LITHIUM-ENRICHED SOLID SOLUTION ANODE COMPOSITE MATERIAL AND PREPARATION METHOD FOR LITHIUM-ENRICHED SOLID SOLUTION ANODE COMPOSITE MATERIAL, LITHIUM-ION BATTERY ANODE PLATE, AND LITHIUM-ION BATTERY

• US 20140099540A1
• Filed: 12/09/2013
• Published: 04/10/2014
• Est. Priority Date: 09/17/2012
• Status: Abandoned Application

• Current Assignee: Huawei Technologies Co., Ltd. (Huawei Investment & Holding Co., Ltd.)
• Original Assignee: Huawei Technologies Co., Ltd. (Huawei Investment & Holding Co., Ltd.)
• Inventors: Chen, Chaohui
• Application Number:
  US14/100,899
• Publication Number:
  US 20140099540A1
• Time in Patent Office: Days
• US Class Current: 429/211
• CPC Class Codes: C01G 45/1257 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
• CPC Class Codes: C01G 51/04 Oxides; Hydroxides
• CPC Class Codes: C01G 51/56 of the type [MnO3]2-, e.g. Li2[CoxMn1-xO3], Li2[MyCoxMn1-x-yO3
• CPC Class Codes: C01G 53/04 Oxides; Hydroxides
• CPC Class Codes: C01G 53/56 of the type [MnO3]2-, e.g. Li2[NixMn1-xO3], Li2[MyNixMn1-x-yO3
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Embodiments of the present application provide a lithium-enriched solid solution anode composite material, which includes xLi₂MnO₃.(1-x)MO and a LiMePO₄ layer that is clad on a surface of xLi₂MnO₃.(1-x)MO, where x<1, M is one or more selected from: Ni, Co, Mn, Ti, and Zr, and Me is one or more selected from: Co, Ni, V, and Mg. The lithium-enriched solid solution anode composite material has high stability in an electrolyte, may improve a cycle life, discharge capacity, rate performance, and initial charge-discharge efficiency of a lithium-ion battery, and is applicable in a condition of a high voltage greater than 4.6V. The embodiments of the present application further provide a preparation method for the lithium-enriched solid solution anode composite material, a lithium-ion battery anode plate containing the lithium-enriched solid solution anode composite material, and a lithium-ion battery containing the lithium-ion battery anode plate.

Claims

1. A lithium-enriched solid solution anode composite material, comprising:

xLi₂MnO₃.(1-x)MO and a LiMePO₄ layer that is clad on a surface of xLi₂MnO₃.(1-x)MO, wherein x<

1, M is one or more selected from;

Ni, Co, Mn, Ti, and Zr, and Me is one or more selected from;

Co, Ni, V, and Mg.

2. The lithium-enriched solid solution anode composite material according to claim 1, wherein a thickness of the LiMePO₄ layer is 1-10 nm.

3. The lithium-enriched solid solution anode composite material according to claim 1, wherein a part of Me in LiMePO₄ is clad on the surface of xLi₂MnO₃.(1-x)MO, and the other part of Me is embedded in a crystal lattice of xLi₂MnO₃.(1-x)MO.

4. A preparation method for a lithium-enriched solid solution anode composite material, the method comprising:

obtaining a compound xLi₂MnO₃.(1-x)MO, wherein x<

1, and M is one or a combination of;

Ni, Co, Mn, Ti, and Zr;

mixing ammonium dihydrogen phosphate, glycolic acid, Me(NO₃)₂, and lithium nitrate at a molar ratio of 1-3;

0.01-0.5;

1;

1-5, so as to obtain a Me-containing mixed solution; and

adding xLi₂MnO₃.(1-x)MO to the Me-containing mixed solution at a molar ratio of 50-100;

1, and performing ultrasonic dispersion, and placing, in a water bath, the Me-containing mixed solution that has undergone ultrasonic dispersion, and baking for 4-24 h in a stirring condition at a temperature of 50-100°

C.; and

grinding a baked solid product into powder, and then placing the powder in a furnace and annealing for 12-48 h at a temperature of 350-800°

C., so as to obtain a lithium-enriched solid solution anode composite material formed of xLi₂MnO₃.(1-x)MO and a LiMePO₄ layer that is clad on a surface of xLi₂MnO₃.(1-x)MO, wherein x<

1, M is one or more selected from;

Ni, Co, Mn, Ti, and Zr, and Me is one or more selected from;

Co, Ni, V, and Mg.

5. The preparation method for a lithium-enriched solid solution anode composite material according to claim 4, wherein annealing for 12-48 h at a temperature of 350-800°

C. comprises annealing for 24 h at a temperature of 450°

C.

6. The preparation method for a lithium-enriched solid solution anode composite material according to claim 4, wherein the molar ratio of the ammonium dihydrogen phosphate, glycolic acid, Me(NO₃)₂, and lithium nitrate is 1:

0.05;

1;

1, wherein Me is one or more selected from;

Co, Ni, V, and Mg.

7. The preparation method for a lithium-enriched solid solution anode composite material according to claim 4, wherein the molar ratio at which xLi₂MnO₃.(1-x)MO is added to the Me-containing mixed solution is 75:

1.

8. The preparation method for a lithium-enriched solid solution anode composite material according to claim 4, wherein baking comprises baking for 12 h in a stirring condition at a temperature of 80°

C.

9. A lithium-ion battery anode plate, comprising a current collector and a lithium-enriched solid solution anode composite material coated on the current collector, wherein the lithium-enriched solid solution anode composite material is formed by xLi₂MnO₃.(1-x)MO and a LiMePO₄ layer that is clad on a surface of xLi₂MnO₃.(1-x)MO, wherein x<

1, M is one or more selected from;

Ni, Co, Mn, Ti, and Zr, and Me is one or more selected from;

Co, Ni, V, and Mg.

10. A lithium-ion battery, comprising:

a lithium-ion battery anode plate;

a lithium-ion battery cathode plate;

a membrane;

an electrolyte; and

wherein the lithium-ion battery anode plate comprises a current collector and a lithium-enriched solid solution anode composite material coated on the current collector, and the lithium-enriched solid solution anode composite material is formed by xLi₂MnO₃.(1-x)MO and a LiMePO₄ layer that is clad on a surface of xLi₂MnO₃.(1-x)MO, wherein x<

1, M is one or more selected from;

Ni, Co, Mn, Ti, and Zr, and Me is one or more selected from;

Co, Ni, V, and Mg.