or more of a grained host matrix material 0.5 to 60 μ

m in average particle size, said grained host matrix material comprising a Si powder with a purity of less than 99% which contains an impurity comprising one or more elements selected from the group consisting of Al, Ca, Cr, Fe, Mg, Mn, and Ni.

92. A rechargeable battery according to claim 91, wherein said Si powder comprises particles whose surfaces are partially covered by one or more materials selected from the group consisting of Cu, Ni, Ag and Sn.

93. A rechargeable battery according to claim 91 or 92, wherein the electrode material layer comprises a mixture of said granted host matrix material and an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials.

94. An electrode structural body comprising a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector, wherein said electrode material layer contains 35% by weight or more of a grained host matrix material of 0.5 to 60 μ

m in average particle size and has a density in a range of 1.00 to 6.56 g/cm³, said grained host matrix material comprising a grained material composed of at least an element selected from the group consisting of Si, Ge, Sn, Pb, In, Mg and Zn, said electrode material layer comprising a mixture of said grained host matrix material, an electrically said grained host matrix material, an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials, and a binder, and said collector being constituted by a metallic material which is inactive in a battery reaction selected from the group consisting of Cu, Ni, Fe, Ti, and alloys of two or more these metals.

95. A rechargeable battery comprising at least an anode, a cathode, and an electrolyte and in which charging and discharging are alternately operated using oxidation-reduction reaction of an active material of said anode, characterized in that said anode comprises a plate shaped collector having opposite surfaces and an electrode material layer formed on at least one of said opposite surfaces of said collector, said electrode material layer containing 35% by weight or more of a grained host matrix material of 0.5 to 60 μ

m in average particle size and having a density in a range of 1.00 to 6.56 g/cm³, said grained host matrix material comprising a grained material composed of at least an element selected from the group consisting of Si, Ge, Sn, Pb, In, Mg and Zn, said electrode material layer comprising a mixture of said grained host matrix material, an electrically conductive auxiliary comprising one or more materials selected from the group consisting of carbonous materials and metallic materials, and a binder, and said collector being constituted by a metallic material which is inactive in a battery reaction selected from the group consisting of Cu, Ni, Fe, Ti, and alloys of two or more these metals.