CN114759181A - 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 PDFInfo
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- 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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- 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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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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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, a polymerization inducer and the solvent to obtain a styrene mixed solution; (2) mixing the metal mixed solution, the styrene mixed solution, ammonia water and alkali liquor to carry out coprecipitation reaction to obtain a precursor material; (3) the precursor material is mixed with a lithium source and then calcined, and the surface of the precursor material is coated with solid electrolyte in situ to obtain the cathode material for the solid battery.
Description
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 the all solid-state lithium battery, the most widely used materials are lithium transition metal oxides because they have superior properties such as good cycle stability and higher operating voltage. However, the positive electrode and the solid electrolyte have poor solid-solid contact wettability, and high interface contact resistance is generated. Due to the excessive electrochemical potential difference, lithium ions are transferred from the solid electrolyte to the metal oxide positive electrode, and finally a space charge layer is formed. The formation of a high resistance space charge layer severely reduces the migration kinetics of lithium ions at the interface. During the charge and discharge processes, the local deformation of the electrode material is aggravated by the interface strain/stress caused by the volume change of the layered positive electrode, the charge transfer resistance is increased, and the electrochemical performance is seriously deteriorated due to side reactions caused by a poor interface structure.
In order to achieve good interface compatibility, strategies such as embedding an artificial buffer layer, modifying an electrode or a solid electrolyte are adopted in the prior art. In order to achieve better ion transmission and interface contact, the surface of the positive electrode material is often designed to be coated with a solid electrolyte in situ, so as to improve compatibility with the solid electrolyte layer, and the electrochemical performance of the prepared composite material is obviously improved.
CN112164776A discloses a composite coated all-solid-state battery anode material and a preparation method thereof, and an all-solid-state battery, wherein the composite coated all-solid-state battery anode material comprises an anode material and a composite coating layer coated on the surface of the anode material; the composite coating layer is formed by compositely coating 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 calcined to prepare the catalyst.
CN107452954A discloses a preparation method of a lithium-rich manganese-based composite positive electrode material for a solid-state battery, the preparation method includes: the method comprises the following steps: mixing the lithium-rich manganese-based composite anode material according to the mass ratio, and then ball-milling the material by using a planet ball, wherein the ball-milling rotation speed is 300-.
The positive electrode material for the solid-state battery in the scheme can only be coated with the solid electrolyte on the limited surface, and 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 positive electrode material for a solid-state battery and a preparation method and application thereof.
In order to achieve the purpose, 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, a polymerization inducer and the solvent to obtain a styrene mixed solution;
(2) simultaneously 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, calcining 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-state battery.
In the process of preparing the precursor of the anode material, Polystyrene (PS) is polymerized in situ on the surface of the precursor, the PS is uniformly nested on the surface of the ternary precursor particles, and then in the calcination process of preparing the anode material, a pore structure is left after the PS reacts, so that the surface porosity of the ternary material is improved, the surface of the ternary material is coated with the solid electrolyte, the pores on the surface of the anode material are favorable for realizing full liquid phase coating of the solid electrolyte, the contact area of the anode 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 in step (1) comprises any one of nickel chloride, nickel acetate, nickel nitrate or nickel sulfate or a combination of at least two of them.
Preferably, the cobalt source comprises any one of cobalt chloride, cobalt acetate, cobalt nitrate or cobalt sulphate, or a combination of at least two thereof.
Preferably, the manganese source comprises any one of manganese chloride, manganese acetate, manganese nitrate or manganese sulphate or a combination of at least two of these.
Preferably, the molar concentration of the 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 or 1mol/L, etc.
Preferably, the molar concentration of the 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 the 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, or the like.
Preferably, the total concentration of the metal elements in the metal mixed solution is 0.25-1.5 mol/L, for example: 0.25mol/L, 0.5mol/L, 0.8mol/L, 1mol/L or 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 inducer 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 styrene in the styrene mixed solution is 5-20 g/L, for example: 5g/L, 8g/L, 10g/L, 15g/L or 20g/L, etc.
Preferably, the alkali solution in step (2) comprises sodium carbonate solution, sodium bicarbonate solution or sodium hydroxide solution.
Preferably, the temperature of the coprecipitation reaction is 50-80 ℃, 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 particle size of the precursor material in the step (2) is 3-15 μm, for example: 3 μm, 5 μm, 10 μm, 12 μm, 15 μm, or the like.
Preferably, the molar ratio of the metal element in the precursor material in the step (3) to the lithium element in the lithium source is 1 (1.03-1.08), such as: 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 deg.C, 680 deg.C, 700 deg.C, 750 deg.C, or 800 deg.C.
