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A preparation method of doped coating type single crystal ternary positive electrode material

A positive electrode material and coating technology, which is applied in the field of preparation of doped and coated single crystal positive electrode materials, can solve problems such as complicated steps, residual lithium on the structure surface, and lithium detachment from the structure, so as to improve surface stability and increase battery life. Effects of improving chemical properties and particle cracking

Active Publication Date: 2020-10-13
CNGR ADVANCED MATERIAL CO LTD
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Problems solved by technology

At present, the preparation of ternary nickel-cobalt-manganese cathodes with high capacity, high power, good cycle stability, and excellent safety performance is still not ideal. At present, the mainstream is still secondary particle polycrystalline cathodes, because the structural stability of secondary particles is relatively Poor so its voltage platform is still low
Coated and doped single crystal cathode is a good solution, but the current method still has great limitations, such as in the application number 201711173950 "Preparation method of high voltage single crystal lithium ion ternary cathode material ", the application number is 201610443127 "a doped micron-scale single crystal ternary cathode material and its preparation method" in the preparation method disclosed in the Chinese patent, the annealing temperature is too high, easy to make the structural lithium out and cause structural surface residues Too much lithium, and the steps are complicated, and the doping is not uniform enough

Method used

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  • A preparation method of doped coating type single crystal ternary positive electrode material
  • A preparation method of doped coating type single crystal ternary positive electrode material
  • A preparation method of doped coating type single crystal ternary positive electrode material

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preparation example Construction

[0030] A method for preparing a doped and coated single crystal ternary positive electrode material, comprising the following steps:

[0031] S1: Lithium oxide, three oxides of nickel, cobalt, manganese and oxide M c o d Mix and ball mill in proportion; the mass ratio of Li: (Ni+Co+Mn+M) is (1.02-1.12). The oxides of nickel are NiO, Ni 3 o 4 , NiO 2 、Ni 2 o 3 At least one of the cobalt oxides is Co 3 o 4 、CoO 2 、Co 2 o 3 At least one of the manganese oxides is MnO, Mn 3 o 4 , MnO 2 , Mn 2 o 3 At least one of the M c o d for Al 2 o 3 、TiO 2 , ZrO 2 , CaO, MgO at least one. In the implementation process, the conditions used for the ball milling reaction are: the speed is 250-350 rpm, the mass ratio of the ball to material is (1-3): 1, and the ball milling time is 1-4h. The appropriate ball milling conditions ensure the oxidation of the positive electrode material. The material can be fully mixed evenly, and the particle size of the mixture after ball milli...

Embodiment 1

[0037] Will Li 2 O, NiO, Co 2 o 3 , Mn 2 o 3 and Al 2 o 3 Mix and ball mill in proportion; the mass ratio of Li:(Ni+Co+Mn+Al) is 1.02:1. During the implementation, the rotational speed of the ball mill was 180rpm, the mass ratio of the ball to material was 3:1, and the ball milling time was 3h. Then the ball-milled mixture was sintered in an air atmosphere, specifically, the temperature was raised to 490° C. at a rate of 3° C. / min and then kept for 6 hours. Then it was sintered under an oxygen atmosphere, specifically, the temperature was raised to 810°C at a rate of 3°C / min and then kept for 20 hours to obtain a composition of LiNi 0.809 mn 0.13 co 0.06 al 0.001 o 2 single crystal ternary cathode material. Then the LiNi 0.809 mn 0.13 co 0.06 al 0.001 o 2 The single crystal ternary cathode material is ball milled with CaO nanoparticles (20 nm) according to the molar ratio of Ca:(Ni+Co+Mn+Al) of 0.05:1, wherein the ball mill speed is 270rpm, and the mass ratio ...

Embodiment 2

[0039] Will Li 2 O, NiO, Co 3 o 4 , Mn 3 o 4 and TiO 2 Mix and ball mill in proportion; the mass ratio of Li:(Ni+Co+Mn+Ti) is 1.06:1. During the implementation process, the speed of the ball mill was 185rpm, the mass ratio of the ball to material was 3:1, and the ball milling time was 2.5 h. Then the ball-milled mixture was sintered in an air atmosphere, specifically, the temperature was raised to 580° C. at a rate of 3° C. / min and then kept for 4 hours. Then it was sintered under an oxygen atmosphere, specifically, the heating rate was increased to 860 °C at a rate of 2 °C / min and then kept for 14 h to obtain a composition of LiNi 0.809 mn 0.13 co 0.06 Ti 0.001 o 2 single crystal ternary cathode material. Then the LiNi 0.809 mn 0.13 co 0.06 Ti 0.001 o 2 The single crystal ternary cathode material is based on Ti:(Ni+Co+Mn+Ti) molar ratio of 0.05:1 and TiO 2 Nanoparticles (40nm) were mixed ball milled, wherein the speed of the ball mill was 270rpm, the mass rat...

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Abstract

The invention discloses a method for preparing a doped-coated single crystal ternary positive electrode material in the technical field of lithium-ion batteries, which includes lithium oxide, three oxides of nickel, cobalt, and manganese, and oxide M c o d Proportionally mixed ball milling and two-stage sintering; the way of coating is to use nano-scale oxide N a o b Mix and sinter with doped single crystal ternary material. The present invention directly adopts oxide as the doping source, avoiding OH ‑ or CO 3 2‑ The water vapor or carbon dioxide gas generated after thermal decomposition ensures the stability of the solid-state reaction and reduces the possibility of crystal cracking. The use of nano-scale oxides ensures the uniformity of doping and the controllable thickness of the retaliation. The doping coating method adopted in the present invention improves the electrochemical performance of the single crystal ternary cathode material in terms of cycle, rate and the like.

Description

technical field [0001] The invention relates to the technical field of lithium-ion batteries, in particular to a method for preparing a doped-coated single-crystal cathode material. Background technique [0002] Lithium-ion batteries have great prospects for application in new energy vehicles due to their high capacity, low pollution, and high power. The ternary nickel-cobalt-manganese has a good development space as the positive electrode of lithium-ion batteries due to its strong comprehensive performance. At present, the preparation of ternary nickel-cobalt-manganese cathodes with high capacity, high power, good cycle stability, and excellent safety performance is still not ideal. At present, the mainstream is still secondary particle polycrystalline cathodes, because the structural stability of secondary particles is relatively Poor so its voltage platform is still low. Coated and doped single crystal cathode is a good solution, but the current method still has great li...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/505H01M4/525
CPCH01M4/505H01M4/525Y02E60/10C01G53/50C01P2002/52C01P2004/84C01P2004/03H01M10/0525
Inventor 管剑訚硕罗标刘辉
Owner CNGR ADVANCED MATERIAL CO LTD
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