阅读说明：本技术 一种镍钴锰三元前驱体材料的制备方法 (A kind of preparation method of nickel-cobalt-manganese ternary persursor material ) 是由 许益伟 吉同棕 周浩 王明 余凡 毛秦钟 王寅峰 钱志挺 吴海军 于 2019-07-21 设计创作，主要内容包括：本发明属于锂离子电池制备技术领域,具体涉及一种镍钴锰三元前驱体材料的制备方法,其包括以下步骤：(1)以可溶性盐硫酸镍、硫酸锰、硫酸钴为原料,配制一定浓度的镍钴锰盐溶液；(2)配制的镍钴锰溶液按照一定比例加入水杨酸钠组成混合溶液,再加入碱液做为沉淀剂,进行共沉淀反应,得到混合浆料；(3)共沉淀反应分为两个阶段,高pH成核阶段和低pH生长阶段,其中低pH生长阶段加入一定比例的络合剂进行沉淀反应,整个共沉淀反应过程使用浓缩机提升固含量；(4)最后将所得的产物进行陈化、洗涤、烘干,得到镍钴锰前驱体。采用本发明的制备方法可以得到球形度高、表面致密的镍钴锰前驱体。(The invention belongs to lithium ion battery preparation technical fields, more particularly to a kind of preparation method of nickel-cobalt-manganese ternary persursor material, it is the following steps are included: (1) using soluble-salt nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, prepares certain density nickel cobalt manganese salt solution；(2) sodium salicylate composition mixed solution is added in the nickel cobalt manganese solution prepared according to a certain percentage, adds lye as precipitating reagent, carries out coprecipitation reaction, obtain mixed slurry；(3) coprecipitation reaction is divided into two stages, high pH nucleation stage and low pH growth phase, wherein a certain proportion of complexing agent, which is added, in low pH growth phase carries out precipitation reaction, entire coprecipitation reaction process promotes solid content using thickener；(4) finally resulting product is aged, washed, dried, obtain nickel cobalt manganese presoma.High, surface compact the nickel cobalt manganese presoma using the available sphericity of preparation method of the invention.)

1. a kind of preparation method of nickel-cobalt-manganese ternary persursor material, which is characterized in that the preparation method comprises the following steps:

(1) using soluble-salt nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, certain density nickel cobalt manganese sulfate liquor is prepared；

(2) sodium salicylate composition mixed solution is added in the nickel cobalt manganese solution prepared according to a certain percentage, lye as precipitating reagent, into Row coprecipitation reaction, obtains mixed slurry；

(3) coprecipitation reaction is divided into two stages, high pH nucleation stage and low pH growth phase, wherein low pH growth phase is added A certain proportion of complexing agent carries out precipitation reaction, and entire coprecipitation reaction process promotes solid content using thickener；

(4) finally resulting product is aged, washed, dried, obtain nickel cobalt manganese presoma.

2. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (1) the nickel cobalt manganese sulfate liquor molar concentration prepared in is 1.5mo1/L~2.0mo1/L, and nickel cobalt mn sulphate mixing is molten In liquid, the molar ratio of nickel cobalt manganese is x:y:z, wherein x+y+z=1；The chemical formula of the nickel cobalt manganese presoma is (NixCoyMnz) OH₂, wherein x+y+z=1.

3. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (2) complexing agent sodium salicylate molar concentration is 0.01~0.2mol/L in；Lye is sodium hydroxide solution, and molar concentration content is 10mol/L。

4. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (2) coprecipitation reaction Process control conditions in are as follows: 1000~1100r/min of mixing speed, pH value 9~12, reaction temperature 45~ 60 DEG C, protective atmosphere is nitrogen atmosphere.

5. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (3) complexing agent being added in is ammonium hydroxide, and the ammonium hydroxide molar concentration of addition is 0.1~0.3mol/L.

6. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (3) PH nucleation stage pH is 11~12 in, and low PH growth phase pH is 9~11.

7. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (3) it is 5~8g/L that low pH growth phase, which keeps ammonia value, in.

8. a kind of preparation method of nickel-cobalt-manganese ternary persursor material according to claim 1, which is characterized in that step (4) the drying process temperature described in is 100~150 DEG C.

Technical field

The present invention relates to lithium ion battery preparation technical fields, and in particular to a kind of system of nickel-cobalt-manganese ternary persursor material Preparation Method.

Background technique

In recent years, all kinds of new energy motor power technologies are grown rapidly, and are vied each other, using electric drive as representative, excitation One new technological change.Power supply used in electric car currently on the market is all lithium dynamical battery mostly, lithium battery with Its high-energy density, long-life and high security are generally approved by enterprise and users.Currently on the market the lithium of mainstream from Sub- battery includes LiFePO4, nickle cobalt lithium manganate etc., and wherein the advantage of its high-energy density of ternary material nickle cobalt lithium manganate causes Research extensively.And for the performance of ternary material, it is mainly influenced by nickel cobalt manganese presoma, so for nickel cobalt manganese presoma Preparation method improve it is most important.

