WO2023005031A1

WO2023005031A1 - Preparation method for nickel-cobalt-manganese ternary precursor material and lithium ion battery

Info

Publication number: WO2023005031A1
Application number: PCT/CN2021/127128
Authority: WO
Inventors: 高琦; 文定强; 郑江峰; 张颖; 吴浩; 黄仁忠; 罗敏
Original assignee: 广东佳纳能源科技有限公司; 清远佳致新材料研究院有限公司
Priority date: 2021-07-29
Filing date: 2021-10-28
Publication date: 2023-02-02
Also published as: CN113582252B; CN113582252A

Abstract

Provided are a preparation method for a nickel-cobalt-manganese ternary precursor material, a ternary positive electrode material, and a lithium ion battery. The preparation method comprises: (a) mixing crude solid cobalt hydroxide, a soluble ammonium salt, and ammonia water, and after an ammonia leaching reaction, performing solid-liquid separation to obtain a first filtrate and a first filter residue; leaching the first filter residue by using a sulfuric acid solution, and performing solid-liquid separation to obtain a second filtrate and a second filter residue; (b) extracting the first filtrate in step (a) to obtain an extract, and then stripping the extract by using an acid solution to obtain a stripping solution and a raffinate; adding manganese powder and/or nickel powder to the stripping solution for reaction, then adding a fluoride for reaction, and performing solid-liquid separation to obtain a third filtrate and a third filter residue; (c) adding a sulfuric acid solution and manganese powder into the second filter residue in step (a), and after the reaction, performing solid-liquid separation to obtain a fourth filtrate and a fourth filter residue; (d) combining the third filtrate and the fourth filtrate to obtain a nickel-cobalt-manganese sulfate mixed solution, adding the sulfate mixed solution according to the ratio of nickel, cobalt, and manganese in the ternary precursor material to obtain a ternary precursor mixed solution, mixing the ternary precursor mixed solution with a precipitant and a complexing agent, after a coprecipitation reaction, performing solid-liquid separation, and drying to obtain the nickel-cobalt-manganese ternary precursor material. Also provided are the ternary positive electrode material made of the nickel-cobalt-manganese ternary precursor, and the lithium ion battery comprising a battery positive electrode made of the ternary positive electrode material. By means of the method, all-component recovery of nickel, cobalt, and manganese in the crude cobalt hydroxide is realized, a high-purity and low-impurity nickel-cobalt-manganese ternary precursor material is prepared, and full recycling of valuable metals in the crude cobalt hydroxide is realized.

Description

A kind of preparation method of nickel-cobalt-manganese ternary precursor material and lithium ion battery

This application claims the priority of the Chinese patent application with the application number 202110864024.1 and the title of the invention "a method for preparing a nickel-cobalt-manganese ternary precursor material and a lithium-ion battery" submitted at the China Patent Office on July 29, 2020. rights, the entire contents of which are incorporated in this application by reference.

technical field

The present application relates to the technical field of preparation of cathode materials for lithium-ion batteries, in particular, to a method for preparing a nickel-cobalt-manganese ternary precursor material and a lithium-ion battery.

Background technique

The nickel-cobalt-manganese ternary precursor is the front-end raw material for the preparation of lithium-ion battery cathode materials, and it is also a highly customized standard product. The performance indicators of the finished ternary precursor will affect the physical and chemical properties of the finished cathode material, which in turn will affect the electrochemical performance of lithium batteries. make an impact. The nickel-cobalt-manganese ternary precursor is actually a nickel-cobalt-manganese hydroxide, and its preparation method is mainly co-precipitation method, using nickel salt, cobalt salt, and manganese salt as raw materials, and saline-alkali neutralization in ammonia water and alkali solution Reaction, nickel cobalt manganese hydroxide precipitation.

