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A modified lithium-rich manganese-based positive electrode material and preparation method thereof

A lithium-rich manganese-based, positive electrode material technology, applied in the direction of positive electrodes, active material electrodes, battery electrodes, etc., can solve problems such as structural damage, spinel structure collapse, accelerated capacity, etc., and achieve a simple and easy-to-control, excellent preparation method Effects of cycle performance and good rate performance

Active Publication Date: 2021-01-26
宁波富理电池材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, there are many literatures and patents at home and abroad have reported Al 2 o 3 , MnO 2 , AlPO 4 , ZrO 2 、TiO 2 Coating lithium-rich materials with other metal oxides can reduce the first irreversible capacity loss of lithium-rich materials and improve the cycle performance of materials, but their rate performance has not been effectively improved.
As A.Manthiram et al. (US7678503B2) reported a modification method of oxide-coated lithium-rich cathode materials, the oxides include Al 2 o 3 , ZrO 2 , CeO 2 , SiO 2 One or more of ZnO and ZnO, although the initial discharge capacity and coulombic efficiency of the material have been improved after coating modification, the rate performance of the lithium-rich material has not been significantly improved by coating; the publication number is JP-A-2002 -260659 Japanese patent using spinel LiMn 2 o 4 Coating the positive electrode material improves its cycle performance at high temperature, but during the charging and discharging process, the valence state change of Mn is prone to produce the Jahn-Teller effect, resulting in the collapse of the spinel structure, especially in the high temperature and high voltage system. Obviously, accelerated capacity decay

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  • A modified lithium-rich manganese-based positive electrode material and preparation method thereof
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  • A modified lithium-rich manganese-based positive electrode material and preparation method thereof

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preparation example Construction

[0049] The present invention also provides a method for preparing the modified lithium-rich manganese-based positive electrode material described in the above technical solution, comprising the following steps:

[0050] a) will M' 2+ metal salts and M" 3+ The metal salt is dissolved in the dispersion liquid of the lithium-rich material, and then an interlayer anion agent and a precipitant are added to adjust the pH value of the reaction system to react to obtain a lithium-rich manganese-based cathode material precursor;

[0051] b) Calcining the lithium-rich manganese-based cathode material precursor obtained in step a), to obtain a modified lithium-rich manganese-based cathode material.

[0052] The present invention first M' 2+ metal salts and M" 3+ The metal salt is dissolved in the dispersion liquid of the lithium-rich material, and then an interlayer anion agent and a precipitating agent are added to adjust the pH value of the reaction system for the reaction to obtain...

Embodiment 1

[0078] (1) The lithium-rich manganese-based cathode material Li[Li 0.144 Ni 0.136 co 0.136 mn 0.544 ]O 2 Disperse in deionized water, prepare 100g / L lithium-rich manganese-based positive electrode material dispersion liquid, according to the mass ratio of lithium-rich manganese-based positive electrode material and metal composite oxide 99:1 composite preparation drug raw material dosage, Co(NO 3 ) 2 ·6H 2 O and Al(NO 3 ) 3 9H 2 O is added to the above-mentioned dispersion liquid according to the molar ratio of 2:1, and then gradually added Na with a molar ratio of 1:12 2 CO 3 Mixed solution with NaOH, adjust the pH of the reaction system to 10, then place it in a water bath at 100°C for 12 hours, centrifuge and dry to obtain a lithium-rich manganese-based cathode material precursor;

[0079] (2) Calcining the lithium-rich manganese-based cathode material precursor obtained in step (1) at 500° C. for 4 hours to obtain a modified lithium-rich manganese-based cathode m...

Embodiment 2

[0084] (1) The lithium-rich manganese-based cathode material Li[Li 0.144 Ni 0.136 co 0.136 mn 0.544 ]O 2 Disperse in deionized water, prepare 100g / L lithium-rich manganese-based positive electrode material dispersion liquid, according to the mass ratio of lithium-rich manganese-based positive electrode material and metal composite oxide 99.5:0.5 composite drug raw material dosage, Co(NO 3 ) 2 ·6H 2 O and Al(NO 3 ) 3 9H 2 O is added to the above-mentioned dispersion liquid according to the molar ratio of 2:1, and then gradually added Na with a molar ratio of 1:12 2 CO 3 Mixed solution with NaOH, adjust the pH of the reaction system to 10, then place it in a water bath at 100°C for 12 hours, centrifuge and dry to obtain a lithium-rich manganese-based cathode material precursor;

[0085] (2) Calcining the lithium-rich manganese-based cathode material precursor obtained in step (1) at 500° C. for 4 hours to obtain a modified lithium-rich manganese-based cathode material....

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Abstract

The invention provides a modified lithium-rich manganese-based positive electrode material, which is composed of a lithium-rich material and a metal composite oxide; the metal composite oxide is made of layered double hydroxyl composite metal hydroxide. Compared with the prior art, the metal composite oxide in the modified lithium-rich manganese-based cathode material provided by the present invention has a stable spinel structure, which can not only stabilize the surface structure of the lithium-rich material, but also stabilize the three-dimensional structure of the spinel structure. The channels are beneficial for the intercalation and extraction of lithium ions, so that the obtained modified lithium-rich manganese-based cathode materials also have good rate performance. Experimental results show that the first coulombic efficiency of the modified lithium-rich manganese-based cathode material provided by the present invention is about 91%, and it has better cycle performance and better rate performance than pure lithium-rich manganese-based cathode material.

Description

technical field [0001] The invention relates to the technical field of lithium ion batteries, and more specifically relates to a modified lithium-rich manganese-based positive electrode material and a preparation method thereof. Background technique [0002] Lithium-ion batteries have the advantages of no memory effect, high safety, high specific energy, and low self-discharge rate, and are widely used in mobile devices, notebook computers, mobile phone communications, and power batteries. At present, power batteries face problems such as short cruising range, poor cycle performance and insufficient safety, which seriously restrict their rapid development and application. In recent years, the specific discharge capacity of lithium-rich manganese-based cathode materials has reached 300mAh / g, and its energy density can exceed 300Wh / Kg, which is regarded as an ideal choice for a new generation of power lithium batteries. However, Li-rich manganese-based cathode materials have ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/36H01M4/505H01M4/525H01M10/0525
CPCH01M4/362H01M4/505H01M4/525H01M10/0525H01M2004/021H01M2004/028Y02E60/10
Inventor 张国华夏永高刘兆平
Owner 宁波富理电池材料科技有限公司