CN108807951B - Preparation method of lithium battery positive electrode active material - Google Patents
Preparation method of lithium battery positive electrode active material Download PDFInfo
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- CN108807951B CN108807951B CN201810894850.9A CN201810894850A CN108807951B CN 108807951 B CN108807951 B CN 108807951B CN 201810894850 A CN201810894850 A CN 201810894850A CN 108807951 B CN108807951 B CN 108807951B
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
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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
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Abstract
A method for preparing a positive active material of a lithium battery includes the following steps: 1) reacting LiNO with a catalyst3、Mn(NO3)2、Co(NO3)2·6H2O and Ni (NO)3)2·6H2Dispersing O into deionized water, 2) dropwise adding the mixed solution obtained in the step 1) into a citric acid-ethylene glycol aqueous solution to form gel, and then removing water at 140 ℃; 3) pulverizing the gel with water removed, and heating at 400 deg.C for 4 hr; 4) calcining the dry glue treated in the step 3) at the temperature of 700-1000 ℃ for 12h to obtain powder. The NCM111 of the material has the first discharge specific capacity of 203.2 mA.h.g at the voltage of 2.5-4.5V‑1The coulombic efficiency was 88.5%. The capacity retention rate at 50 th cycle was 88.4%, respectively.
Description
Technical Field
The invention relates to a lithium ion battery, in particular to a preparation method of a lithium battery positive electrode active material.
Background
At present, the preparation of the ternary material of the positive electrode of the lithium battery mainly adopts a coprecipitation method to synthesize a ternary precursor, and then adopts a high-temperature solid phase method to synthesize a final product. The coprecipitation method mainly has the defects of high synthesis temperature, low uniformity of the generated ternary cathode material and unsuitability for the cathode ternary material produced by the coprecipitation method under the condition of high requirement on the stability of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a lithium battery anode ternary material with low synthesis temperature and high uniformity of the produced ternary anode material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a ternary material of a positive electrode of a lithium battery comprises the following steps: 1) uniformly mixing soluble lithium salt, soluble manganese salt, soluble nickel salt and soluble cobalt salt, and dispersing the mixture into deionized water to form a multi-element mixed solution;
2) dripping the mixed solution obtained in the step 1) into a citric acid-ethylene glycol aqueous solution to form gel, and removing water at 140 ℃; the ratio of citric acid to metal ions is 1: 1;
3) pulverizing the gel with water removed, and heating at 400 deg.C for 4 hr;
4) calcining the dry glue treated in the step 3) at the temperature of 700-1000 ℃ for 12h to obtain powder.
5) 1 mol. L-1The ammonia water is placed in a water bath at the temperature of 85-90 ℃ and then is continuously stirred;
6) slowly dropping Al (OH) into the ammonia water solution of the step 53Suspending the solution to form a precipitate;
7) after the reaction for 1 to 2 hours in the step 6), 1 mol.L is added into the mixture-1The nitric acid is used for hydrolyzing and peptizing the precipitate, and the clear AlOOH sol is obtained after continuous stirring and aging for 15-20 h;
8) taking the powder prepared in the step 4), putting the powder into the sol in the step 7) at a solid-to-liquid ratio of 40-60g/L, continuously stirring and heating, and evaporating and drying;
9) reacting the product of step 8) with LiOH H2Mixing O uniformly, and keeping the temperature of 800 ℃ for 20 hours in an oxygen atmosphere to obtain a required product; the LiOH. H2Li in O+For Li in step 1)+2 times of the content.
In the above preparation method of the ternary positive electrode material for a lithium battery, preferably, the calcination temperature in the step 4) is 900 ℃.
The gel dispersion system of the present invention is a heterogeneous system with a high degree of dispersion. The sol has the ionic radius of 1-100 nm, a large phase interface, high surface energy and strong adsorption performance. Various ionic materials of the lithium ion battery active material are uniformly adsorbed on the surface by utilizing the adsorption capacity of the sol, the organic components of the gel are removed by calcining to obtain the powder of the active material, and the sol is not required to be heated in the adsorption process, so that the energy is saved.
In the above method for preparing a positive active material for a lithium battery, preferably, Li is contained in the multi-component mixed solution+: Mn2+: Co2+：Ni2+And the ion total concentration is 2-2.5 mol/L (1: 1:1: 1).
In the above method for preparing the positive electrode active material of the lithium battery, preferably, the nickel salt is at least one of nickel nitrate, nickel chloride, nickel acetate and nickel sulfate; the manganese salt is at least one of manganese nitrate, manganese chloride, manganese acetate and manganese sulfate; the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; the lithium salt is at least one of lithium sulfate, lithium chloride, lithium nitrate and lithium acetate.
In the above method for preparing the lithium battery positive active material, preferably, the gel is crushed and then ball-milled for 2 to 5 hours.
