CN111244437A - Preparation method of ternary precursor raw material - Google Patents
Preparation method of ternary precursor raw material Download PDFInfo
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- CN111244437A CN111244437A CN202010060085.8A CN202010060085A CN111244437A CN 111244437 A CN111244437 A CN 111244437A CN 202010060085 A CN202010060085 A CN 202010060085A CN 111244437 A CN111244437 A CN 111244437A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a ternary precursor raw material, which specifically comprises the following steps: 1) removing iron from the sulfate stock solution, and filtering to obtain sulfate initial solution; 2) standing the initial sulfate solution obtained in the previous step, and extracting to obtain a purified sulfate solution; 3) adding sulfuric acid into the sulfate purification solution obtained in the previous step to perform a homoionic effect reaction, centrifuging and rinsing to obtain a high-purity sulfate wet product; 4) and drying the high-purity sulfate wet product obtained in the previous step to obtain the high-purity sulfate crystal.
Description
Technical Field
The invention belongs to the technical field of preparation of ternary precursor raw materials, and particularly relates to a preparation method of a ternary precursor raw material.
Background
Under the drive of the energy technology revolution and the emerging technology, the lithium ion battery is widely applied as a novel green secondary battery. The main components of the lithium ion battery are a positive electrode, a negative electrode, an electrolyte, a diaphragm and the like. The most promising lithium ion battery anode material is nickel cobalt lithium manganate (NCM) ternary material. The precursor product of the ternary composite anode material is obtained by taking nickel, cobalt and manganese salts as raw materials and adjusting the proportion of nickel, cobalt and manganese according to different requirements. Because the nickel-cobalt-manganese ternary material lithium battery has the advantages of high specific capacity, good safety, good cycling stability and the like, the nickel-cobalt-manganese ternary material lithium battery is widely applied to the fields of notebook computers, digital equipment, electric bicycles, mobile communication, electric tools and the like.
The key technology of the nickel-cobalt-manganese ternary positive electrode material is synthesis of a ternary precursor material, the nickel-cobalt-manganese ternary positive electrode material is industrially prepared by a chemical coprecipitation method, and the key of the preparation process is to obtain a high-purity nickel-cobalt-manganese soluble solution, wherein the nickel-cobalt-manganese soluble solution requires very low content of other elements besides nickel-cobalt-manganese elements, and otherwise the performance and the morphology of the material are influenced.
In the prior art for producing the ternary precursor nickel cobalt manganese sulfate raw material, the impurity removal aspect is as follows: the fluoride is mainly used for removing calcium and magnesium impurities, but the fluoride has high requirements on equipment, the impurities are not thoroughly removed, and the product recovery rate is low. In the aspect of crystallization: mainly adopts an MVR evaporation crystallization method, the method has high energy consumption and low yield, and impurities are mixed in the product, so that the purity of the product is not enough. Aiming at the high requirement on the raw material content in the preparation of the ternary precursor in the industry, how to solve the problem of the impurity removal and purification method of the ternary precursor raw material has important significance.
Disclosure of Invention
In order to meet the high requirement on the content of raw materials in the preparation of a ternary precursor, the invention provides a preparation method of a ternary precursor raw material, in particular to a method for impurity removal and purification of nickel cobalt manganese sulfate as the ternary precursor raw material, wherein the impurity content of nickel sulfate, cobalt sulfate and manganese sulfate crystals as the prepared ternary precursor raw materials is less than or equal to 45ppm of sodium, less than or equal to 40ppm of potassium, less than or equal to 30ppm of calcium, less than or equal to 40ppm of magnesium, less than or equal to 5ppm of iron, less than or equal to 3ppm of zinc, less than or equal to 1ppm of copper and less than or equal to 1ppm of lead.
A preparation method of a ternary precursor raw material specifically comprises the following steps:
1) removing iron from the sulfate stock solution, and filtering to obtain sulfate initial solution;
2) standing the initial sulfate solution obtained in the previous step, and extracting to obtain a purified sulfate solution;
3) adding sulfuric acid into the sulfate purification solution obtained in the previous step to perform a homoionic effect reaction, centrifuging and rinsing to obtain a high-purity sulfate wet product;
4) and drying the high-purity sulfate wet product obtained in the previous step to obtain a high-purity sulfate crystal, wherein in the impurity contents of nickel sulfate, cobalt sulfate and manganese sulfate crystals, the content of sodium is less than or equal to 45ppm, the content of potassium is less than or equal to 40ppm, the content of calcium is less than or equal to 30ppm, the content of magnesium is less than or equal to 40ppm, the content of iron is less than or equal to 5ppm, the content of zinc is less than or equal to 3ppm, the content of copper is less than or equal to 1ppm and the content of lead is less than or.
The sulfate stock solution in the step 1) of the invention is one or a mixture of nickel sulfate, cobalt sulfate and manganese sulfate.
