CN114759181B - Positive electrode material for solid-state battery, and preparation method and application thereof - Google Patents

Positive electrode material for solid-state battery, and preparation method and application thereof Download PDF

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CN114759181B
CN114759181B CN202210561780.1A CN202210561780A CN114759181B CN 114759181 B CN114759181 B CN 114759181B CN 202210561780 A CN202210561780 A CN 202210561780A CN 114759181 B CN114759181 B CN 114759181B
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positive electrode
electrode material
solid
mixed solution
manganese
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CN114759181A (en
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石佳敏
张坤
华文超
许开华
李聪
杨幸
薛晓斐
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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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
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 provides a positive electrode material for a solid-state battery, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing a nickel source, a cobalt source and a manganese source with a solvent to obtain a metal mixed solution, and mixing styrene and a polymerization inducer with the solvent to obtain a styrene mixed solution; (2) Mixing the metal mixed solution, the styrene mixed solution, ammonia water and alkali liquor for coprecipitation reaction to obtain a precursor material; (3) The method comprises the steps of mixing a precursor material with a lithium source, then carrying out calcination treatment, and carrying out surface in-situ coating solid electrolyte treatment to obtain the positive electrode material for the solid battery.

Description

Positive electrode material for solid-state battery, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a positive electrode material for a solid-state battery, and a preparation method and application thereof.
Background
For the positive electrode of all solid-state lithium batteries, the most widely used materials are lithium transition metal oxides, because they have superior properties, such as good cycling stability and higher operating voltages. However, the solid-solid contact wettability of the positive electrode and the solid electrolyte is poor, resulting in a high interface contact resistance. Due to the excessive electrochemical potential difference, lithium ions are transferred from the solid electrolyte to the metal oxide positive electrode, eventually forming a space charge layer. The formation of a highly resistive space charge layer severely reduces the mobility kinetics of lithium ions at the interface. In the charge-discharge process, interfacial strain/stress caused by volume change of the layered positive electrode may aggravate local deformation of the electrode material, increase charge transfer resistance, and side reactions caused by poor interface structure may cause serious deterioration of electrochemical performance.
In order to achieve good interface compatibility, strategies such as embedding an artificial buffer layer, modifying an electrode or solid electrolyte are adopted in the prior art. In order to achieve better ion transport and interface contact, the surface of the positive electrode material is often designed to be coated with a solid electrolyte in situ to improve the compatibility with the solid electrolyte layer, and the electrochemical performance of the prepared composite material is obviously improved, however, the positive electrode material usually presents a solid sphere state, has lower porosity and exposes a limited surface area.
CN112164776a discloses a composite coated all-solid-state battery positive electrode material, a preparation method thereof and an all-solid-state battery, wherein the composite coated all-solid-state battery positive electrode material comprises a positive electrode material and a composite coating layer coated on the surface of the positive electrode material; the composite coating layer is formed by composite coating of lithium-containing metal oxide and a conductive material. The preparation method can adopt a dry mixing process or a wet mixing process to prepare precursor powder, and then the precursor powder is prepared by calcination.
CN107452954a discloses a preparation method of a lithium-rich manganese-based composite positive electrode material for a solid-state battery, which comprises the following steps: step one: mixing the lithium-rich manganese-based composite positive electrode material according to the mass ratio, and then ball-milling the mixture by using a planetary ball, wherein the ball-milling speed is 300-450r/min, the ball-milling time is 16-22h, and finally the positive electrode material powder with the particle size of 9 mu m is obtained.
The positive electrode material for the solid-state battery can only coat the solid electrolyte on the limited surface, which is not beneficial to the transmission of lithium ions. Therefore, a positive electrode material having a good structure should be studied to realize a more excellent lithium ion transport channel.
