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High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method

A composite positive electrode material and lithium-ion battery technology, applied in battery electrodes, circuits, electrical components, etc., can solve problems such as expensive cobalt, low safety of LiCoO2, and easy damage to the crystal structure

Active Publication Date: 2014-05-14
湖南美特新材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the actual specific capacity of lithium cobalt oxide is about 145mA h / g, which is far lower than its theoretical specific capacity of 274mA h / g
In addition, due to the high price of cobalt, the high cost of lithium cobaltate material preparation also restricts the further development of this material
In order to make the material exhibit a higher specific capacity, the charge cut-off voltage of the material can be increased, thereby increasing the volumetric energy density of the material, but when charged to a higher voltage, the crystal structure of the material is easily destroyed
In addition, LiCoO prepared by prior art 2 Less secure and more expensive

Method used

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  • High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method
  • High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method
  • High-voltage high-compaction composite positive electrode material of lithium ion battery and preparation method

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Experimental program
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Effect test

Embodiment 1

[0027] with TiO 2 , Li 2 CO 3 and Co 3 o 4 As the raw material, the molar ratio of substances is n(TiO 2 ):n(Li 2 CO 3 ):n(Co 3 o 4 )=0.005:0.5:0.995 After mixing with a high-efficiency mixer, calcination at 1000°C for 6 hours to obtain Ti-doped LiCo 0.995 Ti 0.005 o 2 Matrix A (particle size D 50 is 12 μm). With Li 2 CO 3 and Ni 0.6 co 0.2 mn 0.2 (OH) 2 The precursor is the raw material, and the molar ratio of the substances is n(Li 2 CO 3 ):n(Ni 0.6 co 0.2 mn 0.2 (OH) 2 )=0.5:1 After mixing with a high-efficiency mixer, calcination at 1000°C for 6 hours to synthesize LiNi 0.6 co 0.2 mn 0.2 o 2 Matrix B (particle size D 50 is 6 μm). Substrate A: Substrate B: Flux (flux is MgO and LiF, the mass ratio is 1:1) mass ratio = 50:50:0.08, mixed with a high-efficiency mixer for 30 minutes, and then added to account for the total mass of matrix A and matrix B 0.5% PVDF NMP solution (solid content: 10%), dispersed and kneaded for 1 hour, then calcined at 1...

Embodiment 2

[0029] With MgO, Li 2 CO 3 and Co 3 o 4 As raw material, the material molar ratio is n(MgO):n(Li 2 CO 3 ):n(Co 3 o 4 )=0.002:0.5:0.998, mixed with a high-efficiency mixer, and then fired at 1000°C for 10 hours to obtain Mg-doped LiCo 0.998 Mg 0.002 o 2 Matrix A (particle size D 50 15-16μm). With Li 2 CO 3 and Ni 0.6 co 0.2 mn 0.2 (OH) 2 The precursor is the raw material, and the molar ratio of the substances is n(Li 2 CO 3 ):n(Ni 0.6 co 0.2 mn 0.2 (OH) 2 )=0.5:1 After mixing with a high-efficiency mixer, calcining at 900°C for 8 hours to synthesize LiNi 0.6 co 0.2 mn 0.2 o 2 Matrix B (particle size D 50 6-7μm). Substrate A: Substrate B: Flux (TiO 2 with MgF 2 , the mass ratio is 1:1) mass ratio = 50:50:0.08, first mix with a high-efficiency mixer for 30 minutes, then add 0.5% PVDF NMP solution (solid content is 10%), disperse and knead for 1 hour and then heat at 900 ° C Roasting 12h. Using aluminum nitrate as the coating source, through a wet pr...

Embodiment 3

[0031] With CeO 2 , Li 2 CO 3 and Co 3 o 4 As the raw material, the molar ratio of substances is n(CeO 2 ):n(Li 2 CO 3 ):n(Co 3 o 4 )=0.1:0.5:0.9, mixed with a high-efficiency mixer, and then fired at 700°C for 10 hours to obtain Ce-doped LiCo 0.9 Ce 0.1 o 2Matrix A (particle size D 50 6-8μm). With Li 2 CO 3 and Ni 0.6 co 0.2 mn 0.2 (OH) 2 The precursor is the raw material, and the molar ratio of the substances is n(Li 2 CO 3 ):n(Ni 0.6 co 0.2 mn 0.2 (OH) 2 )=0.5:1 After mixing with a high-efficiency mixer, calcination at 950°C for 10 hours to synthesize LiNi 0.6 co 0.2 mn 0.2 o 2 Matrix B (particle size D 50 12-14μm). Substrate A: Substrate B: Flux (TiO 2 With LiF, the mass ratio is 1:1) mass ratio = 60:40:0.1, first mix with a high-efficiency mixer for 30 minutes, then add 0.5% PVDF NMP solution (solid content is 10%), disperse and knead for 1 hour at 950 ° C Roasting at high temperature for 10h. Finally, the liquid phase method was used to co...

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Abstract

The invention relates to a high-voltage high-compaction composite positive electrode material of a lithium ion battery. The composite positive electrode material comprises LiCo<1-x>NxMyO<2-y>, wherein the x is more than or equal to 0.002 and is less than or equal to 0.1, the y is more than or equal to 0 and is less than or equal to 0.05, the M is at least one of F<-1>,S<2->, Cl<-> and PO4<3->,and the N is at least one of Ti<4+>, Zr<4+>, Mn<3+>, Sn<4+>, Ce<4+>, Ir<4+>, Mg<2+>, Al<3+>, V<5+>, Nb<3+> and La<3+>; the composite positive electrode material also comprises LiNimConMn<1-m-n>O2 and a coating compound coating the surfaces of the LiCo<1-x>NxMyO<2-y> and the LiNimConMn<1-m-n>O2, wherein the m is more than or equal to 0.2 and is less than or equal to 0.8, the n is more than or equal to 0.1 and less than or equal to 0.4, the 1-m-n is more than or equal to 0 and is less than or equal to 0.7, the coating compound is at least one of an oxide compound of Mc and Li2MdO3, and the Mc and the Md are independent from each other and are respectively selected from one of Al, Ti, Mn, Zr and Sn. The high-voltage high-compaction composite positive electrode material provided by the invention has the advantages that the security is high, the cost is low, the compacted density is greater than or equal to 4.10g / cm<3>, the charging cut-off voltage of the lithium ion battery prepared from the material is greater than or equal to 4.3V, the first reversible capacity at the cut-off voltage of 4.4V is greater than or equal to 180mA.h / g, and the composite positive electrode material is applied to a high voltage condition and has excellent electrochemical properties.

Description

technical field [0001] The invention belongs to the field of lithium-ion batteries, and in particular relates to a high-voltage, high-pressure lithium-ion battery composite cathode material and a preparation method. Background technique [0002] As a new type of green energy storage device, lithium-ion battery occupies a pivotal position in the field of secondary batteries due to its superior performance. With the rapid development of the 4G mobile phone market and small electric tools, higher requirements are placed on the energy density and safety performance of lithium-ion batteries. The batteries of Apple and Samsung's new generation of high-end electronic products have been replaced with high-voltage batteries with a charging cut-off voltage of 4.3V or 4.35V. With the increase of the charging cut-off voltage, the energy density of the battery has been significantly improved, which is of great significance for meeting the higher volume specific energy and battery life r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505H01M4/525
CPCH01M4/505H01M4/525H01M4/62Y02E60/10
Inventor 李碧平米成欧阳全胜朱贤徐刘志立汤志军熊学
Owner 湖南美特新材料科技有限公司
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