The iron removal in the step 1) is carried out by adding an oxidant or an alkaline neutralizer, wherein the oxidant comprises but is not limited to hydrogen peroxide, manganese dioxide and potassium permanganate, the alkaline neutralizer comprises but is not limited to ammonia water, sodium hydroxide, manganese hydroxide, cobalt hydroxide and nickel hydroxide, the iron removal reaction temperature is 60-80 ℃, and the reaction time is 0.5-3.0 h.
Standing for 8.0-24h in the step 2); the extraction is carried out by using an extracting agent including but not limited to triethanolamine solution, ammonium acetate solution, citric acid solution and EDTA solution; the concentration of the extracting agent is 5-25%, and the extracting agent: the volume ratio of the treatment liquid is 0.1-1.0: 100.
and 3) carrying out the same ion effect reaction, adding a sulfuric acid or sulfurous acid solution, wherein the mass fraction is 60-98%, the reaction time is 0.5-5h, the reaction is carried out at normal temperature and normal pressure, and the stirring force is 200-500 r/min.
Centrifuging and rinsing in the step 3), wherein sulfate mother liquor is used for rinsing in the process, the pH is 5-7, and the concentration of the mother liquor is 2-5 mol/L.
And 4), drying in the step 4) is vacuum drying or airflow drying.
Compared with the prior art, the invention has the advantages that:
1. the method has the advantages of simple process steps, stable process parameters and low requirements on equipment, and the equipment commonly used under the normal pressure condition can meet the requirements.
2. The medicament used by the invention is conventional, has various types, low price and low cost. And the used medicament and the used extracting agent are pollution-free and environment-friendly.
3. In the impurity contents of nickel sulfate, cobalt sulfate and manganese sulfate crystals of the ternary precursor raw material prepared by the method, sodium is less than or equal to 45ppm, potassium is less than or equal to 40ppm, calcium is less than or equal to 30ppm, magnesium is less than or equal to 40ppm, iron is less than or equal to 5ppm, zinc is less than or equal to 3ppm, copper is less than or equal to 1ppm and lead is less than or equal to 1ppm, and the quality is higher than the domestic industrial standard.
Drawings
FIG. 1 is a schematic flow diagram of the preparation process of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1:
1) taking 500ml of nickel sulfate leachate containing impurities in a certain factory, heating and stirring by using a magnetic stirrer, setting the temperature at 60 ℃, adding 10ml of 27% hydrogen peroxide solution, and stirring and reacting for 0.5h, wherein the impurity content of the solution is shown in the table below;
2) adjusting the pH value to 5-6 by using an ammonia water solution, and filtering to obtain a nickel sulfate initial solution; standing for 8h, taking the upper layer liquid, adding an EDTA solution, and extracting to obtain a nickel sulfate purified solution;
3) adding 80% sulfuric acid solution into the purified solution to perform a homoionic effect reaction, wherein the stirring force is 300r/min, the reaction time is 2 hours, centrifuging the slurry, and rinsing by using nickel sulfate solution with the same concentration;
4) and drying the rinsed nickel sulfate wet product by using a vacuum drying oven to obtain the high-purity nickel sulfate crystal.
Example 2:
1) taking 1000ml of cobalt sulfate mixed leachate of a certain factory, wherein the impurity content of the solution is shown in the following table, heating and stirring by using a magnetic stirrer, setting the temperature at 80 ℃, adding 20ml of 15% hydrogen peroxide solution, and stirring and reacting for 0.5 h;
2) adjusting the pH value to 5-6 by using a sodium hydroxide solution, filtering to obtain a cobalt sulfate initial solution, standing for 10 hours, taking an upper layer liquid, adding a triethanolamine solution, and extracting to obtain a cobalt sulfate purified solution;
3) adding 85% sulfuric acid solution into the purified solution to perform a homoionic effect reaction, wherein the stirring force is 400r/min, the reaction time is 1h, centrifuging the slurry, and rinsing the slurry by using cobalt sulfate solution with the same concentration;
4) and drying the wet cobalt sulfate product obtained by rinsing by using a vacuum drying oven to obtain high-purity cobalt sulfate crystals.
Example 3:
1) taking 1000ml of leaching solution containing miscellaneous manganese sulfate in a certain factory, heating and stirring by using a magnetic stirrer at 75 ℃ under the condition that the impurity content of the solution is as shown in the following table, adding 10g of manganese dioxide, and stirring and reacting for 0.5 h;
2) regulating the pH value to 5-6 by using a manganese hydroxide solution, filtering to obtain a manganese sulfate initial solution, standing for 12 hours, taking an upper layer liquid, and adding an EDTA solution for extraction to obtain a manganese sulfate purified solution;
3) adding 90% sulfuric acid solution into the purified solution to perform a homoionic effect reaction, wherein the stirring force is 250r/min, the reaction time is 0.5h, centrifuging the slurry, and rinsing by using 3mol/L manganese sulfate solution;
4) and drying the wet manganese sulfate product obtained by rinsing by using a vacuum drying oven to obtain the high-purity manganese sulfate crystal.
