Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery

• US 20070031730A1
• Filed: 10/10/2006
• Published: 02/08/2007
• Est. Priority Date: 09/18/1998
• Status: Active Grant

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Kawakami, Soichiro, Asao, Masaya
• Granted Patent: US 7,534,528 B2
• Time in Patent Office: Days
• US Class Current: 429/218.100
• CPC Class Codes: C22C 13/00 Alloys based on tin
• CPC Class Codes: C22C 45/00 Amorphous alloys making amorphous non-ferrous alloys C22C1/11
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/38 of elements or alloys
• 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 4/40 Alloys based on alkali metals
• CPC Class Codes: H01M 4/405 Alloys based on lithium
• CPC Class Codes: H01M 4/66 Selection of materials
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

An electrode material for an anode of a rechargeable lithium battery, containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition. For said formula Sn.A.X, A indicates at least one kind of an element selected from a group consisting of transition metal elements, X indicates at least one kind of an element selected from a group consisting of O, F, N, Mg, Ba, Sr, Ca, La, Ce, Si, Ge, C, P. B Pb Bi, Sb, Al, Ga, In, Tl Zn, Be, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, As, Se, Te, Li and S, where the element X is not always necessary to be contained. The content of the constituent element Sn of the amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %. An electrode structural body for a rechargeable lithium battery, comprising said electrode material for an anode and a collector comprising a material incapable of being alloyed with lithium in electrochemical reaction, and a rechargeable lithium battery having an anode comprising said electrode structural body.

Claims

1-58. -58. (canceled)

59. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, X indicates at least one kind of an element selected from the group consisting of O, F, N, Mg, Ba, Sr, Ca, La, Ce, Si, Ge, C, P, B, Pb, Bi, Sb, Al, Ga, In, Tl, Zn, Be, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, As, Se, Te, Li and S, where the element X is optionally present and the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %, wherein said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 1 m²/g, wherein if said particulate comprising said amorphous Sn.A.X alloy contains O, then said particulate comprising said amorphous Sn.A.X alloy contains O in an amount in the range of from 0.05% by weight to 5% by weight, and wherein if said particulate comprising said amorphous Sn.A.X alloy contains F, then said particulate comprising amorphous Sn.A.X alloy contains F in an amount in the range of from 0.05% by weight to 5% by weight.

60. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.2°

.

61. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.5°

.

62. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 1.0°

.

63. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=40°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.5°

.

64. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=40°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 1.0°

.

65. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 500 Å

.

66. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 200 Å

.

67. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 100 Å

.

68. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has an average particle size in a range of from 0.5 μ

m to 20 μ

m.

69. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has an average particle size in a range of from 0.5 μ

m to 10 μ

m.

70. An electrode material according to claim 59, wherein said transition metal element comprises at least one kind of an element selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, Ir, Pt, Au, Ti, V, Y, Sc, Zr, Nb, Hf. Ta, and W.

71. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy contains said alloy in an amount of more than 30% by weight.

72. An electrode material according to claim 59, wherein said electrode material contains a binder comprising a polymer which is either water-soluble or water-insoluble.

73. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy contains said alloy in an amount in a range of from 80% by weight to 100% by weight.

74. An electrode material according to claim 72, wherein the amount of said binder contained is in a range of from 1% by weight to 10% by weight.

85. An electrode material according to claim 59, wherein said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 5 m²/g.

86. An electrode material according to claim 59, wherein said amorphous Sn.A.X alloy contains Li in an amount in a range of from 2 atomic % to 30 atomic %.

88. An electrode structural body comprising said electrode material according to claim 59 and a collector comprising a material incapable of being alloyed with lithium in electrochemical reaction.

89. An electrode structural body according to claim 88, wherein the amount of said particulate comprising said amorphous Sn.A.X alloy in said electrode structural body is at least 25% by weight.

90. An electrode structural body according to claim 88, wherein said particulate comprising said amorphous Sn.A.X alloy in said electrode structural body contains at least 30% by weight of said amorphous Sn.A.X alloy.

91. An electrode structural body according to claim 88, wherein said electrode structural body has an electrode material layer comprising said electrode material and a binder on said collector.

92. An electrode structural body according to claim 91, wherein said binder comprises a polymer which is either water-soluble or water-insoluble.

93. A process for producing an electrode structural body, said process comprises a step of arranging said electrode material according to claim 59 on a collector.

94. A process for producing an electrode structural body according to claim 93, wherein said step includes a step of arranging said particulate comprising said amorphous Sn.A.X alloy on said collector by way of press forming.

95. A process for producing an electrode structural body according to claim 93, wherein said step includes a step of preparing a paste material by mixing said particulate comprising said amorphous Sn.A.X alloy with a binder and arranging said paste material on said collector.

96. A process for producing an electrode structural body according to claim 95, wherein a binder comprising a water-soluble polymer material is used as said binder.

75. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, and X indicates at least one kind of an element selected from the group consisting of O, F, N, Mg, Ba, Sr, Ca, La, Ce, Si, Ge, C, P, B, Pb, Bi, Sb, Al, Ga, In, Ti, Zn, Be, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, As, Se, Te, Li and S, where the element X is optionally present and the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %, wherein said particulate comprising said amorphous Sn.A.X alloy contains C, and said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 1 m²/g, wherein if said particulate comprising said amorphous Sn.A.X alloy contains O, then said particulate comprising said amorphous Sn.A.X alloy contains O in an amount in the range of from 0.05% by weight to 5% by weight, and wherein if said particulate comprising said amorphous Sn.A.X alloy contains F, then said particulate comprising amorphous Sn.A.X alloy contains F in an amount in the range of from 0.05% by weight to 5% by weight.