Preferably, the time of the calcination treatment is 10-15 h, such as: 10h, 11h, 12h, 13h, 14h or 15h, etc.
Preferably, the mass ratio of the solid electrolyte coating layer to the nickel-cobalt-manganese positive electrode material in the positive electrode material for the solid-state battery in the step (3) is (0.05-0.2): 1, for example: 0.05:1, 0.08:1, 0.1:1, 0.15:1, 0.2:1, etc.
Preferably, the temperature of the in-situ coating solid electrolyte treatment is 200-300 ℃, for example: 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃ or the like.
Preferably, the in-situ coating solid electrolyte treatment time is 0.2-0.8 h, for example: 0.2h, 0.3h, 0.5h, 0.6h or 0.8h and the like.
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 invention provides a positive electrode plate, which comprises the positive electrode material for solid-state batteries as described in the second aspect.
In a fourth aspect, the 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 surface of ternary precursor particles under the in-situ polymerization rate of the surface of the precursor material to form a composite material, and the composite material is subjected to lithiation and calcination and then subjected to in-situ coating by a solid electrolyte, so that the preparation of the composite electrode material which is in good contact with a solid electrolyte layer can be realized.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive electrode material for a solid-state battery, which is prepared by the following steps:
(1) dissolving nickel nitrate, cobalt nitrate and manganese nitrate into water according to the molar ratio of nickel, cobalt and manganese elements of 8:1:1 to prepare a solution with the metal concentration of 1.5 mol/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, 32 wt.% of 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 at 70 ℃ in a nitrogen atmosphere, finishing the reaction until the particle size of a 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 according to the Li/metal molar ratio of 1.02:1 at 700 ℃ for 9h to obtain a ternary cathode material with high surface porosity; then the anode material and the solid electrolyte (L) are mixed by a liquid phase method under the nitrogen atmosphere2S and P2S5And (3) adding the mixture into an acetonitrile solution according to the mass ratio of 0.85:0.15, mixing at 50 ℃, stirring for 2h, centrifugally drying at 60 ℃, collecting a solid, and burning at 260 ℃ for 0.5h to obtain the cathode material for the solid-state battery.
Example 2
The embodiment provides a positive electrode material for a solid-state battery, which is prepared by the following steps:
the embodiment provides a positive electrode material for a solid-state battery, which is prepared by the following steps:
(1) dissolving nickel nitrate, cobalt nitrate and manganese nitrate into water according to the molar ratio of nickel, cobalt and manganese elements of 6:2:2 to prepare a solution with the 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, 32 wt.% of 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 at 70 ℃ in a nitrogen atmosphere, finishing the reaction until the particle size of a 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 according to the Li/metal molar ratio of 1.02:1 at 700 ℃ for 9h to obtain a ternary cathode material with high surface porosity; then the anode material and the solid electrolyte (L) are mixed by a liquid phase method under the nitrogen atmosphere2S and P2S5And (4) adding the mixture into an acetonitrile solution according to the mass ratio of 0.9:0.1, mixing and stirring for 2 hours at 50 ℃, centrifugally drying at 60 ℃, collecting solids, and burning for 0.5 hour at 260 ℃ to obtain the cathode 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 the other conditions and parameters were exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the amount of styrene added in step (1) was 20g, and the other conditions and parameters were exactly the same as in example 1.
Example 5
The present example is different 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 is different 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 completely the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that no styrene was added, and the 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 the other conditions and parameters were exactly the same as in example 1.
And (3) performance testing:
the positive electrode materials for the solid-state batteries prepared in examples 1 to 6 and comparative examples 1 to 2 were assembled in the same process, and then performance tests were performed, and the test results showed that the positive electrode materials for the solid-state batteries prepared in examples 1 to 2 of the present invention had better performance, and the performance of the prepared solid-state batteries was significantly better than that of the other examples and comparative examples.
As can be seen from comparison of example 1 with examples 3 to 4, in the production of the positive electrode material for solid-state batteries according to the present invention, the mass concentration of styrene in a styrene mixed solution can influence the performance of a prepared material, the mass concentration of styrene is controlled to be 5-20 g/L, the performance of the prepared anode material is good, if the mass concentration of styrene is too low, the amount of polystyrene embedded in a precursor is too small, holes in the surface of the sintered anode material are few, a sufficient position cannot be provided for a solid electrolyte, the contact between the material and the solid electrolyte is poor, the performance of the material is influenced, if the mass concentration of styrene is too large, the polystyrene is excessively distributed on the surface of the precursor or even inside the precursor, a large number of holes or even hollows appear after sintering, the performance of the anode material is influenced, and the solid electrolyte enters the inside of the material in the subsequent coating process to further influence the performance of the material.