With the rapid development of global electrification and new energy vehicles, the demand for cobalt as a necessary raw material for the preparation of lithium batteries will continue to grow rapidly in the future. Ensuring stable supply of raw materials and reducing production costs are the primary tasks of ternary precursor manufacturers. Restricted by the cobalt ore import policy, most of the cobalt ore imported into China is an intermediate product of cobalt hydroxide. At present, the following methods are mostly used: acid dissolution of cobalt intermediate products-extraction and copper removal-chemical impurity removal-extraction and impurity removal-pure cobalt solution process. If the crude cobalt salt is leached by the traditional acid method, a large number of impurities such as calcium, magnesium, and manganese will enter the leachate, making the subsequent purification and impurity removal process complicated, the process flow is long, the consumption of impurity remover, acid and alkali is large, and the nickel, Elements such as manganese are difficult to fully recover, resulting in waste.

technical problem

At present, there is no method with good repeatability and simple operation to solve the above problems, so the industrial application of nickel-cobalt-manganese ternary precursors is limited by the cost to a certain extent. Therefore, it is necessary to provide a method for preparing a low-cost, low-impurity nickel-cobalt-manganese ternary precursor.

technical solution

The first purpose of the present application is to provide a method for preparing a nickel-cobalt-manganese ternary precursor material to completely or partially solve the above-mentioned problems. The method uses crude solid cobalt hydroxide as a raw material to realize the The three elements of nickel, cobalt and manganese are fully recovered, and the recovery rate of the three elements of nickel, cobalt and manganese reaches 99.3%. The raw materials for the preparation of ternary lithium-ion battery precursors can be quickly obtained, and high-purity, low-impurity nickel-cobalt-manganese ternary precursor materials can be prepared. The full recovery of valence metals.

The second purpose of the present application is to provide a nickel-cobalt-manganese ternary positive electrode material prepared from the above-mentioned nickel-cobalt-manganese ternary precursor material.

The third object of the present application is to provide a lithium ion battery comprising the above-mentioned nickel-cobalt-manganese ternary positive electrode material.

In order to realize the above-mentioned purpose of the present application, the following technical solutions are specially adopted:

A method for preparing a nickel-cobalt-manganese ternary precursor material provided by the application comprises the following steps:

(a), mixing the crude solid cobalt hydroxide, soluble ammonium salt, and ammonia water, and after ammonia leaching reaction, solid-liquid separation to obtain the first filtrate and the first filter residue; using sulfuric acid solution to leach the first filter residue, After leaching, solid-liquid separation is performed to obtain a second filtrate and a second filter residue;

(b), using a mixed solution of the extraction phase P507 and sulfonated kerosene to extract the first filtrate in step (a) to obtain an extract, and then use an acid solution to back-extract the extract to obtain a back-extraction liquid and raffinate; adding manganese powder and/or nickel powder to react in the stripping liquid, then adding fluoride to react, then solid-liquid separation to obtain the third filtrate and the third filter residue;

(c), add sulfuric acid solution and manganese powder in the described second filter residue in step (a), after reaction, solid-liquid separation obtains the 4th filtrate and the 4th filter residue;

(d), combining the third filtrate and the fourth filtrate to obtain a nickel-cobalt-manganese sulfate mixed solution, and adding the sulfate according to the ratio of nickel, cobalt, and manganese in the ternary precursor material Mixing the solution to obtain a ternary precursor mixed solution, mixing the ternary precursor mixed solution with a precipitating agent and a complexing agent, after a co-precipitation reaction occurs, separating the solid from the liquid, and drying the obtained solid to obtain the nickel-cobalt-manganese Ternary precursor material.

According to the application, the crude solid cobalt hydroxide contains a large amount of magnesium, a small amount of nickel, manganese, copper, zinc, iron, aluminum, calcium and other impurity elements.

According to the application, after ammonia leaching, cobalt, manganese, nickel, copper and other elements in the crude cobalt hydroxide will enter the leaching solution in an ionic state. In the ammonia leaching solution, due to the high ammonia content, it can react with the P507 sulfonated kerosene extraction system. Design the saponification section, at this moment cobalt, manganese, nickel, copper, zinc, iron, magnesium in the ammonia leaching solution can enter organic phase, be the mixed solution of ammoniacal ammonium salt in the aqueous phase, the organic phase of load passes acid solution (preferably sulfuric acid solution) for stripping, cobalt, manganese, nickel, copper, magnesium and other elements can be separated into the stripping solution; then the copper powder is replaced by adding nickel powder and/or manganese powder to remove trace copper ions; adding fluorine The compound forms magnesium fluoride to precipitate to remove traces of magnesium ions, and after filtration, a sulfate solution containing only three elements of cobalt, manganese and nickel can be obtained.