The impurity content data in the examples are given in the following table:
and (4) conclusion: as can be seen from the data table, the impurity contents of the ternary precursor raw materials of nickel sulfate, cobalt sulfate and manganese sulfate crystals obtained by the method are all lower than the industrial standard.
Although the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. The preparation method of the ternary precursor raw material is characterized by comprising the following steps:
1) removing iron from the sulfate stock solution, and filtering to obtain sulfate initial solution;
2) standing the initial sulfate solution obtained in the previous step, and extracting to obtain a purified sulfate solution;
3) adding sulfuric acid into the sulfate purification solution obtained in the previous step to perform a homoionic effect reaction, centrifuging and rinsing to obtain a high-purity sulfate wet product;
4) and drying the high-purity sulfate wet product obtained in the previous step to obtain a high-purity sulfate crystal, wherein in the impurity contents of nickel sulfate, cobalt sulfate and manganese sulfate crystals, the content of sodium is less than or equal to 45ppm, the content of potassium is less than or equal to 40ppm, the content of calcium is less than or equal to 30ppm, the content of magnesium is less than or equal to 40ppm, the content of iron is less than or equal to 5ppm, the content of zinc is less than or equal to 3ppm, the content of copper is less than or equal to 1ppm and the content of lead is less than or.
2. The method for preparing a ternary precursor starting material as claimed in claim 1, wherein: the sulfate stock solution in the step 1) is one or a mixture of nickel sulfate, cobalt sulfate and manganese sulfate.
3. The method for preparing a ternary precursor starting material as claimed in claim 1, wherein: the iron removal in the step 1) is carried out by adding an oxidant or an alkaline neutralizer, wherein the oxidant is hydrogen peroxide, manganese dioxide and potassium permanganate, the alkaline neutralizer is ammonia water, sodium hydroxide, manganese hydroxide, cobalt hydroxide and nickel hydroxide, the iron removal reaction temperature is 60-80 ℃, and the reaction time is 0.5-3.0 h.
4. The method for preparing a ternary precursor starting material as claimed in claim 1, wherein: standing for 8.0-24h in the step 2); the extraction is carried out by using an extracting agent including but not limited to triethanolamine solution, ammonium acetate solution, citric acid solution and EDTA solution; the concentration of the extracting agent is 5-25%, and the extracting agent: the volume ratio of the treatment liquid is 0.1-1.0: 100.
5. the method for preparing a ternary precursor starting material as claimed in claim 1, wherein: and 3) carrying out the same ion effect reaction, adding a sulfuric acid or sulfurous acid solution, wherein the mass fraction is 60-98%, the reaction time is 0.5-5h, the reaction is carried out at normal temperature and normal pressure, and the stirring force is 200-500 r/min.
6. The method for preparing a ternary precursor starting material as claimed in claim 1, wherein: centrifuging and rinsing in the step 3), wherein sulfate mother liquor is used for rinsing in the process, the pH is 5-7, and the concentration of the mother liquor is 2-5 mol/L.
7. The method for preparing a ternary precursor starting material as claimed in claim 1, wherein: and 4) drying, namely drying by adopting vacuum drying or airflow drying.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112897599A (en) * | 2021-05-08 | 2021-06-04 | 蜂巢能源科技有限公司 | Crystallization method of nickel sulfate, cobalt sulfate and manganese sulfate |
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| CN101824550A (en) * | 2009-03-02 | 2010-09-08 | 姚龚斌 | Extracting and purifying technology of high purity nickel |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN103496746A (en) * | 2013-08-27 | 2014-01-08 | 中南大学 | Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization |
| CN109518005A (en) * | 2018-10-29 | 2019-03-26 | 安徽寒锐新材料有限公司 | A kind of production method of battery grade cobalt sulfate crystal |
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- 2020-01-19 CN CN202010060085.8A patent/CN111244437B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824550A (en) * | 2009-03-02 | 2010-09-08 | 姚龚斌 | Extracting and purifying technology of high purity nickel |
| CN102627333A (en) * | 2012-04-24 | 2012-08-08 | 中南大学 | Method for refined nickel sulfate |
| CN103496746A (en) * | 2013-08-27 | 2014-01-08 | 中南大学 | Method for preparing cell-grade high-purity manganese sulfate by low-grade manganese ore high-pressure crystallization |
| CN109518005A (en) * | 2018-10-29 | 2019-03-26 | 安徽寒锐新材料有限公司 | A kind of production method of battery grade cobalt sulfate crystal |
Non-Patent Citations (1)
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| 邢学永等: "硫酸锰溶液净化技术研究现状与分析", 《云南冶金》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112897599A (en) * | 2021-05-08 | 2021-06-04 | 蜂巢能源科技有限公司 | Crystallization method of nickel sulfate, cobalt sulfate and manganese sulfate |
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