CN113285178A - Oxide-coated lithium lanthanum zirconium oxide material, diaphragm material, lithium battery and preparation method - Google Patents
Oxide-coated lithium lanthanum zirconium oxide material, diaphragm material, lithium battery and preparation method Download PDFInfo
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- CN113285178A CN113285178A CN202110518813.XA CN202110518813A CN113285178A CN 113285178 A CN113285178 A CN 113285178A CN 202110518813 A CN202110518813 A CN 202110518813A CN 113285178 A CN113285178 A CN 113285178A
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- Prior art keywords
- lanthanum zirconium
- zirconium oxide
- oxide
- lithium lanthanum
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 58
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- 230000000903 blocking effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides an oxide-coated lithium lanthanum zirconium oxide material which is of a core-shell structure and comprises lithium lanthanum zirconium oxide and an oxide coating layer coated on the surface of the lithium lanthanum zirconium oxide. The application also provides a method for preparing the oxide-coated lithium lanthanum zirconium oxide material, wherein an oxide coating layer is formed on the surface of the lithium lanthanum zirconium oxide by a coprecipitation method to obtain the modified lithium lanthanum zirconium oxide, and the modified lithium lanthanum zirconium oxide is subjected to heat treatment at the temperature of 200-600 ℃ to obtain the oxide-coated lithium lanthanum zirconium oxide material. The application also provides a diaphragm material and a preparation method thereof and a lithium battery based on the oxide-coated lithium lanthanum zirconium oxide material and the preparation method thereof. The oxide coating on the surface of the oxide-coated lithium lanthanum zirconium oxide material is very stable, and after the oxide coating is coated on the surface of a diaphragm to obtain the diaphragm material and further manufacture a lithium battery, the organic electrolyte can not form a lithium carbonate layer on the surface of the diaphragm material, so that the lithium battery has higher safety, lithium ion conductivity and cycling stability.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to an oxide-coated lithium lanthanum zirconium oxide material and a preparation method thereof, a diaphragm material and a preparation method thereof, and a lithium battery.
Background
In the construction of lithium batteries, a separator is one of the key components, and functions to separate the positive electrode from the negative electrode material, allowing lithium ions to pass while blocking electrons from passing. The performance of the diaphragm directly influences the characteristics of internal resistance, cycle performance, safety and the like of the battery, and the diaphragm with excellent performance plays a crucial role in improving the comprehensive performance of the lithium ion battery.
The traditional lithium ion battery diaphragm mainly comprises polypropylene, polyethylene terephthalate and composite materials of the diaphragms. These materials have the disadvantage of low melting point, about 130 ℃ to 160 ℃, and are easily melted by shrinkage under high temperature conditions. When the battery is out of control thermally, the diaphragm is easy to shrink greatly and melt and break, so that short circuit between the positive electrode and the negative electrode is formed, and safety accidents are caused.
In the prior art, a layer of modified film is formed on the surface of the diaphragm by coating oxides such as nano silicon dioxide, aluminum oxide and the like, so that the thickness of the diaphragm is reduced, the volume of the battery is reduced, the thermal stability is improved, and the safety performance of the battery is improved on the premise that the film has higher strength. However, since conventional oxides such as nano-silica and alumina are insulators and have low ionic conductivity, the coating on the surface of the separator may cause large internal resistance, which affects battery performance. The garnet-structured lithium lanthanum zirconium oxide solid electrolyte has high chemical and electrochemical stability and high lithium ion conductivity, and is considered to be one of the most promising solid electrolytes. However, the electrolyte material can generate a lithium carbonate layer with poor conductivity by surface chemical reaction in an organic electrolyte, and the performance of the battery can be affected when the lithium carbonate layer is coated on the surface of the diaphragm and used in a lithium battery.
In view of various defects of the prior art, the inventors of the present application have conducted extensive studies to provide a novel oxide-coated lithium lanthanum zirconium oxide-coated separator material, a method for preparing the same, and a lithium battery comprising the same.
