Ternary positive electrode precursor and preparation method and application thereof

A technology of precursors and positive electrodes, which is applied in the field of ternary positive electrode precursors and their preparation, can solve the problems of complex control conditions in the synthesis process, great influence on the growth process of precursors, and the reduction of lithium ion diffusion coefficient, so as to improve the high-temperature cycle. performance, inhibition of mixed discharge of nickel and lithium, and good cycle performance

Inactive Publication Date: 2021-05-07
SHANGHAI CENAT NEW ENERGY
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Problems solved by technology

Although this method successively modifies the ternary cathode material by doping and coating, the rate performance and cycle performance of the material are significantly improved, but the preparation process of the material is relatively complicated, which is not conducive to industrial production.
[0004] CN108550822A discloses a lanthanum, magnesium co-doped high-nickel ternary lithium battery positive electrode material, uniformly mix nickel source, cobalt source, manganese source, lanthanum source, magnesium source and add precipitant and chelating agent to prepare NCM precursor slurry material, through pre-sintering and sintering to synthesize lanthanum-doped high-nickel ternary cathode material Li 1.05-x Mg x Ni 1-2y-z co y mn y La z o 2 , although the present invention overcomes the shortcoming of poor cycle stability of traditional high-nickel ternary positive electrode materials, since the synthesis of the material occurs in the precursor co-precipitation step, this has a great influence on the growth process of the precursor, and the synthesis The condition control relationship of the process is complex
[0005] CN106920934A discloses a method for preparing a co-doped modified ternary precursor based on high-nickel materials and a positive electrode material. Mixing nickel-cobalt-magnesium mixed solution, ammonia water, and sodium hydroxide solution in a heating reactor for co-doping The precipitation reaction obtains a co-doped modified ternary precursor precursor based on high-nickel materials. Since the material prepared by this method is lithium nickelate as the main material, it is inevitable that the nickel content is often higher than the lithium content (Li 1-x Ni 1+x o 2 ), so divalent nickel will always appear in the lithium layer, resulting in a decrease in the lithium ion diffusion coefficient of the material

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  • Ternary positive electrode precursor and preparation method and application thereof
  • Ternary positive electrode precursor and preparation method and application thereof
  • Ternary positive electrode precursor and preparation method and application thereof

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Embodiment 1

[0054] This embodiment provides a ternary positive electrode precursor, the chemical formula of the precursor is Ni 0.5 co 0.2 mn 0.3 CO 3 0.002Mg(BO 2 ) 2 0.0005 Ce 2 (CO 3 ) 3 , with an average particle size of 9 μm.

[0055] The preparation method of the ternary positive electrode precursor is as follows:

[0056] (1) Nickel sulfate, cobalt sulfate, manganese sulfate, magnesium sulfate and cerium sulfate are according to chemical formula Ni 0.5 co 0.2 mn 0.3 CO 3 0.002Mg(BO 2 ) 2 0.0005 Ce 2 (CO 3 ) 3 Add the ratio of deionized water to prepare a 2mol / L main metal salt solution, add sodium metaborate to deionized water to prepare a 0.01mol / L solution, and add ammonium carbonate to deionized water to prepare a 8mol / L precipitant solution;

[0057] (2) Add the main metal salt solution, sodium metaborate solution and ammonium carbonate solution in step (1) into the reaction kettle at a ratio of 100:40:25.5 through a metering pump, and carry out a co-precipitat...

Embodiment 2

[0060] This embodiment provides a ternary positive electrode precursor, the chemical formula of the precursor is Ni 0.6 co 0.2 mn 0.2 CO 3 0.004Mg(BO 2 ) 2 0.001Ce 2 (CO 3 ) 3 , with an average particle size of 10 μm.