97. An electrode material according to claim 75, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.2°

.

98. An electrode material according to claim 75, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.5°

.

99. An electrode material according to claim 75, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=25°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 1.0°

.

100. An electrode material according to claim 75, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=40°

to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 0.5°

.

101. An electrode material according to claim 75, wherein said amorphous Sn.A.X alloy has a peak in a range of 2θ

=40 to 50°

in X-ray diffraction pattern obtained using a CuKα

radiation source, having a half width of more than 1.0°

.

102. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 500 Å

.

103. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 200 Å

.

104. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy has a crystallite size calculated from X-ray diffraction analysis, which is less than 100 Å

.

105. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy has an average particle size in a range of from 0.5 μ

m to 20 μ

m.

106. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy has an average particle size in a range of from 0.5 μ

m to 10 μ

m.

107. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy contains said alloy in an amount of more than 30% by weight.

108. An electrode material according to claim 75, wherein said electrode material contains a binder comprising a polymer which is either water-soluble or water-insoluble.

109. An electrode material according to claim 75, wherein said particulate comprising said amorphous Sn.A.X alloy contains said alloy in an amount in a range of from 80% by weight to 100% by weight.

110. An electrode material according to claim 108, wherein the amount of said binder contained is in a range of from 1% by weight to 10% by weight.

76. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, and X indicates at least one kind of an element selected from a group (a) consisting of Pb, Bi, Al, Ga, In, Tl, Zn, Be, Mg, Ca, and Sr;

a group (b) consisting of rare earth elements; and

a group (c) consisting of metalloide elements, wherein said group (b) consisting of rare earth elements consists of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and said group (c) consisting of metalloide elements consists of B, C, Si, P, Ge, As, Se, Sb, and Te, where the content of the constituent element Sn of the amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic % and said particulate comprising said amorphous Sn.A.X has a specific surface area of more than 1 m²/g.

77. An electrode material according to claim 76, wherein said amorphous Sn.A.X alloy contains two kinds of elements selected from said group (a), said group (b), and said group (c).

78. An electrode material according to claim 76, wherein said amorphous Sn.A.X alloy contains three kinds of elements selected from said group (a), said group (b), and said group (c).

79. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, and X indicates one kind of an element selected from the group consisting of Pb, Bi, Al, Ga, In, T, Zn, Be, Mg, Ca, and Sr and one kind of an element selected from the group consisting of rare earth elements, wherein said group consisting of rare earth elements consists of La, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, and Lu, and wherein the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %.

84. An electrode material according to claim 79, wherein said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 1 m²/g.

80. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said amorphous Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition elements, and X indicates one kind of an element selected from the group consisting of Pb, Bi, Al, Ga, In, Ti, Zn, Be, Mg, Ca, and Sr and one kind of an element selected from a group consisting of metalloide elements in X, wherein said group consisting of metalloide elements consists of B, C, Si, P, Ge, As, Se, Sb, and Te, and wherein the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %, and said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 1 m²/g.

81. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, and X indicates at least one kind of an element selected from the group consisting of metalloide elements and one kind of an element selected from the group consisting of rare earth elements, wherein said group consisting of rare earth elements consists of La, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, and Lu, and said group consisting of metalloide elements consists of B, C. Si, P, Ge, As, Se, Sb, and Te, and wherein the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %.

82. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A comprises one kind of an element selected from the group consisting of Co, Ni, Fe, Cr, and Cu, and X comprises one kind of an element selected from the group consisting of Si, Ge, Al, Zn, Ca, La, and Mg, and wherein the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %.

83. An electrode material according to claim 82, wherein said amorphous Sn.A.X alloy further contains one kind of an element selected from the group consisting of C, B, and P.

87. An electrode material containing a particulate comprising an amorphous Sn.A.X alloy with a substantially non-stoichiometric ratio composition, wherein in said formula Sn.A.X, A indicates at least one kind of an element selected from the group consisting of transition metal elements, X indicates at least one kind of an element selected from the group consisting of O, F, N, Mg, Ba, Sr, Ca, La, Ce, Si, Ge, C, P, B, Pb, Bi, Sb, Al, Ga, In, Tl, Zn, Be, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu, As, Se, Te, Li and S, where the element X is optionally present and the content of the constituent element Sn of said amorphous Sn.A.X alloy is Sn/(Sn+A+X)=20 to 80 atomic %, wherein said amorphous Sn.A.X alloy contains at least one kind of an element selected from the group consisting of N and S in an amount in a range of from 1 atomic % to 30 atomic %, wherein if said particulate comprising said amorphous Sn.A.X alloy contains O, then said particulate comprising said amorphous Sn.A.X alloy contains O in an amount in the range of from 0.05% by weight to 5% by weight, and wherein if said particulate comprising said amorphous Sn.A.X alloy contains F, then said particulate comprising amorphous Sn.A.X alloy contains F in an amount in the range of from 0.05% by weight to 5% by weight.

111. An electrode material according to claim 87, wherein said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 1 m²/g.

112. An electrode material according to claim 87, wherein said particulate comprising said amorphous Sn.A.X alloy has a specific surface area of more than 5 m²/g.

113. An electrode material according to claim 87, wherein said amorphous Sn.A.X alloy contains Li in an amount in a range of from 2 atomic % to 30 atomic %.