In some preferred embodiments of the present application, in step (b), after stripping the extract phase P507 and the sulfonated kerosene solution, 5mol/L hydrochloric acid solution can be added for washing and purification; the obtained washing solution after phase separation can be After removing trace iron and zinc by N235 organic solution, it can be recycled.

In some preferred embodiments of the present application, in step (a), the molar ratio of the ammonia water to the soluble ammonium salt is 1 to 3.5:1, including but not limited to 3.5:1, 4:1, 5: 1, 6:1, 7:1, 8:1, 9:1, and 10:1.

Preferably, the total ammonium concentration in the leaching system in step (a) is 110-160g/L, including but not limited to 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L;

In the embodiment, the total ammonium concentration refers to the ammonium content in the solution in the leaching system, including ammonia water and ammonium in soluble ammonium salts, providing ammonium ions can promote the complexation reaction of each reactant.

In some embodiments, the total ammonium concentration in the leaching system is 110-160 g/L. If the total ammonium concentration provided is too low, the yield during the preparation process will be low, the leaching effect will be poor, the concentration of valuable metals in the leach solution will be low, and the waste water will be The processing capacity is large; if the concentration is too high, the effect on the improvement of the leaching rate is not obvious, and with the increase of the total ammonium concentration, the volatilization of ammonia gas will also increase, and the additional operating environment will dissolve in the solution after a certain level. The nickel-cobalt-manganese metal ions in the compound form precipitates again. Therefore, the total ammonium concentration range value provided by the examples of the present application improves the output, improves the leaching effect and improves the leaching rate.

Preferably, the soluble ammonium salt includes at least one of ammonium sulfate, ammonium bicarbonate, ammonium carbonate and ammonium chloride;

Preferably, during the ammonia leaching reaction, the temperature of the solution system is 40-60°C, including but not limited to 40, 50, and 60°C.

In some preferred embodiments of the present application, in step (a), during the leaching of the first filter residue, the molar concentration of the sulfuric acid solution is 0.5-1 mol/L, including but not limited to 0.5, 0.6, 0.8, 1mol/L. However, when the concentration of sulfuric acid is too low, the effect of leaching the impurity ions wrapped in the first filter residue is poor. When the concentration of sulfuric acid is too high, a part of manganese and cobalt ions will be dissolved and enter the second filtrate, resulting in valuable metal ions Loss, the concentration range of the sulfuric acid solution provided in the examples of the present application can well solve the above problems.

In some preferred embodiments of the present application, during the leaching process, compressed air is also introduced, and the flow rate of the compressed air is 2-3m ³ /h, including but not limited to 2, 2.5, 3m ³ /h The purpose of feeding compressed air is to maintain the valuable metal cobalt and manganese remaining in the first filter residue in an oxidizing atmosphere, so that it remains in the second filter residue, while the calcium, magnesium, aluminum, iron in the first filter residue The plasma enters the persulfuric acid leaching system and enters the second filtrate; because the acidity in the leaching system is low, the flow range of the compressed air provided in the embodiment of the present application can create a suitable oxidation atmosphere.

Preferably, after the leaching, the pH of the solution system is 2.0-3.5, including but not limited to 2.0, 2.5, 3.0, 3.5;

Preferably, during the leaching process, the temperature of the solution system is 40-50°C, such as 40, 45, 50°C;

Preferably, during the leaching process, stirring is performed at a speed of 160-200 rpm, such as 160, 170, 190, 200 rpm;

Preferably, the reaction time of the leaching is 1-3 hours.

In some preferred embodiments of the present application, in step (b), in the mixed solution of the extract phase P507 and sulfonated kerosene, the volume ratio of the extract phase P507 is 20% to 30%, such as 20%, 25%, 30%, the volume ratio of the organic phase to the aqueous phase in the mixed solution is 1:2-2:1, such as 1:2, 1:1, 2:1.

In some preferred embodiments of the present application, in step (b), during the reaction of adding manganese powder and/or nickel powder, the amount of manganese powder and/or nickel powder added is the theoretical molar amount 5 to 10 times of that, for example 5, 6, 7, 8, 9, 10 times; wherein, the theoretical molar amount of manganese powder and/or nickel powder is calculated according to the reaction Mn+Cu ²⁺ →Mn ²⁺ +Cu, manganese and /or the theoretical molar amount of nickel powder is the molar amount of ^Cu in the solution. The range value of the theoretical molar dosage of manganese powder and/or nickel powder provided by the embodiments of the present application improves the solubility of manganese powder and/or nickel powder, reduces the number of filter residues after filtration, improves the purity of copper powder replaced and improves copper removal effect, and meet the requirements of the back-end design.