Disclosure of Invention
The present application aims to provide an oxide-coated lithium lanthanum zirconium oxide material and a preparation method thereof, a diaphragm material and a preparation method thereof, a lithium battery and a preparation method thereof, wherein an oxide coating layer on the surface of the oxide-coated lithium lanthanum zirconium oxide material is very stable, the oxide coating layer is coated on the surface of the diaphragm to obtain the diaphragm material, and after the lithium battery is further manufactured, an organic electrolyte does not form a lithium carbonate layer on the surface of the diaphragm material, so that the lithium battery can have high safety, lithium ion conductivity and cycle stability at the same time.
In order to solve the technical problem, the present application provides an oxide-coated lithium lanthanum zirconium oxide material, the oxide-coated lithium lanthanum zirconium oxide material is a core-shell structure, including lithium lanthanum zirconium oxide, and the oxide coating layer coated on the surface of lithium lanthanum zirconium oxide.
The application also provides a method for preparing the oxide-coated lithium lanthanum zirconium oxide material, which comprises the following steps:
s11, forming an oxide coating layer on the surface of the lithium lanthanum zirconium oxide by a coprecipitation method to obtain modified lithium lanthanum zirconium oxide;
s12, carrying out heat treatment on the modified lithium lanthanum zirconium oxide, wherein the heat treatment temperature is 200-600 ℃, and obtaining the oxide-coated lithium lanthanum zirconium oxide material.
The application also provides a diaphragm material, which comprises a diaphragm and a coating layer coated on the diaphragm, wherein the coating layer is an oxide-coated lithium lanthanum zirconium oxide material; the oxide-coated lithium lanthanum zirconium oxide material is any one of the above oxide-coated lithium lanthanum zirconium oxide materials, or is an oxide-coated lithium lanthanum zirconium oxide material obtained by any one of the above methods for preparing the oxide-coated lithium lanthanum zirconium oxide material.
The present application also provides a method of preparing a separator material, comprising the steps of:
s21, mixing the components in a mass ratio of 1: a: b, mixing the oxide-coated lithium lanthanum zirconium oxide material, a polymer and a dispersing solvent to obtain diaphragm slurry; a is more than or equal to 1 and less than or equal to 9, and b is more than or equal to 20 and less than or equal to 500;
s22, coating the diaphragm slurry on the surface of the diaphragm to obtain a diaphragm material;
the oxide-coated lithium lanthanum zirconium oxide material is any one of the above oxide-coated lithium lanthanum zirconium oxide materials, or is an oxide-coated lithium lanthanum zirconium oxide material obtained by any one of the above methods for preparing the oxide-coated lithium lanthanum zirconium oxide material.
The application also provides a lithium battery, wherein the diaphragm material in the lithium battery is any one of the diaphragm materials, or the diaphragm material prepared by any one of the above methods for preparing the diaphragm material.
The application also provides a preparation method of the lithium battery, and the lithium battery is prepared by taking any one of the diaphragm materials or the diaphragm material prepared by any one of the methods for preparing the diaphragm material as the diaphragm material.
The oxide coating on the surface of the oxide-coated lithium lanthanum zirconium oxide material is very stable, the membrane material is obtained by coating the oxide coating on the surface of the membrane, and after a lithium battery is further manufactured, the organic electrolyte can not form a lithium carbonate layer on the surface of the membrane material, so that the lithium battery can have high safety, lithium ion conductivity and circulation stability at the same time. In addition, the method for preparing the oxide-coated lithium lanthanum zirconium oxide material, the method for preparing the diaphragm material and the method for preparing the lithium battery have the advantages of simple process, low energy consumption, environmental friendliness and easiness in realization of industrial production.
The foregoing description is only an overview of the technical solutions of the present application, and in order to make the technical means of the present application more clearly understood, the present application may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present application more clearly understood, the following preferred embodiments are described in detail with reference to the accompanying drawings.
Drawings
FIG. 1 is a TEM morphology of the Li-Si-O coated tantalum doped lithium lanthanum zirconium oxide material of the second embodiment.
FIG. 2 is a sectional SEM topography of the Li-Si-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material in the second embodiment.
Fig. 3 is a diagram illustrating battery performance test results of the Li-Si-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene separator material on a lithium iron phosphate positive electrode and a lithium metal negative electrode in the second embodiment.
