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Preparation method of lithium ion battery high-nickel cathode material

A technology for lithium-ion batteries and positive electrode materials, applied in battery electrodes, positive electrodes, secondary batteries, etc., can solve problems such as instability of oxyhydroxides, safety issues, and influence on oxidation effects

Active Publication Date: 2020-10-27
WANHUA CHEM GRP CO LTD
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Problems solved by technology

Such as Chinese invention patent application CN 109809500 A has proposed a kind of utilization H 2 o 2 method of oxidizing the precursor and sintering the cathode material in air, but according to H 2 o 2 It can be seen from the physical and chemical properties of the co-precipitation method and the process conditions for the preparation of hydroxides that in the process of high temperature liquid phase oxidation, H 2 o 2 It will decompose itself and form explosive gas with the volatilized ammonia water in the precursor slurry, which will affect the oxidation effect and have safety problems
[0006] In addition, Chinese invention patent applications CN 103178263 A and CN 109461907 A both mentioned a method of using an oxidant to pre-oxidize the precursor to obtain an oxyhydroxide, and then prepare a nickel-cobalt-aluminum or nickel-cobalt-manganese ternary positive electrode material. The oxyhydroxides are not stable during the sintering process, and will decompose and release oxygen to reduce to divalent oxides at high temperatures. This method can only increase the content of trivalent nickel in the material as much as possible and reduce the phenomenon of cation mixing. The sintering process High concentrations of oxygen are still required as reaction atmosphere or pure oxygen atmosphere
As mentioned above, for industrial production, long-term high-temperature calcination, accompanied by the use of a large amount of oxygen, will bring great economic and safety costs, and how to ensure the uniform distribution of oxygen during the preparation process will also affect the design of the production line. , operation, and product quality control have brought a lot of trouble

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  • Preparation method of lithium ion battery high-nickel cathode material
  • Preparation method of lithium ion battery high-nickel cathode material
  • Preparation method of lithium ion battery high-nickel cathode material

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preparation example Construction

[0056] A method for preparing a high-nickel positive electrode material for a lithium-ion battery, characterized in that it comprises the following steps:

[0057] (1) Preparation of cathode material precursor:

[0058] According to the chemical formula LiNi x co y m z o 2 A salt solution containing a certain stoichiometric ratio of Ni, Co and M elements is obtained under alkaline conditions by adding a complexing agent and using a coprecipitation reaction to obtain a solution containing Ni x co y m z (OH) 2 alkaline slurry.

[0059]In a specific embodiment, where x≥0.6, 0.05≤y≤0.4, 0≤z≤0.4, and x+y+z=1, M is one or more of +4-valent metal elements, preferably One or more of Mn, Ti or Zr. The salt solution of Ni, Co, and M elements is preferably a sulfate salt of Ni, Co, and M elements, which is regulated to an alkaline environment by using NaOH solution, for example, using a NaOH solution with a concentration of 2mol / L to adjust the pH value to 10-14 , the complexin...

Embodiment 1

[0079] The chemical formula of the high-nickel cathode material of the present embodiment is LiNi 0.83 co 0.12 mn 0.05 o 2 , including the following steps:

[0080] 1) Calculate and weigh the sulfate salts of Ni, Co, and Mn based on the ratio of molar ratio Ni:Co:Mn=0.83:0.12:0.05, add deionized water to mix and prepare a solution with a metal concentration of 2mol / L and add it to the reactor , adjust the reaction temperature to 60°C, inject ammonia water to keep the ammonia concentration at 0.5mol / L, inject 2mol / L NaOH solution to adjust the pH value to 11.5, stir at 500r / min, and react for 15h.

[0081] 2) After the reaction is over, add Na to the reactor 2 S 2 o 8 solution, keep Na in the kettle 2 S 2 o 8 The concentration of the solution was 1.2 mol / L, the pH value was adjusted to be kept at 12 by injecting 2 mol / L NaOH solution, the reaction temperature was 40° C., the stirring speed was 400 r / min, and the reaction was carried out for 6 hours.

[0082] 3) Filter...

Embodiment 2

[0085] The chemical formula of the high-nickel cathode material of the present embodiment is LiNi 0.75 co 0.15 mn 0.1 o 2 , including the following steps:

[0086] 1) Calculate with the ratio of molar ratio Ni:Co:Mn=0.75:0.15:0.1 and weigh the corresponding sulfate, add deionized water to mix and prepare a solution with a metal concentration of 2mol / L and add it to the reactor to adjust the reaction The temperature was 60°C, ammonia water was injected to keep the ammonia concentration at 0.5mol / L, 2mol / L NaOH solution was injected to adjust the pH value to 11.2, the stirring speed was 500r / min, and the reaction was carried out for 15h.

[0087] 2) After the reaction is over, add (NH 4 ) 2 S 2 o 8 solution, kept in the kettle (NH 4 ) 2 S 2 o 8 The solution concentration was 0.5 mol / L, the pH value was adjusted to 12 by injecting 2 mol / L NaOH solution, the reaction temperature was 80° C., the stirring speed was 400 r / min, and the reaction was carried out for 6.5 h.

...

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Abstract

The invention belongs to the technical field of lithium ion battery cathode materials, and specifically relates to a preparation method of a lithium ion battery high-nickel cathode material. An oxidizing agent is added into precursor alkaline slurry prepared through a coprecipitation method for precursor pre-oxidation, then the pre-oxidized precursor is converted into a polycrystalline mixture byadjusting a drying process, and then the polycrystalline mixture and a lithium source are mixed in air or a low-oxygen-concentration mixed atmosphere to be sintered at a time to obtain a target product. According to the preparation method disclosed by the invention, alkali liquor can be recycled to realize precursor pre-oxidation, the sintering time and temperature are shortened, the residual alkali value is reduced, and the crystallinity of the material is improved. In the calcining process, oxygen demand is low, safety is good, and the method is more suitable for industrial large-scale production.

Description

technical field [0001] The invention belongs to the technical field of positive electrode materials for lithium ion batteries, and in particular relates to a preparation method for high nickel positive electrode materials for lithium ion batteries. Background technique [0002] In recent years, with the vigorous development of emerging green energy, various efficient and environmentally friendly energy storage devices have been widely used in various fields of social production. Among them, lithium-ion batteries have become one of the indispensable industrial products for smart application scenarios such as electric vehicles, energy storage, and 3C portable smart products due to their advantages such as high energy density, excellent charging and discharging performance, and low pollution. However, with the large-scale application of lithium-ion batteries, the market's demand for high energy density is becoming more and more urgent, which greatly promotes the development and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/525H01M4/505H01M4/62H01M10/0525
CPCH01M4/505H01M4/525H01M4/62H01M10/0525H01M2004/028Y02E60/10
Inventor 王帅刚张洁韩玉振刘逸群李倩岳宝玉陈睿王洪湖
Owner WANHUA CHEM GRP CO LTD
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