Preferably, during the reaction, the temperature of the solution system is 80-90°C, such as 80, 85, 90°C; more preferably, the reaction time is 1-3h. The increase or extension of the reaction temperature and reaction time is conducive to the improvement of the copper removal effect, but with the continuous improvement, the improvement effect is limited, but it will lead to a decrease in efficiency and an increase in equipment load, which is not conducive to large-scale industrialization. If the temperature is low or the reaction time is short, the replacement reaction is incomplete, and the copper removal effect is limited. Therefore, the reaction temperature and reaction time range values provided in the examples of the present application improve the effect of copper replacement and removal, improve production efficiency, reduce equipment load, and facilitate large-scale industrialization.

In some preferred embodiments of the present application, in step (b), during the process of adding fluoride for reaction, the amount of fluoride added is 10 to 15 times the theoretical amount, such as 10, 11, 12, 13, 14, 15 times; Wherein, when generating precipitation MgF2, the theoretical molar consumption of fluoride is 2 times of the magnesium ion molar quantity in the solution.

Preferably, the reaction time is 1 to 3 hours;

Preferably, the fluoride includes sodium fluoride and/or potassium fluoride, more preferably sodium fluoride.

In some preferred embodiments of the present application, in step (c), the concentration of the sulfuric acid solution is 1-2 mol/L, such as 1, 1.5, 2 mol/L;

Preferably, the added amount of the manganese powder is 1.1 to 1.8 times the theoretical amount, and the theoretical amount is the theoretical molar amount of the complete reaction of the manganese powder with the high-valent cobalt and high-valent manganese in the second filter residue, calculated by the following equation: Mn ^{4 +} +Mn→2Mn ²⁺ , 2Co ³⁺ +Mn→2Co ²⁺ +Mn ²⁺ , such as 1.1, 1.2, 1.3, 1.5, 1.8 times;

Preferably, during the reaction, stirring is performed at a speed of 160-200 rpm;

Preferably, the reaction time is 1 to 3 hours;

Preferably, during the reaction, the temperature of the solution system is 80-90°C, such as 80, 85, 90°C;

Preferably, sodium chlorate is added to the fourth filtrate to remove iron.

In some preferred embodiments of the present application, in step (d), the molar ratio of nickel-manganese-cobalt in the ternary precursor mixed solution is 33.3-90:5-33.3:5-33.3, including but not limited to 90:5:5, 33.3:33.3:33.3, 80:10:10, 60:20:20, 50:20:30;

Preferably, in the ternary precursor mixed solution, the molar concentration of metal ions is 1.2-2.2 mol/L, including but not limited to 1.2, 1.5, 1.8, 2.0, 2.2 mol/L.

In some preferred embodiments of the present application, in step (d), the co-precipitation reaction is carried out by conventional methods, the preferred precipitating agent is lye, and the preferred complexing agent is ammonia water.

In some preferred embodiments of the present application, in step (d), the particle size of the nickel-cobalt-manganese ternary precursor material is D50=3˜15 μm.

A nickel-cobalt-manganese ternary positive electrode material is mainly prepared from the nickel-cobalt-manganese ternary precursor material prepared by the preparation method, and has the advantages of high purity and low impurities.

Beneficial effect

Compared with the prior art, the beneficial effects of the present application are:

(1) The preparation method of the nickel-cobalt-manganese ternary precursor material provided by this application uses crude solid cobalt hydroxide as a raw material, and realizes the recovery of the three elements of nickel, cobalt and manganese in the crude cobalt hydroxide.

(2) The preparation method provided by this application can quickly obtain raw materials for the preparation of ternary lithium-ion battery precursors, and prepare high-purity, low-impurity nickel-cobalt-manganese ternary precursor materials, and its impurity indicators are better than national standards , so as to realize the full recycling of the valuable metals in the crude cobalt hydroxide.

(3) The preparation method provided by the present application has short process, high efficiency, easy operation and low production cost, and is suitable for industrial mass production.

Description of drawings

In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the description of the specific embodiments or prior art. Obviously, the accompanying drawings in the following description The drawings are some implementations of the present application. For those skilled in the art, other drawings can also be obtained according to these drawings without creative work.