Disclosure of Invention
The invention aims to provide a solid-state battery cathode material, a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a positive electrode material for a solid-state battery, the method comprising the steps of:
(1) Mixing a nickel source, a cobalt source and a manganese source with a solvent to obtain a metal mixed solution, and mixing styrene and a polymerization inducer with the solvent to obtain a styrene mixed solution;
(2) Mixing the metal mixed solution, the styrene mixed solution, ammonia water and alkali liquor simultaneously to carry out coprecipitation reaction to obtain a precursor material;
(3) And mixing the precursor material with a lithium source, then carrying out calcination treatment to obtain a nickel cobalt manganese positive electrode material, and carrying out surface in-situ coating solid electrolyte treatment on the nickel cobalt manganese positive electrode material to obtain the positive electrode material for the solid battery.
In the process of preparing the precursor of the positive electrode material, polystyrene (PS) is polymerized in situ on the surface of the precursor, the polystyrene is uniformly nested on the surface of ternary precursor particles, a hole structure is left after the polystyrene reacts in the subsequent calcination process of preparing the positive electrode material, the surface porosity of the ternary material is improved, the surface of the ternary material is coated with solid electrolyte, the holes on the surface of the positive electrode material are favorable for realizing full liquid phase coating of the solid electrolyte, the contact area between the positive electrode active material and the solid electrolyte layer can be increased, a stable interface layer is constructed, and long circulation is realized.
Preferably, the nickel source of step (1) comprises any one or a combination of at least two of nickel chloride, nickel acetate, nickel nitrate or nickel sulfate.
Preferably, the cobalt source comprises any one or a combination of at least two of cobalt chloride, cobalt acetate, cobalt nitrate or cobalt sulfate.
Preferably, the manganese source comprises any one or a combination of at least two of manganese chloride, manganese acetate, manganese nitrate or manganese sulfate.
Preferably, the molar concentration of nickel element in the metal mixed solution is 0.2-1 mol/L, for example: 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, etc.
Preferably, the molar concentration of cobalt element in the metal mixed solution is 0.01-0.3 mol/L, for example: 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L or 0.3mol/L, etc.
Preferably, the molar concentration of manganese element in the metal mixed solution is 0.01-1 mol/L, for example: 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, etc.
Preferably, the total concentration of the metal elements in the metal mixed solution is 0.25 to 1.5mol/L, for example: 0.25mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 1.5mol/L, etc.
Preferably, the polymerization initiator of step (1) comprises 2,2' -azobis (2-methylpropionamide) dihydrochloride.
Preferably, the mass concentration of the polymerization initiator in the styrene mixed solution is 1-3 g/L, for example: 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, etc.
Preferably, the mass concentration of the styrene in the styrene mixed solution is 5-20 g/L, for example: 5g/L, 8g/L, 10g/L, 15g/L, 20g/L, etc.
Preferably, the lye of step (2) comprises sodium carbonate solution, sodium bicarbonate solution or sodium hydroxide solution.
Preferably, the temperature of the coprecipitation reaction is 50 to 80 ℃, for example: 50 ℃, 55 ℃,60 ℃, 70 ℃ or 80 ℃ and the like.
Preferably, the coprecipitation reaction is carried out under an inert atmosphere.
Preferably, the gas of the inert atmosphere comprises nitrogen.
Preferably, the precursor material of step (2) has a particle size of 3 to 15 μm, for example: 3 μm, 5 μm, 10 μm, 12 μm or 15 μm, etc.
Preferably, the molar ratio of the metal element in the precursor material and the lithium element in the lithium source in step (3) is 1 (1.03-1.08), for example: 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, or 1:1.08, etc.
Preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
Preferably, the temperature of the calcination treatment is 650 to 800 ℃, for example: 650 ℃, 680 ℃, 700 ℃, 750 ℃ or 800 ℃ and the like.
Preferably, the calcination treatment is performed for 10 to 15 hours, for example: 10h, 11h, 12h, 13h, 14h or 15h, etc.