Compared with the prior art, the invention has the advantages that: in the present invention, Al is used2O3Coated LiNi1/3 Co1/3 Mn1/3O2Wherein the core also has lithium ion, and can be used for Al2O3Lithium ions on the cladding layer are replenished. The NCM111 of the material has the first discharge specific capacity of 203.2 mA.h.g at the voltage of 2.5-4.5V-1The coulombic efficiency was 88.5%. The discharge specific capacity retention rate of the 50 th cycle is 88.4 percent respectively.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Examples
A method for preparing a positive active material of a lithium battery includes the following steps: 1) reacting LiNO with a catalyst3、Mn(NO3)2、Co(NO3)2·6H2O and Ni (NO)3)2·6H2O is dispersed in deionized water, the Li+: Mn2+: Co2+：Ni2+1:1:1: 1; the Mn (NO)3)2Is Mn (NO) with the mass fraction of 50 percent3)2An aqueous solution;
2) dripping the mixed solution obtained in the step 1) into a citric acid-ethylene glycol aqueous solution to form gel, and removing water at 140 ℃; the ratio of citric acid to metal ions is 1: 1;
3) crushing the gel with the water removed, ball-milling for 3 hours, and then heating at 400 ℃ for 4 hours;
4) calcining the dry glue treated in the step 3) at 900 ℃ for 12h to obtain powder; the material capacity retention rate is best under the condition of calcining at 900 ℃, and the capacity retention rate is more than 95% under the condition of discharge rate of 1C.
5) 1 mol. L-1The ammonia water is placed in a water bath at 90 ℃ and then is continuously stirred;
6) slowly dropping Al (OH) into the ammonia water solution of the step 53Suspending the solution to form a precipitate;
7) after the reaction for 1.2h in the step 6), 1 mol. L is added-1The nitric acid is used for hydrolyzing and peptizing the precipitate, and the clear AlOOH sol is obtained after continuous stirring and aging for 15-20 h;
8) taking the powder prepared in the step 4), putting the powder into the sol in the step 7) at a solid-to-liquid ratio of 40-60g/L, continuously stirring and heating, and evaporating and drying;
9) reacting the product of step 8) with LiOH H2Mixing O uniformly, and keeping the temperature of 800 ℃ for 20 hours in an oxygen atmosphere to obtain a required product; LiOH. H2Li in O+For Li in step 1)+2 times of the content.
In this example, Al is used2O3Coated LiNi1/3Co 1/3Mn1/3O2Wherein the core also has lithium ion, and can be used for Al2O3Lithium ions on the cladding layer are replenished. The first discharge specific capacity of the NCM111 of the material of the embodiment can reach 203.2 mA.h.g at the voltage of 2.5-4.5V-1The coulombic efficiency was 88.5%. The discharge specific capacity retention rate of the 50 th cycle is 88.4 percent respectively.
Claims (4)
1. A preparation method of a lithium battery positive electrode active material is characterized by comprising the following steps: 1) uniformly mixing soluble lithium salt, soluble manganese salt, soluble nickel salt and soluble cobalt salt, and dispersing the mixture into deionized water to form a multi-element mixed solution; li in the multi-component mixed solution+: Mn2+: Co2+：Ni2+1:1:1:1, and the total ion concentration is 2-2.5 mol/L;
2) dripping the mixed solution obtained in the step 1) into a citric acid-ethylene glycol aqueous solution to form gel, and removing water at 140 ℃; the ratio of citric acid to metal ions is 1: 1;
3) pulverizing the gel with water removed, and heating at 400 deg.C for 4 hr;
4) calcining the dry glue treated in the step 3) at the temperature of 700-1000 ℃ for 12h to obtain powder;
5) 1 mol. L-1The ammonia water is placed in a water bath at the temperature of 85-90 ℃ and then is continuously stirred;
6) slowly dropping Al (OH) into the ammonia water solution of the step 53Suspending the solution to form a precipitate;
7) after the reaction for 1 to 2 hours in the step 6), 1 mol.L is added into the mixture-1The nitric acid is used for hydrolyzing and peptizing the precipitate, and the clear AlOOH sol is obtained after continuous stirring and aging for 15-20 h;
8) taking the powder prepared in the step 4), putting the powder into the sol in the step 7) at a solid-to-liquid ratio of 40-60g/L, continuously stirring and heating, and evaporating and drying;
9) reacting the product of step 8) with LiOH H2Mixing O uniformly, and keeping the temperature of 800 ℃ for 20 hours in an oxygen atmosphere to obtain a required product; the LiOH. H2Li in O+For Li in step 1)+2 times of the content.
2. The method of preparing a positive active material for a lithium battery as claimed in claim 1, wherein: the temperature of calcination in the step 4) is 900 ℃.
3. The method for preparing a positive active material for a lithium battery as claimed in claim 1, wherein the nickel salt is at least one of nickel nitrate, nickel chloride, nickel acetate, and nickel sulfate; the manganese salt is at least one of manganese nitrate, manganese chloride, manganese acetate and manganese sulfate; the cobalt salt is at least one of cobalt nitrate, cobalt chloride, cobalt acetate and cobalt sulfate; the lithium salt is at least one of lithium sulfate, lithium chloride, lithium nitrate and lithium acetate.
4. The method of preparing a positive active material for a lithium battery as claimed in claim 1, wherein the gel is ball-milled for 2 to 5 hours after being pulverized.
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| CN104319385A (en) * | 2014-09-19 | 2015-01-28 | 青岛乾运高科新材料股份有限公司 | Method for preparing nickel cobalt lithium manganese |
| CN105702940B (en) * | 2016-04-29 | 2018-09-21 | 青岛乾运高科新材料股份有限公司 | A method of cladding nickel-cobalt lithium manganate cathode material |
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