Fig. 1 is the process flow chart of the preparation method of nickel-cobalt-manganese ternary precursor material in the embodiment of the present application;

Fig. 2 is the XRD pattern of the 10.0 μm N _i0.60 Co _0.20 Mn _0.20 (OH) ₂ precursor synthesized in Example 1 of the present application.

Embodiments of the present invention

The technical solutions of the present application will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but those skilled in the art will understand that the following described embodiments are part of the embodiments of the present application, not all of them. It is only used to illustrate the application and should not be considered as limiting the scope of the application. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the scope of protection of this application. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

Unless otherwise specified, the chemical composition of the crude cobalt hydroxide used in the examples of the present application is shown in Table 1.

Table 1 crude cobalt hydroxide chemical composition table

Example 1

The preparation method of the nickel-cobalt-manganese ternary precursor material provided in this embodiment, referring to Figure 1, specifically includes the following steps:

(1) Put crude cobalt hydroxide, ammonium sulfate, ammonia water, etc. into reaction tank A, and leaching for 3 hours at a stirring speed of 200rpm, a liquid-solid ratio of 8:1, and 50°C, wherein the total ammonium concentration is 160g/ L; the molar ratio of ammonia water to ammonium salt is 2.5:1; filter to obtain the first filtrate and the first filter residue.

(2) The first filtrate obtained in step (1) is mixed with 25% P507+75% sulfonated kerosene solution according to the ratio of 1:1 for extraction; 2.0mol/L sulfuric acid is used for back extraction, and the obtained raffinate is passed through After degreasing, it can return to step (1) for recycling. After stripping the P507 sulfonated kerosene solution, add 5mol/L hydrochloric acid solution for washing and purification; the washing solution obtained after phase separation can be recycled after removing trace iron and zinc with N235 organic solution.

(3) drop the first filter residue obtained in step (1) into reaction tank B, and add concentrated sulfuric acid and tap water in the tank, control initial sulfuric acid concentration to be 0.5mol/L, reaction temperature is at 50 ℃, and stirring is 200rpm, After reacting for 3 hours, after the reaction, filter, and the obtained second filtrate is a sulfate solution containing magnesium, iron, calcium, aluminum and other elements, which can be sent to the sewage treatment workshop for treatment. The second filter residue is high-valent cobalt manganese oxide.

(4) Put the stripping solution obtained in step (2) into reaction tank C, add manganese powder to remove copper, wherein the amount of manganese powder added is 10 times the theoretical amount, the reaction temperature is 80°C, the stirring speed is 200rpm, and the reaction is 1h Finally, add 12 times the theoretical amount of sodium fluoride to remove magnesium, react for 3 hours to filter, and the third filtrate is a high-purity high-purity cobalt, nickel, and manganese mixed sulfate solution. The third filter residue is a mixture of copper and magnesium fluoride.

(5) the second filter residue that step (3) obtains is dropped into reaction tank D, add a certain amount of sulfuric acid and manganese powder, wherein the initial concentration of sulfuric acid is 1.5mol/L, and the add-on of manganese powder is 1.5 times of theoretical consumption, The reaction temperature was 80° C., the stirring speed was 200 rpm, and the reaction was carried out for 2 hours. After the reaction, the obtained product was filtered, and the fourth filtrate was a cobalt- and manganese-containing sulfate solution without filter residue.

(6) According to the molar ratio of the ternary precursor material nickel, manganese and cobalt, the three elements are 60:20:20, the filtrate obtained in step (4) and step (5) has just been added during the batching process, and the total amount of nickel, cobalt, manganese and three elements is configured. 2mol/L nickel cobalt manganese sulfate solution.

(7) The sulfate solution of nickel, cobalt and manganese configured in step (6), 10mol/L liquid caustic soda, and 8mol/L ammonia water are added in parallel to the reactor with bottom liquid for coprecipitation reaction, wherein the coprecipitation process continues to feed nitrogen protection, the bottom liquid is a mixed solution of ammonia + sodium hydroxide with an ammonium root concentration of 2.0-5.5g/L and a pH of 11.50-12.50, and the volume of the bottom liquid is half of the effective volume of the reactor; Atmosphere protection, the nitrogen flow rate is 0.5m3/h, the pH is between 10.50-11.00, the concentration of free ammonia in the solution is 8.0-10.0g/L, the stirring speed is 230rpm, the flow rate of the ternary liquid is controlled at 400L/h, the particle size in the kettle Stop the machine after the D50 reaches 10um, and the obtained precipitate can be obtained after centrifugal washing, drying, sieving and demagnetization to obtain the ternary precursor material.