The main method of nickel cobalt manganese presoma is prepared at this stage are as follows: nickel cobalt manganese solid salt is configured to a certain concentration by the first step And ratio mixed solution, mixed solution and precipitating reagent, complexing agent co-precipitation are crystallized；Second step carries out slurry old Change, washing, drying, mixing, be sieved, except the processes such as iron obtain nickel cobalt manganese hydroxide precursor.

Conventional method is easily made due to the characteristic of ammino mixture when preparing bulky grain especially nickelic bulky grain product It is poor in turn result in subsequent positive electrode performance for situations such as balling-up is split, particle is uneven.

Summary of the invention

Based on the above prior art, the purpose of the present invention is to provide a kind of preparation sides of nickel-cobalt-manganese ternary persursor material Method, nickel cobalt manganese presoma produced by the present invention have the advantages that sphericity height, surface compact, compacted density are high.

In order to achieve the goal above, the technical solution adopted by the present invention are as follows:

A kind of preparation method of nickel-cobalt-manganese ternary presoma, comprising the following steps:

(1) using soluble-salt nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, it is molten to prepare certain density nickel cobalt mn sulphate Liquid；

(2) sodium salicylate composition mixed solution is added in the nickel cobalt manganese solution prepared according to a certain percentage, and lye is as precipitating Agent carries out coprecipitation reaction, obtains mixed slurry；

(3) coprecipitation reaction is divided into two stages, high pH nucleation stage and low pH growth phase, wherein low pH growth phase A certain proportion of complexing agent is added and carries out precipitation reaction, entire coprecipitation reaction process promotes solid content using thickener；

(4) finally resulting product is aged, washed, dried, obtain nickel cobalt manganese presoma.

In order to preferably realize the present invention, further, the nickel cobalt manganese sulfate liquor molar concentration prepared in step (1) For 1.5mo1/L~2.0mo1/L, in the nickel cobalt mn sulphate mixed solution, the molar ratio of nickel cobalt manganese is x:y:z, wherein x+y+z =1；The chemical formula of the nickel cobalt manganese presoma is (NixCoyMnz) OH₂, wherein x+y+z=1.

In order to preferably realize the present invention, further, in step (2) complexing agent sodium salicylate molar concentration be 0.01~ 0.2mol/L；Lye is sodium hydroxide solution, and molar concentration content is 10mol/L.

In order to preferably realize the present invention, further, coprecipitation reaction Process control conditions in step (2) are as follows: stirring 1000~1100r/min of speed, pH value 9~12,45~60 DEG C of reaction temperature, protective atmosphere is nitrogen atmosphere.

In order to preferably realize the present invention, further, the complexing agent being added in step (3) is ammonium hydroxide, the ammonium hydroxide of addition Molar concentration is 0.1~0.3mol/L.

In order to preferably realize the present invention, further, PH nucleation stage pH is 11~12 in step (3), low PH growth Stage pH is 9~11.

In order to preferably realize the present invention, it is 5~8g/L that further, in step (3) low pH growth phase, which keeps ammonia value,.

In order to preferably realize the present invention, further, drying process temperature described in step (4) is 100~150 DEG C.

Beneficial effect

Beneficial effects of the present invention are as follows:

1, the method for preparation nickel cobalt manganese presoma provided by the technology of the present invention, by the nickel cobalt manganese solution of preparation according to certain Ratio is added sodium salicylate and forms mixed solution, adds sodium hydroxide as precipitating reagent, carries out coprecipitation reaction, be divided into two Complexing agent ammonium hydroxide is added in low pH growth phase in stage, high pH nucleation stage and low pH growth phase, and simultaneous reactions process uses Thickener promotes solid content；Finally resulting product is aged, washed, is dried, nickel cobalt manganese presoma is obtained, for spherical shape The particle of degree height, surface compact.

2, conventional method due to ammino mixture characteristic, when preparing bulky grain especially nickelic bulky grain product, easily It causes ball to split, situations such as particle is uneven, in turn results in that subsequent positive electrode performance is poor, and the present invention compensates for the prior art Deficiency uses coprecipitation reaction technique, and operating process is controllably easy to operate to equipment and correlated condition, is suitable as mass production It uses, there is very high economic and practical.

Detailed description of the invention

Fig. 1 illustrates the process flow chart of nickel cobalt manganese hydroxide preparation method provided in an embodiment of the present invention；

Fig. 2 is 3000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 1 is prepared；

Fig. 3 is 5000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 1 is prepared；

Fig. 4 is 3000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 2 is prepared；

Fig. 5 is 5000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 2 is prepared；

Fig. 6 is 2000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 3 is prepared；

Fig. 7 is 5000 times of scanning electron microscope (SEM) photographs of the nickel cobalt manganese hydroxide that the embodiment of the present invention 3 is prepared；

Specific embodiment

Invention is further described in detail combined with specific embodiments below.