Fig. 4 is a diagram of battery performance test results of the Li-Si-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene separator material versus a 622 type ternary nickel cobalt manganese positive electrode and a lithium metal negative electrode in example two.
FIG. 5 is a TEM morphology of the Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide material of the third embodiment.
FIG. 6 is a cross-sectional SEM topography of the Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material in the third embodiment.
Fig. 7 is a diagram of battery performance test results of the Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene separator material on a lithium iron phosphate positive electrode and a lithium metal negative electrode in the third embodiment.
Fig. 8 is a graph of battery performance test results of the Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene separator material versus a 622-type ternary nickel cobalt manganese positive electrode and a lithium metal negative electrode in the third embodiment.
Fig. 9 is a TEM topography of the pure lithium lanthanum zirconium oxide material in comparative example one.
FIG. 10 is a sectional SEM topography of the pure lithium lanthanum zirconium oxygen coated polypropylene separator material in comparative example.
Fig. 11 is a graph of battery performance test results of the pure lithium lanthanum zirconium oxygen coated polypropylene separator material versus lithium iron phosphate positive electrode and lithium metal negative electrode in comparative example one.
Fig. 12 is a graph of battery performance test results of the pure lithium lanthanum zirconium oxygen coated polypropylene separator material of comparative example one versus a 622 type ternary nickel cobalt manganese positive electrode and a lithium metal negative electrode.
FIG. 13 is a TEM topography of a corundum material in a comparative example.
FIG. 14 is a sectional SEM topography of a corundum coated polypropylene separator material in a comparative example.
Fig. 15 is a diagram showing the results of the battery performance tests of the corundum-coated polypropylene separator material on a lithium iron phosphate positive electrode and a lithium metal negative electrode in the comparative example.
Fig. 16 is a graph showing the results of testing the performance of the corundum-coated polypropylene separator material in the comparative example on a 622 type ternary nickel cobalt manganese positive electrode and a lithium metal negative electrode.
Detailed Description
To further clarify the technical measures and effects taken by the present application to achieve the intended purpose, the present application will be described in detail below with reference to the accompanying drawings and preferred embodiments.
While the present application has been described in terms of specific embodiments and examples for achieving the desired objects and objectives, it is to be understood that the invention is not limited to the disclosed embodiments, but is to be accorded the widest scope consistent with the principles and novel features as defined by the appended claims.
In an exemplary embodiment, an oxide-coated lithium lanthanum zirconium oxide material is provided, wherein the oxide-coated lithium lanthanum zirconium oxide material has a core-shell structure and comprises lithium lanthanum zirconium oxide and an oxide coating layer coated on the surface of the lithium lanthanum zirconium oxide.
It should be noted that, in the present embodiment, the oxide coating layer on the surface of the oxide-coated lithium lanthanum zirconium oxide material is stable, and after the oxide coating layer is coated on the surface of the diaphragm to obtain the diaphragm material, and the diaphragm material is further manufactured into the lithium battery, the organic electrolyte does not form a lithium carbonate layer on the surface of the diaphragm material, so that the lithium battery can have high safety, lithium ion conductivity and cycling stability at the same time.
In an embodiment of the present application, the lithium lanthanum zirconium oxide is a pure lithium lanthanum zirconium oxide material, or a lithium lanthanum zirconium oxide material doped with at least one element selected from tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium, and barium.
In another embodiment of the present application, the oxide is MOxAnd X is a natural number, and M is at least one selected from silicon, aluminum, titanium, zirconium and niobium.
In another embodiment of the present application, the lithium lanthanum zirconium oxygen D50Is 50-500 nm. For example, about 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 250nm, 280nm, 300nm, 320nm, 330nm, 350nm, 370nm, 400nm, 420nm, 450nm, 480nm, and 500 nm. More preferably, D of the lithium lanthanum zirconium oxide50Is 100-300 nm.
In another embodiment of the present application, the oxide coating layer has a thickness of 5-100 nm. For example: 5nm, 7nm, 10nm, 15nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, and 100 nm. Preferably, the thickness of the oxide coating layer is 5-20 nm.