The XRD test was carried out on the material obtained in Example 1, and the test results are shown in Figure 2. From Figure 2, it can be seen that the synthesized nickel-cobalt-manganese ternary precursor material has a complete crystal structure, no miscellaneous peaks, and high crystallinity.

Example 2

The preparation method of the nickel-cobalt-manganese ternary precursor material provided in this embodiment specifically includes the following steps:

(1) Put crude cobalt hydroxide, ammonium sulfate, ammonia water, etc. into the reaction tank A, and leaching for 3 hours at a stirring speed of 200rpm, a liquid-solid ratio of 8:1, and 50°C, wherein the total ammonium concentration is 150g/ L; the molar ratio of ammonia water to ammonium salt is 3.0:1; filter to obtain the first filtrate and the first filter residue.

(3) drop the first filter residue obtained in step (1) into reaction tank B, and add concentrated sulfuric acid and tap water in the tank, control initial sulfuric acid concentration to be 0.5mol/L, reaction temperature is at 50 ℃, and stirring is 200rpm, React for 2 hours. After the reaction, filter. The second filtrate obtained is a sulfate solution containing magnesium, iron, calcium, aluminum and other elements, which can be sent to the sewage treatment workshop for treatment. The second filter residue is high-valent cobalt manganese oxide.

(4) Put the stripping solution obtained in step (2) into reaction tank C, add manganese powder to remove copper, wherein the amount of manganese powder added is 8 times the theoretical amount, the reaction temperature is 80 ° C, the stirring speed is 200 rpm, and the reaction is 1h Finally, add 10 times the theoretical amount of sodium fluoride to remove magnesium, react for 2 hours to filter, and the third filtrate is a high-purity high-purity cobalt, nickel, and manganese mixed sulfate solution. The third filter residue is a mixture of copper and magnesium fluoride.

(5) the second filter residue that step (3) obtains is dropped into reaction tank D, add a certain amount of sulfuric acid and manganese powder, wherein the initial concentration of sulfuric acid is 1.2mol/L, and the add-on of manganese powder is 1.3 times of theoretical consumption, The reaction temperature was 80° C., the stirring speed was 200 rpm, and the reaction was carried out for 2 hours. After the reaction, the obtained product was filtered, and the fourth filtrate was a cobalt- and manganese-containing sulfate solution without filter residue.

(6) According to the molar ratio of the ternary precursor material nickel, manganese and cobalt, the three elements are 50:20:30, the filtrate obtained in step (4) and step (5) has just been added during the batching process, and the total amount of nickel, cobalt, manganese and three elements is configured. 2mol/L nickel cobalt manganese sulfate solution.

(6) The sulfate solution of nickel, cobalt and manganese configured in step (6), 10mol/L liquid caustic soda, and 8mol/L ammonia water are added in parallel to the reactor with bottom liquid for coprecipitation reaction, wherein the coprecipitation process continues to feed nitrogen Protection, the bottom liquid is a mixed solution of ammonia + sodium hydroxide with an ammonium root concentration of 4.0-5.5g/L and a pH of 11.50-12.50. The volume of the bottom liquid is half of the effective volume of the reactor; Atmosphere protection, the nitrogen flow rate is 0.5m3/h, the pH is 10.50-11.00, the concentration of free ammonia in the solution is 8.0-10.0g/L, the stirring speed is 230rpm, the flow rate of the ternary liquid is controlled at 400L/h, and the particle size D50 in the kettle reaches Shut down after 10um, and the obtained precipitate can be obtained after centrifugal washing, drying, sieving and demagnetization to obtain the ternary precursor material.

Example 3

(4) Put the stripping solution obtained in step (2) into reaction tank C, add nickel powder to remove copper, wherein the amount of nickel powder added is 8 times the theoretical amount, the reaction temperature is 90 ° C, the stirring speed is 200 rpm, and the reaction is 1 h Finally, add 10 times the theoretical amount of sodium fluoride to remove magnesium, react for 2 hours to filter, and the third filtrate is a high-purity high-purity cobalt, nickel, and manganese mixed sulfate solution. The third filter residue is a mixture of copper and magnesium fluoride.