Compared with the embodiment 1 and the embodiments 5 to 6, in the preparation process of the cathode material for the solid-state battery, the mass ratio of the cathode material to the solid electrolyte influences the performance of the prepared material, the mass ratio of the cathode material to the solid electrolyte is controlled to be 1: 0.05-0.2, the quality of the prepared material is good, 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, and the performance of the cathode material is influenced.
Compared with the comparative examples 1 and 2, the preparation method has the advantages that in the process of preparing the precursor of the cathode material, Polystyrene (PS) is polymerized in situ on the surface of the precursor, the polystyrene is uniformly nested on the surface of the ternary precursor particles, a pore structure is left after the polystyrene reacts in the subsequent calcining process for preparing the cathode material, the surface porosity of the ternary material is improved, the surface of the ternary material is coated with the solid electrolyte, the pores on the surface of the cathode material are favorable for realizing sufficient liquid phase coating of the solid electrolyte, the contact area of the cathode 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 description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a positive electrode material for a solid-state battery is characterized by comprising the following steps:
(1) mixing a nickel source, a cobalt source, a manganese source and a solvent to obtain a metal mixed solution, and mixing styrene, a polymerization inducer and the solvent to obtain a styrene mixed solution;
(2) mixing the metal mixed solution, the styrene mixed solution, ammonia water and alkali liquor to carry out coprecipitation reaction to obtain a precursor material;
(3) and mixing the precursor material with a lithium source, calcining 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-state battery.
2. The method according to claim 1, wherein the nickel source of step (1) comprises any one of nickel chloride, nickel acetate, nickel nitrate or nickel sulfate or a combination of at least two thereof;
preferably, the cobalt source comprises any one of cobalt chloride, cobalt acetate, cobalt nitrate or cobalt sulfate or a combination of at least two thereof;
preferably, the manganese source comprises any one of manganese chloride, manganese acetate, manganese nitrate or manganese sulphate or a combination of at least two thereof;
preferably, the molar concentration of the nickel element in the metal mixed solution is 0.2-1 mol/L;
preferably, the molar concentration of the cobalt element in the metal mixed solution is 0.01-0.3 mol/L;
preferably, the molar concentration of the manganese element in the metal mixed solution is 0.01-1 mol/L;
preferably, the total concentration of the metal elements in the metal mixed solution is 0.25-1.5 mol/L.
3. The preparation method according to claim 1 or 2, wherein the polymerization-inducing agent of step (1) comprises 2, 2' -azobis (2-methylpropionamide) dihydrochloride;
preferably, the mass concentration of the polymerization inducer in the styrene mixed solution is 1-3 g/L;
preferably, the mass concentration of the styrene in the styrene mixed solution is 5-20 g/L.
4. The method according to any one of claims 1 to 3, wherein the alkali solution of step (2) comprises a sodium carbonate solution, a sodium bicarbonate solution or a sodium hydroxide solution;
preferably, the temperature of the coprecipitation reaction is 50-80 ℃;
preferably, the coprecipitation reaction is carried out under an inert atmosphere;
preferably, the gas of the inert atmosphere comprises nitrogen.
5. The method according to any one of claims 1 to 4, wherein the particle size of the precursor material in the step (2) is 3 to 15 μm.
6. The method according to any one of claims 1 to 5, wherein the molar ratio of the metal element in the precursor material in step (3) to the lithium element in the lithium source is 1 (1.03-1.08);
preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate;
preferably, the temperature of the calcination treatment is 650-800 ℃;
preferably, the time of the calcination treatment is 10-15 h.
7. The production method according to any one of claims 1 to 6, 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 the step (3) is (0.05 to 0.2): 1;
preferably, the temperature of the in-situ coating solid electrolyte treatment is 200-300 ℃;
preferably, the in-situ coating solid electrolyte treatment time is 0.2-0.8 h.
8. A positive electrode material for a solid-state battery, characterized in that it is produced by the method according to any one of claims 1 to 7.
9. A positive electrode sheet, characterized by comprising the positive electrode material for solid-state batteries according to claim 8.
10. A solid-state battery comprising the positive electrode tab of claim 9.
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| CN113793976A (en) * | 2021-09-08 | 2021-12-14 | 远景动力技术(江苏)有限公司 | Semi-solid lithium ion battery and preparation method thereof |
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