Preferably, the mass ratio of the solid electrolyte coating layer and the nickel cobalt manganese positive electrode material in the positive electrode material for solid-state battery in the step (3) is (0.05 to 0.2) 1, for example: 0.05:1, 0.08:1, 0.1:1, 0.15:1, or 0.2:1, etc.
Preferably, the temperature of the in-situ coated solid electrolyte treatment is 200-300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃ or 300 ℃ and the like.
Preferably, the time of the in-situ coating solid electrolyte treatment is 0.2 to 0.8h, for example: 0.2h, 0.3h, 0.5h, 0.6h, 0.8h, etc.
In a second aspect, the present invention provides a positive electrode material for a solid-state battery, which is produced by the method according to the first aspect.
In a third aspect, the present invention provides a positive electrode sheet comprising the positive electrode material for a solid-state battery according to the second aspect.
In a fourth aspect, the present invention provides a solid-state battery comprising the positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
in the process of preparing the ternary precursor, the polystyrene is uniformly embedded into the surfaces of the ternary precursor particles below the in-situ polymerization script on the surfaces of the precursor materials to form the composite material, and the composite material is subjected to lithiation and calcination on the basis of the composite material and then is subjected to in-situ coating of the solid electrolyte, so that the preparation of the composite electrode material which is in good contact with the solid electrolyte layer can be realized.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a positive electrode material for a solid-state battery, and the preparation method of the positive electrode material for the solid-state battery is as follows:
(1) Nickel nitrate, cobalt nitrate and manganese nitrate are dissolved in water according to the molar ratio of nickel, cobalt and manganese elements of 8:1:1 to prepare a solution with metal concentration of 1.5mol/L. 10g of styrene monomer, 100g of polyvinylpyrrolidone PVP and 900g of deionized water are added into the reaction in advance and stirred under nitrogen;
(2) Adding a metal solution, 32wt.% industrial ammonia water and a sodium hydroxide solution into a reaction kettle in proportion, then adding 2.6g of 2,2' -azobis (2-methylpropionamide) dihydrochloride, reacting in a nitrogen atmosphere at 70 ℃, ending after the particle size of the product reaches 10 mu m, and centrifugally washing for three times by using ethanol and pure water to obtain a ternary precursor;
(3) Calcining lithium hydroxide and a ternary precursor for 9 hours at 700 ℃ according to the molar ratio of Li to metal of 1.02:1 to obtain a ternary positive electrode material with high surface porosity; then the positive electrode material is reacted with a solid electrolyte (L) 2 S and P 2 S 5 Molar ratio=7:3), adding the mixture into acetonitrile solution according to the mass ratio of 0.85:0.15, mixing and stirring for 2 hours at 50 ℃, centrifuging and drying at 60 ℃, collecting solid, and burning for 0.5 hour at 260 ℃ to obtain the positive electrode material for the solid-state battery.
Example 2
The embodiment provides a positive electrode material for a solid-state battery, and the preparation method of the positive electrode material for the solid-state battery is as follows:
the embodiment provides a positive electrode material for a solid-state battery, and the preparation method of the positive electrode material for the solid-state battery is as follows:
(1) Nickel nitrate, cobalt nitrate and manganese nitrate are dissolved in water according to the molar ratio of nickel, cobalt and manganese elements of 6:2:2 to prepare a solution with metal concentration of 1.2 mol/L. Adding 12g of styrene monomer, 100g of polyvinylpyrrolidone PVP and 900g of deionized water into the reaction in advance, and stirring under nitrogen;
(2) Adding a metal solution, 32wt.% industrial ammonia water and a sodium hydroxide solution into a reaction kettle in proportion, then adding 2.5g of 2,2' -azobis (2-methylpropionamide) dihydrochloride, reacting in a nitrogen atmosphere at 70 ℃, ending after the particle size of the product reaches 6 mu m, and centrifugally washing for three times by using ethanol and pure water to obtain a ternary precursor;
(3) Calcining lithium hydroxide and a ternary precursor for 9 hours at 700 ℃ according to the molar ratio of Li to metal of 1.02:1 to obtain a ternary positive electrode material with high surface porosity; then the positive electrode material is reacted with a solid electrolyte (L) 2 S and P 2 S 5 Molar ratio=7:3), adding the mixture into acetonitrile solution according to the mass ratio of 0.9:0.1, mixing and stirring for 2 hours at 50 ℃, centrifuging and drying at 60 ℃, collecting solid, and burning for 0.5 hour at 260 ℃ to obtain the positive electrode material for the solid-state battery.