It should be noted that the ionic conductivity of the oxide coating layer is lower than that of the lithium lanthanum zirconium oxide, for example, the oxide coating layer is too thick, which may affect the ionic conductivity of the oxide-coated lithium lanthanum zirconium oxide material, for example, the oxide coating layer is too thin, and the protection degree of the oxide coating layer on the lithium lanthanum zirconium oxide is easily insufficient, which may result in the formation of a lithium carbonate layer on the surface of the oxide-coated lithium lanthanum zirconium oxide material. Repeated verification by the inventor of the application proves that the ionic conductivity and the protection effect of the oxide-coated lithium lanthanum zirconium oxide material can be better considered within the thickness range of the oxide coating layer.
In another exemplary embodiment of the present application, a method of preparing an oxide coated lithium lanthanum zirconium oxide material comprises the steps of:
s11, forming an oxide coating layer on the surface of the lithium lanthanum zirconium oxide by a coprecipitation method to obtain modified lithium lanthanum zirconium oxide;
s12, carrying out heat treatment on the modified lithium lanthanum zirconium oxide, wherein the heat treatment temperature is 200-600 ℃, and obtaining the oxide-coated lithium lanthanum zirconium oxide material.
It should be noted that, after the oxide coating layer on the surface of the oxide-coated lithium lanthanum zirconium oxygen material obtained by the method for preparing the oxide-coated lithium lanthanum zirconium oxygen material of the embodiment is very stable and is coated on the surface of the diaphragm to obtain the diaphragm material, and further the diaphragm material is manufactured into the lithium battery, the organic electrolyte does not form a lithium carbonate layer on the surface of the diaphragm material, so that the lithium battery can have high safety, lithium ion conductivity and cycling stability at the same time; meanwhile, the method of the embodiment has the advantages of simple process, low energy consumption, environmental friendliness (low requirement on environmental pollution or environmental protection process), and easy realization of industrial production.
In an embodiment of the present application, the lithium lanthanum zirconium oxide is a pure lithium lanthanum zirconium oxide material, or a lithium lanthanum zirconium oxide material doped with at least one element selected from tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium, and barium. For example: the lithium lanthanum zirconium oxygen is Li7-aLa3Zr2- aTaaO12,0≤a≤2；Li7-bLa3Zr2-bNbbO12,0≤b≤2；Li7-2cLa3Zr2-cWcO12,0≤c≤2；Li7- 3dAldLa3Zr2O12,0≤d≤0.5；Li7-3eGaeLa3Zr2O12,0≤e≤0.5；Li5+fAfLa2M2O12A is Sr, Ca or Ba, M is Nb or Ta, and f is more than or equal to 0 and less than or equal to 1; for example: pure lithium lanthanum zirconium oxide material (Li)7La3Zr2O12) Tantalum doped lithium lanthanum zirconium oxide (Li)6.4La3Zr1.4Ta0.6O12) Niobium doped lithium lanthanum zirconium oxygen (Li)6.4La3Zr1.4Nb0.6O12) Aluminum doped lithium lanthanum zirconium oxygen (Li)6.25Al0.25La3Zr2O12) Gallium doped lithium lanthanum zirconium oxygen (Li)6.25Ga0.25La3Zr2O12)。
In another embodiment of the present application, the lithium lanthanum zirconium oxygen D50Is 50-500nm, such as 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 150nm, 180nm, 200nm, 250nm, 280nm, 300nm, 320nm, 330nm, 350nm, 370nm, 400nm, 420nm, 450nm, 480nm, and 500 nm. More preferably, D of the lithium lanthanum zirconium oxide50Is 100-300 nm.
It should be noted that step S12 allows the co-precipitated precursor of the coating layer to react to form an oxide coating layer through a heat treatment step, and to be in close contact with the lithium lanthanum zirconium oxide surface. In another embodiment of the present application, the heat treatment time of the step S12 is preferably 2-6 hours, and the heat treatment temperature is 200-.
In another embodiment of the present application, the heat treatment of step S12 is performed under air atmosphere conditions. The preparation method does not need special atmosphere conditions, has low requirements on preparation equipment and low cost, and is easy for industrial production.