(5) the second filter residue that step (3) obtains is dropped into reaction tank D, add a certain amount of sulfuric acid and manganese powder, wherein the initial concentration of sulfuric acid is 1.2mol/L, and the add-on of manganese powder is theoretical consumption: 1.3 times, The reaction temperature was 80° C., the stirring speed was 200 rpm, and the reaction was carried out for 2 hours. After the reaction, the obtained product was filtered, and the fourth filtrate was a cobalt- and manganese-containing sulfate solution without filter residue.

(6) According to the molar ratio of the three elements of nickel, manganese and cobalt as the ternary precursor material is 87:05:08, the filtrate obtained in step (4) and step (5) has just been added during the batching process, and the total amount of nickel, cobalt, manganese and three elements 2mol/L nickel cobalt manganese sulfate solution.

(7) The sulfate solution of nickel, cobalt and manganese configured in step (6), 10mol/L liquid caustic soda, and 8mol/L ammonia water are added in parallel to the reactor with bottom liquid for coprecipitation reaction, wherein the coprecipitation process continues to feed nitrogen Protection, the bottom liquid is a mixed solution of ammonia + sodium hydroxide with an ammonium root concentration of 4.0-5.5g/L and a pH of 11.50-12.50. The volume of the bottom liquid is half of the effective volume of the reactor; Atmosphere protection, the nitrogen flow rate is 0.5m3/h, the pH is 10.80-11.10, the concentration of free ammonia in the solution is 6.0-10.0g/L, the stirring speed is 230rpm, the flow rate of the ternary liquid is controlled at 400L/h, and the particle size D50 in the kettle reaches Shut down after 10um, and the obtained precipitate can be obtained after centrifugal washing, drying, sieving and demagnetization to obtain the ternary precursor material.

Comparative example 1

The preparation steps of Comparative Example 1 are basically the same as that of Example 1, except that in step (4): only 5 times of the theoretical amount of sodium fluoride is added.

Comparative example 2

The preparation steps of Comparative Example 2 are basically the same as those of Example 1, except that in step (4): no manganese powder is added for copper removal.

Test case

The physical and chemical indicators of the nickel-cobalt-manganese ternary precursor materials prepared in Examples 1-3 and Comparative Examples 1-2 were tested, and the test results are shown in Table 2.

Table 2 Physical and chemical indicators of nickel-cobalt-manganese ternary precursor materials

The experimental results show that this application uses crude cobalt hydroxide as a raw material, fully utilizes the nickel and manganese elements contained therein, and the prepared nickel-cobalt-manganese ternary precursor material has the characteristics of high purity and low impurity, and its impurity index All are better than the national standard, thereby realizing the full recovery and utilization of the valuable metals in the crude cobalt hydroxide.

In addition, comparative example 1 is mainly a change in the process. The insufficient amount of sodium fluoride added will lead to incomplete removal of magnesium from the solution, and the remaining 0.0020-0.0040g/L magnesium ions in the solution will be enriched into the nickel prepared in the subsequent process. Among the cobalt-manganese ternary precursors, the impact on product quality is more obvious.

Contrast 2 does not use the process of adding manganese powder to remove copper, 0.0010-0.0020g/L copper ions in the solution, and finally enriches the content of copper in the nickel-cobalt-manganese ternary precursor product to 0.0012wt%, which is difficult to meet the requirements of high-end products .

Although the present application has been illustrated and described with specific embodiments, it should be appreciated that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; those of ordinary skill in the art should understand that: In case of deviating from the spirit and scope of the present application, the technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features thereof may be equivalently replaced; and these modifications or replacements do not make the technical solutions of the corresponding technical solutions Essentially departing from the scope of the technical solutions of the various embodiments of the application; therefore, it is meant to include in the appended claims all such replacements and modifications within the scope of the application.

