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High energy density lithium ion battery oxide positive electrode material and preparation method thereof

A cathode material and hydroxide technology, applied in the field of cathode materials for high energy density lithium ion batteries and their preparation, can solve the problems of flatulence, high surface activity, side reaction batteries and the like

Active Publication Date: 2014-01-15
NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Nickel-based materials have obvious cost advantages. With the increase of nickel content, the capacity of the material can be significantly improved. For example, NCA can reach 180mAh / g at 4.25V. The reaction causes battery flatulence, so these cathode materials need to be modified

Method used

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  • High energy density lithium ion battery oxide positive electrode material and preparation method thereof
  • High energy density lithium ion battery oxide positive electrode material and preparation method thereof
  • High energy density lithium ion battery oxide positive electrode material and preparation method thereof

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preparation example Construction

[0074] The preparation method of the cathode material of the present invention comprises the steps of:

[0075] (a) in Ni 1-y-z co y mn z (OH) 2 Precipitate the hydroxide of Co, or the hydroxide of X and Co on the surface to obtain the core-shell precursor;

[0076] (b) sintering after mixing the core-shell precursor and the lithium source in a molar ratio of 1-1.2;

[0077] (c) depositing the hydroxide of metal M on the surface of the sintered sample;

[0078] (d) sintering at 200-1000° C. for 0.5-24 hours to obtain the positive electrode material,

[0079] Wherein, 0≤y≤1.0, 0≤z≤1.0, 0≤y+z≤1; 0≤b≤1.0, X, M are independently selected from Al, Mg, Cu, Zr, Ti, Cr, V, One or a combination of Fe, Mn, Ni, Y, Zn.

[0080] In the method of the present invention, the prepared precursor has a core-shell structure, and after sintering, the particles form a shell layer with a concentration gradient. By adopting the preparation method, the cladding layer substance can be evenly at...

Embodiment 1

[0109] Prepare the core as LiNi 1 / 3 co 1 / 3 mn 1 / 3 o 2 , the shell is Li[(Ni 1 / 3 co 1 / 3 mn 1 / 3 ) 0.99 Al 0.01 ]O 2 positive electrode material.

[0110] Weigh 13.3234g Al 2 (SO 4 ) 3 18H 2 O, add to 100g water to dissolve completely, add precursor Ni 1 / 3 co 1 / 3 mn 1 / 3 (OH) 2 18.3083g, stirring to form a dispersion of the precursor, adding a concentration of 2% NH 3 ·H 2 O, making Al(OH) 3 Precipitate completely, and the end point pH value is around 9. After the dropwise addition, continue to stir for 60 minutes, stop stirring, filter, wash twice, and dry the coated precursor at 120°C for 12 hours. Its appearance is as follows: figure 1 As shown, the particle size is 1-20 μm. Then lithium hydroxide monohydrate and the dry precursor were mixed evenly at a molar ratio of 1.10, and the mixture was pre-fired at 450°C in air for 5 hours, then heated to 900°C for 12 hours, and cooled naturally to room temperature. The obtained surface is Li[(Ni 1 / 3 co 1 / 3 mn 1 / ...

Embodiment 2

[0115] Prepare the core as LiNi 0.5 co 0.2 mn 0.3 o 2 , the shell is Li[(Ni 0.5 co 0.2 mn 0.3 ) 0.99 Al 0.01 ]O 2 positive electrode material.

[0116] Weigh Al(NO 3 ) 3 9H 2 O 1.4450g, dissolve in 100mL water, add Ni 0.5 co 0.2 mn 0.3 (OH) 2 10.0420g, form the dispersion liquid of the precursor, add ammonia water with a concentration of 1% dropwise, adjust the pH value to about 9.0, continue to adjust the pH value to 11 with concentrated ammonia water, stir for 60 minutes, stop stirring, filter, wash twice with water, and wrap the The coated precursor was dried at 120 °C for 12 hours, and its morphology was as follows image 3 As shown, the particle size is 1-20 μm. Then lithium hydroxide monohydrate and the dry precursor were uniformly mixed at a molar ratio of 1.10, the mixture was calcined at 900° C. for 12 hours in an oxygen atmosphere, and cooled naturally to room temperature. The obtained shell is Li[(Ni 0.5 co 0.2 mn 0.3 ) 0.99 Al 0.01 -]O 2 , t...

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Abstract

The present invention relates to a high energy density lithium ion battery oxide positive electrode material and a preparation method thereof. The positive electrode comprises a positive electrode material main body and a coating layer positioned on the surface of the positive electrode material main body, wherein the coating layer material is one or a combination selected from Al2O3, ZrO2, MgO, SiO2, ZnO2, TiO2 and LiAlO2, the positive electrode material main body comprises a shell layer and a core positioned inside the shell layer, the core material is Li1+x[Ni1-y-zCoyMnz]O2, the shell layer material is Li1+a[Co1-bXb]O2, or the positive electrode material main body is a mixture of Li1+x[Ni1-y-zCoyMnz]O2 and LiCoO2, and x, y, z, a and b are defined in the instruction. The positive electrode material has advantages of high capacity, good cycle performance, low surface activity, high voltage resistance, good safety and the like. The preparation method has a characteristic of simple preparation process, and is suitable for mass production application.

Description

technical field [0001] The invention belongs to the field of energy materials, and relates to a positive electrode material for a high energy density lithium ion battery and a preparation method thereof. technical background [0002] Lithium-ion secondary battery is an ideal energy storage system, which has the advantages of high energy density, good cycle performance, low self-discharge rate and good environmental compatibility. , electric vehicles and power generation and energy storage areas show great potential. [0003] High-capacity cathode materials are the basis and key to the development of high-energy-density lithium-ion batteries, and have become the focus of world research in recent years. Nickel-based materials have obvious cost advantages. With the increase of nickel content, the capacity of the material can be significantly improved. For example, NCA can reach 180mAh / g at 4.25V. The reaction causes battery gassing, so modification of these cathode materials ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/62H01M4/48H01M10/0525
CPCC01G51/42C01G53/50H01M4/525H01M4/131H01M4/485H01M10/0525H01M4/366Y02E60/10H01M4/505H01M2004/028
Inventor 毕玉敬王德宇黎军
Owner NINGBO INST OF MATERIALS TECH & ENG CHINESE ACADEMY OF SCI
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