Example 3
This example differs from example 1 only in that the amount of styrene added in step (1) was 3g, and other conditions and parameters were identical to those of example 1.
Example 4
This example differs from example 1 only in that the styrene addition amount in step (1) was 20g, and other conditions and parameters were exactly the same as in example 1.
Example 5
The present example differs from example 1 only in that the mass ratio of the positive electrode material to the solid electrolyte in step (2) is 1:0.03, and other conditions and parameters are exactly the same as those in example 1.
Example 6
The present example differs from example 1 only in that the mass ratio of the positive electrode material to the solid electrolyte in step (2) is 1:0.3, and other conditions and parameters are exactly the same as in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no styrene was added, and other conditions and parameters were exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that a solid electrolyte was added, and other conditions and parameters were exactly the same as in example 1.
Performance test:
the positive electrode materials for solid-state batteries prepared in examples 1 to 6 and comparative examples 1 to 2 were assembled by the same process, and then subjected to performance test, and the test results showed that the positive electrode materials for solid-state batteries prepared in examples 1 to 2 of the present invention were superior in performance, and the performance of the prepared solid-state batteries was significantly superior to those of the other examples and comparative examples.
As can be seen from comparison between example 1 and examples 3 to 4, in the preparation process of the positive electrode material for a solid-state battery according to the present invention, the mass concentration of styrene in the styrene mixed solution affects the performance of the prepared material, the mass concentration of styrene is controlled to be 5-20 g/L, the performance of the prepared positive electrode material is better, if the mass concentration of styrene is too low, the amount of polystyrene embedded into the precursor is too small, the pores on the surface of the sintered positive electrode material are less, sufficient positions cannot be provided for the solid electrolyte, the contact between the material and the solid electrolyte is poor, the performance of the material is affected, if the mass concentration of styrene is too high, the excessive polystyrene is distributed on the surface or even inside the precursor, a large number of pores even hollows appear after sintering, the performance of the positive electrode material is affected, and the solid electrolyte enters the inside the material during the subsequent coating process further affects the performance of the material.
As can be seen from comparison of examples 1 and examples 5 to 6, in the preparation process of the positive electrode material for a solid-state battery according to the present invention, the mass ratio of the positive electrode material to the solid electrolyte affects the performance of the prepared material, the mass ratio of the positive electrode material to the solid electrolyte is controlled to be 1:0.05-0.2, the prepared material has good quality, if the addition amount of the solid electrolyte is too small, the conductivity of the material is poor, and if the addition amount of the solid electrolyte is too large, the coating layer is too thick, thereby affecting the performance of the positive electrode material.