Claims

A method for preparing a nickel-cobalt-manganese ternary precursor material, characterized in that it comprises the following steps:

(a), mixing the crude solid cobalt hydroxide, soluble ammonium salt, and ammonia water, and after ammonia leaching reaction, solid-liquid separation to obtain the first filtrate and the first filter residue; using sulfuric acid solution to leach the first filter residue, After leaching, solid-liquid separation is performed to obtain a second filtrate and a second filter residue;

(b), using a mixed solution of the extraction phase P507 and sulfonated kerosene to extract the first filtrate in step (a) to obtain an extract, and then use an acid solution to back-extract the extract to obtain a back-extraction liquid and raffinate; adding manganese powder and/or nickel powder to react in the stripping liquid, then adding fluoride to react, then solid-liquid separation to obtain the third filtrate and the third filter residue;

(c), add sulfuric acid solution and manganese powder in the described second filter residue in step (a), after reaction, solid-liquid separation obtains the 4th filtrate and the 4th filter residue;

(d), combining the third filtrate and the fourth filtrate to obtain a nickel-cobalt-manganese sulfate mixed solution, and adding the sulfate according to the ratio of nickel, cobalt, and manganese in the ternary precursor material Mixing the solution to obtain a ternary precursor mixed solution, mixing the ternary precursor mixed solution with a precipitating agent and a complexing agent, after a co-precipitation reaction occurs, separating the solid from the liquid, and drying the obtained solid to obtain the nickel-cobalt-manganese Ternary precursor material.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, characterized in that, in step (a), the molar ratio of the ammonia water to the soluble ammonium salt is 1-3.5:1.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 2, characterized in that the total ammonium concentration in the ammonia water is 110-160 g/L.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 2, wherein the soluble ammonium salt includes at least one of ammonium sulfate, ammonium bicarbonate, ammonium carbonate and ammonium chloride.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 2, characterized in that, during the ammonia leaching reaction, the temperature of the solution system is 40-60°C.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, characterized in that, in step (a), in the process of leaching the first filter residue, the molar concentration of the sulfuric acid solution is 0.5-1.0 mol/L; or/and

During the leaching process, compressed air is also introduced, and the flow rate of the compressed air is 2-3 m3/h.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 6, characterized in that, during the leaching process, the temperature of the solution system is 40-50°C; or/and

During the leaching process, stirring at a speed of 160-200 rpm; or/and

The reaction time of the leaching is 1-3 hours.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 6, characterized in that, after the leaching, the pH of the solution system is 2.0-3.5.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, is characterized in that, in step (b), in the mixed solution of described extraction phase P507 and sulfonated kerosene, extraction phase P507 volume ratio is 20%-30%, the volume ratio of the organic phase to the water phase in the mixed solution is 1:2-2:1.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, is characterized in that, in step (b), in the process of adding manganese powder and/or nickel powder to react, the manganese The amount of nickel powder and/or nickel powder added is 5-10 times of the theoretical molar amount.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 10, characterized in that, during the reaction, the temperature of the solution system is 80-90°C; or/and

The reaction time is 1-3 hours.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, is characterized in that, in step (b), in the process that described adding fluoride reacts, the addition amount of described fluoride is 10 to 15 times the theoretical molar amount; or/and

The fluoride includes sodium fluoride and/or potassium fluoride.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 12, characterized in that the reaction time is 1-3 hours.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 12, characterized in that, in step (c), the concentration of the sulfuric acid solution is 1-2mol/L; or/and

The added amount of the manganese powder is 1.1-1.8 times of the theoretical molar amount.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 12, characterized in that, during the reaction, stirring is performed at a speed of 160-200rpm; or/and

The reaction time is 1 to 3 hours; or/and

During the reaction, the temperature of the solution system is 80-90°C.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, characterized in that sodium chlorate is added to the fourth filtrate to remove iron.
The preparation method of nickel-cobalt-manganese ternary precursor material according to claim 1, is characterized in that, in step (d), in described ternary precursor mixed solution, the molar ratio of nickel, manganese, cobalt is 33.3 ~90:5~33.3:5~33.3.
The method for preparing a nickel-cobalt-manganese ternary precursor material according to claim 17, characterized in that, in the ternary precursor mixed solution, the molar concentration of metal ions is 1.2-2.2 mol/L.
A nickel-cobalt-manganese ternary positive electrode material prepared from the nickel-cobalt-manganese ternary precursor material prepared by the preparation method described in any one of claims 1-18.
A lithium ion battery, comprising the positive electrode of the battery prepared by the nickel-cobalt-manganese ternary positive electrode material according to claim 19.