[0061] The preparation method of the ternary cathode precursor is as follows:

[0062] (1) Nickel sulfate, cobalt sulfate, manganese sulfate, magnesium sulfate and cerium sulfate are according to chemical formula Ni 0.6 co 0.2 mn 0.2 CO 3 0.004Mg(BO 2 ) 2 0.001Ce 2 (CO 3 ) 3 Add the proportion of deionized water to prepare a 1.8mol / L main metal ion solution, add sodium metaborate to deionized water to prepare a 0.015mol / L solution, and add ammonium bicarbonate to deionized water to prepare a 6mol / L precipitant solution;

[0063] (2) Add the main metal ion solution, sodium metaborate solution, and ammonium bicarbonate solution in step (1) to the reaction kettle at a ratio of 100:57.6:31 through a metering pump, and carry out a co-precipitation c...

Embodiment 3

[0066] This embodiment provides a ternary positive electrode precursor, the chemical formula of the precursor is Ni 0.7 co 0.15 mn 0.15 CO 3 0.008Mg(BO 2 ) 2 0.002Ce 2 (CO 3 ) 3 , with an average particle size of 11 μm.

[0067] The preparation method of the ternary cathode precursor is as follows:

[0068] (1) nickel nitrate, cobalt nitrate, manganese nitrate, magnesium nitrate and cerium nitrate according to chemical formula Ni 0.7 co 0.15 mn 0.15 CO 3 0.008Mg(BO 2 ) 2 0.002Ce 2 (CO 3 ) 3 Add the proportion of deionized water to prepare a 1.2mol / L main metal ion solution, add potassium metaborate to deionized water to prepare a 0.02mol / L solution, and add ammonium bicarbonate to deionized water to prepare a 4mol / L precipitant solution;

[0069] (2) The main metal ion solution, potassium metaborate solution, and ammonium bicarbonate solution described in step (1) are added to the reaction kettle at a ratio of 100:67.2:31 through a metering pump, and coprecipi...

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Abstract

The invention provides a ternary positive electrode precursor and a preparation method and application thereof. The chemical formula of the ternary positive electrode precursor is NixCoyMn1-x-yCO3. AMg(BO2)2.BCe2(CO3)3, x is greater than 0 and less than 1, y is greater than 0 and less than 1, a is greater than or equal to 0.001 and less than or equal to 0.1, and b is greater than or equal to 0.0005 and less than or equal to 0.05. The preparation method comprises the following steps: adding a main metal salt solution, a metaborate solution and a precipitator solution into a reaction kettle for reaction, aging and drying to obtain the ternary positive electrode precursor, wherein the main metal salt is nickel salt, cobalt salt, manganese salt, magnesium salt and cerium salt. By selecting raw materials of boron, magnesium, cerium and a precipitator, co-precipitation of boron, magnesium, cerium and nickel cobalt manganese in a precursor stage is realized, and the boron, magnesium and cerium co-doped ternary positive electrode precursor with a stable structure is obtained. The battery finally prepared from the precursor has good cycle performance.

Description

technical field [0001] The invention belongs to the technical field of lithium ion batteries, and relates to a ternary cathode precursor, a preparation method and application thereof. Background technique [0002] With due to Mg 2+ and Li + The radius is close, and the ternary positive electrode material is doped with magnesium to replace some Li ions, which can inhibit the mixed arrangement of nickel and lithium and stabilize the layered structure. Ce doping can improve the stability of the overall structure and improve the cycle performance of the battery. The ternary positive electrode material is doped with boron, The B-O bond energy is strong, which improves the structural stability of the material. At present, the co-doping of boron and magnesium has not been realized in the precursor stage, and the uniform mixing with the main metal elements cannot be achieved. [0003] CN108288694A discloses a kind of Mg 2+ doped AlF 3 The preparation method of the coated ternary...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01G53/00H01M4/505H01M4/525H01M4/62H01M10/0525
CPCC01G53/006C01G53/70H01M4/505H01M4/525H01M4/628H01M10/0525H01M2004/028C01P2004/61Y02E60/10
Inventor 刘海昌时迎华张欣鹏王永华
Owner SHANGHAI CENAT NEW ENERGY
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