As can be obtained by comparing the embodiment 1 with the comparative example 1-2, in the process of preparing the precursor of the positive electrode material, polystyrene (PS) is polymerized in situ on the surface of the precursor, the polystyrene is uniformly nested on the surface of ternary precursor particles, a hole structure is left after the polystyrene reacts in the subsequent calcination process of preparing the positive electrode material, the surface porosity of the ternary material is improved, the solid electrolyte is coated on the surface of the ternary material, the holes on the surface of the positive electrode material are favorable for realizing full solid electrolyte liquid phase coating, the contact area of the positive electrode active material and the solid electrolyte layer can be increased, a stable interface layer is constructed, and long circulation is realized.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (24)

1. A method for preparing a positive electrode material for a solid-state battery, the method comprising the steps of:
(1) Mixing a nickel source, a cobalt source and a manganese source with a solvent to obtain a metal mixed solution, and mixing styrene and a polymerization inducer with the solvent to obtain a styrene mixed solution;
(2) Mixing the metal mixed solution, the styrene mixed solution, ammonia water and alkali liquor for coprecipitation reaction to obtain a precursor material;
(3) And mixing the precursor material with a lithium source, and then carrying out calcination treatment to obtain a nickel cobalt manganese positive electrode material, wherein the nickel cobalt manganese positive electrode material is subjected to surface in-situ coating solid electrolyte treatment to obtain the positive electrode material for the solid battery, the calcination treatment temperature is 650-800 ℃, and the calcination treatment time is 10-15 hours.
2. The method of claim 1, wherein the nickel source of step (1) comprises any one or a combination of at least two of nickel chloride, nickel acetate, nickel nitrate, or nickel sulfate.
3. The method of claim 1, wherein the cobalt source comprises any one or a combination of at least two of cobalt chloride, cobalt acetate, cobalt nitrate, or cobalt sulfate.
4. The method of claim 1, wherein the manganese source comprises any one or a combination of at least two of manganese chloride, manganese acetate, manganese nitrate, or manganese sulfate.
5. The method according to claim 1, wherein the molar concentration of nickel element in the metal mixed solution is 0.2 to 1mol/L.
6. The method according to claim 1, wherein the molar concentration of cobalt element in the metal mixed solution is 0.01 to 0.3mol/L.
7. The method according to claim 1, wherein the molar concentration of manganese element in the metal mixed solution is 0.01 to 1mol/L.
8. The method according to claim 1, wherein the total concentration of the metal elements in the metal mixed solution is 0.25 to 1.5mol/L.
9. The method of claim 1, wherein the polymerization initiator of step (1) comprises 2,2' -azobis (2-methylpropionamide) dihydrochloride.
10. The method according to claim 1, wherein the mass concentration of the polymerization initiator in the styrene mixed solution is 1 to 3g/L.
11. The method according to claim 1, wherein the mass concentration of styrene in the styrene mixed solution is 5 to 20g/L.
12. The process according to claim 1, wherein the lye of step (2) comprises sodium carbonate solution, sodium bicarbonate solution or sodium hydroxide solution.
13. The process according to claim 1, wherein the temperature of the coprecipitation reaction is 50 to 80 ℃.
14. The method of claim 1, wherein the coprecipitation reaction is carried out under an inert atmosphere.
15. The method of claim 14, wherein the inert atmosphere gas comprises nitrogen.
16. The method of claim 1, wherein the precursor material in step (2) has a particle size of 3 to 15 μm.
17. The method of claim 1, wherein the precursor material in step (3) has a molar ratio of metal element to lithium element in the lithium source of 1 (1.03-1.08).
18. The method of claim 1, wherein the lithium source comprises lithium hydroxide and/or lithium carbonate.
19. The method according to claim 1, wherein the mass ratio of the solid electrolyte coating layer to the nickel cobalt manganese positive electrode material in the positive electrode material for a solid-state battery in step (3) is (0.05-0.2): 1.
20. The method of claim 1, wherein the in-situ coated solid electrolyte is treated at a temperature of 200 to 300 ℃.
21. The method of claim 1, wherein the in-situ coated solid electrolyte is treated for a period of time ranging from 0.2 to 0.8 hours.
22. A positive electrode material for a solid-state battery, characterized in that the positive electrode material for a solid-state battery is produced by the method according to any one of claims 1 to 21.
23. A positive electrode sheet comprising the positive electrode material for a solid-state battery according to claim 22.
24. A solid-state battery comprising the positive electrode tab of claim 23.
CN202210561780.1A 2022-05-23 2022-05-23 Positive electrode material for solid-state battery, and preparation method and application thereof Active CN114759181B (en)

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