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Modification method of single-crystal ternary positive electrode material

A cathode material and single crystal technology, which is applied in the field of modification of single crystal ternary cathode materials, can solve the problems of poor cycle performance, large polarization of lithium ion batteries, reduced structural stability of ternary cathode materials, etc. Internal resistance, the effect of improving cycle stability

Inactive Publication Date: 2020-12-15
宜宾锂宝新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is that in the doping modification process in the prior art, the doped ion part does not enter the interior of the ternary positive electrode material, and a similar coating layer is formed on the surface of the material, thereby reducing the impact of the ternary positive electrode material on the charging and discharging process. Structural stability in the medium, while increasing the internal resistance of the material, resulting in large polarization and poor cycle performance of lithium-ion batteries, providing a modification method for single crystal ternary cathode materials

Method used

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  • Modification method of single-crystal ternary positive electrode material
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  • Modification method of single-crystal ternary positive electrode material

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Preparation of zirconium-doped single crystal material LiNi 0.5 co 0.16 Zr 0.04 mn 0.3 o 2 :

[0033] The ternary positive electrode precursor Ni with a particle size of 3.8 μm 0.5 co 0.2 mn 0.3 (OH) 2 , zirconium sulfate, mixed according to the molar ratio of 1:0.04 according to the mass ratio, added in the container containing water, configured into a mixed solution with a solid content of 5-60wt.%, after spray drying, at a temperature of 400 ° C, In an air atmosphere and a box-type furnace, sintering for 10 h at an air flow rate of 40 L / min to obtain a pre-sintered primary sintered material.

[0034] After the pre-fired primary sintered material and lithium carbonate are mixed uniformly according to the molar ratio of (Ni+Co+Mn) / Li of 1:0.525, at a temperature of 950 ° C, in an air atmosphere and a box furnace, ventilate The amount is 40L / min and sintered for 10h to obtain a doped primary sintered material.

[0035] The doped primary sintered material obtai...

Embodiment 2

[0037] Preparation of single crystal material LiNi doped with zirconium and coated with zirconium metaphosphate 0.5 co 0.16 Zr 0.04 mn 0.3 o 2 :

[0038] According to the molar ratio of 1:0.04, 3.8μm Ni 0.5 co 0.2 mn 0.3 (OH) 2 After physical mixing of zirconium sulfate and zirconium sulfate, it is added to an aqueous solution to form a mixed solution with a solid content of 5%wt. After ball milling for 0.5h, it is spray-dried to obtain a mixture, and the dried mixture is dried in an air atmosphere at a temperature of 400°C. And in the box-type furnace, the ventilation rate is 40L / min and the sintering is 10h, and the primary sintered material after pre-sintering is obtained;

[0039] After the pre-fired primary sintered material and lithium carbonate are mixed uniformly according to the molar ratio of (Ni+Co+Mn) / Li of 1:0.525, at a temperature of 950°C, in an air atmosphere and a box furnace, Sintering for 10h at an air flow rate of 40L / min to obtain a doped primary ...

Embodiment 3

[0046] Preparation of aluminum-doped single crystal material LiNi 0.8 co 0.1 mn 0.06 Zr 0.04 o 2 :

[0047] According to the molar ratio of 1:0.03, the 3.4μm Ni 0.8 co 0.1 mn 0.1 (OH) 2 , aluminum nitrate after physical mixing: adding it to an aqueous solution to form a mixed solution with a solid content of 30%wt., ball milling for 0.5h and then spray-drying to obtain the mixture, and drying the dried mixture at a temperature of 700°C in In air atmosphere and box furnace, sintering at 40L / min for 10h to obtain the primary sintered material after pre-sintering;

[0048] After the pre-fired primary sintered material and lithium hydroxide are uniformly mixed according to the molar ratio of (Ni+Co+Mn) / Li being 1.05, at a temperature of 855°C, in an air atmosphere and a box furnace, ventilate The volume is 40L / min and sintered for 10h to obtain a doped primary sintered material;

[0049] The doped primary sintered material obtained above was sintered for 10 hours in an ...

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Abstract

The invention discloses a modification method of a single crystal ternary positive electrode material. The method comprises the following steps: mixing a precursor containing nickel, cobalt and manganese elements with a dopant metal soluble salt, adding pure water, uniformly stirring, and carrying out spray drying to obtain a pretreated precursor; carrying out low-temperature sintering on the pretreated precursor in an oxidizing atmosphere to obtain a low-temperature sintered product; and uniformly mixing the low-temperature sintering product with a lithium source, and carrying out high-temperature sintering in an oxidizing atmosphere to obtain the doped and modified single-crystal ternary positive electrode material. According to the invention, the precursor and the dopant are pre-sintered at a low temperature, most of the pre-sintered dopant uniformly coats the surface of the precursor in an oxide form, and then the pre-sintered precursor and the lithium salt are sintered at a high temperature, so that the dopant is prevented from forming an oxide coating layer on the surface of the ternary positive electrode material, and the internal resistance of the ternary positive electrodematerial is reduced; and the cycling stability of the lithium-ion battery is greatly improved.

Description

technical field [0001] The invention relates to the technical field of lithium ion battery electrode materials, in particular to a method for modifying a single crystal ternary positive electrode material. Background technique [0002] In order to increase the energy density of power battery cells to 300wh / kg, an important technical approach is to increase the voltage of single crystal. High voltage, that is, single crystallization, is a very direct and effective solution to increase energy density. Increasing the charge cut-off voltage will increase the degree of delithiation of the positive electrode, and the corresponding charge and discharge capacity will also increase. Since the primary particles of single crystal products are much larger than those of polycrystalline products, the surface is smoother and the surface negative reaction can be reduced; the larger the primary crystal particles of ternary materials, the more complete the structure, and the higher the therma...

Claims

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Application Information

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IPC IPC(8): C30B29/22C30B1/10H01M4/505H01M4/525H01M10/0525
CPCC30B1/10C30B29/22H01M4/505H01M4/525H01M10/0525Y02E60/10
Inventor 陈德贤张彬张郑颜华
Owner 宜宾锂宝新材料有限公司
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