In another embodiment of the present application, the step S11 includes the steps of:
s111, sequentially adding a dispersion solvent and lithium lanthanum zirconium oxide into a reaction container according to the mass ratio of 10-20:1, and stirring for 1-4 hours to obtain a first suspension;
s112, press MOxCalculating equivalent, mixing the M source with the mass fraction ratio of 1:100-1000 and the first suspension, and stirring for 1-4 hours to obtain a second suspension; the X is a natural number, and the M source comprises a methyl ester compound M (OCH) of M3)2xEthyl ester compound M (OC)2H5)2xPropyl ester compound M (OC)3H7)2xAnd butyl ester compound M (OC)4H9)2xAt least one of; the M is selected from at least one of silicon, aluminum, titanium, zirconium and niobium;
s113, ammonia water is dripped into the second suspension, and the mass ratio of the total mass of ammonia in the ammonia water dripped into the second suspension to the mass of lithium lanthanum zirconium oxide required for obtaining the second suspension is 1-5:1, so that a third suspension is obtained;
s114, filtering the third suspension to obtain suspended particles;
and S115, washing the suspended particles by using a dispersing solvent, and drying the suspended particles to obtain the modified lithium lanthanum zirconium oxide.
The dispersion solvent mainly plays a role of dispersion. The ammonia water in step S113 is a precipitant for precipitating M ions in the solution onto the surface of the lithium lanthanum zirconium oxide, and if the adding speed of ammonia in the ammonia water is increased, the precipitating speed of the M ions is increased, but non-uniformity is easily caused, and if the adding speed of ammonia in the ammonia water is decreased, the precipitating speed of the M ions is decreased, the thickness uniformity is better, but the reaction efficiency is decreased. Through repeated verification of the inventor of the application, when the mass fraction of ammonia in the ammonia water is 10-25% (for example, 10%, 15%, 20%, 25%, etc.), the thickness uniformity and the reaction efficiency can be better considered under the condition that the dropping speed of the ammonia water is 1-5 mL/h.
Further, the step S111 is preferably performed under a protective atmosphere.
Further, the step S112 is preferably performed under a protective atmosphere.
Further, the step S113 is preferably performed under a protective atmosphere.
Further, the protective atmosphere comprises at least one of nitrogen, argon and helium.
It is noted that the protective atmosphere is mainly to avoid the influence of water, carbon dioxide and oxygen in the air on the reaction and to reduce the occurrence of non-target reactions.
Further, in step S113, the second suspension is stirred while ammonia water is dropped. The scheme can further improve the thickness uniformity of M ions precipitated on the surface of the lithium lanthanum zirconium oxide.
Further, the stirring frequency in the steps S111, S112, S113 is preferably 30-50Hz, such as 30Hz, 35Hz, 40Hz, 45Hz, 50 Hz.
It should be noted that the purpose of the stirring in steps S111 and S112 is mainly to mix the corresponding suspensions uniformly, and the prior art capable of achieving the above purpose can achieve the present invention.
Further, the dispersion solvent includes at least one of methanol, ethanol, isopropanol, acetone, butanone, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylformamide.
It should be noted that the dispersion solvents in steps S111 and S115 may be the same or different.
Further, the drying temperature in the step S115 is 80 to 120 ℃, preferably 80 ℃.
In another exemplary embodiment of the present application, a separator material includes a separator and a coating layer coated on the separator, wherein the coating layer is an oxide-coated lithium lanthanum zirconium oxide material; the oxide-coated lithium lanthanum zirconium oxide material is any one of the above oxide-coated lithium lanthanum zirconium oxide materials, or is an oxide-coated lithium lanthanum zirconium oxide material obtained by any one of the above methods for preparing the oxide-coated lithium lanthanum zirconium oxide material.
It should be noted that, the coating layer of the separator material in this embodiment is the oxide-coated lithium lanthanum zirconium oxide material of this application, and the oxide coating layer on the surface of the oxide-coated lithium lanthanum zirconium oxide material of this application is very stable, so that the organic electrolyte of the lithium battery made of the separator material of this embodiment does not form a lithium carbonate layer on the surface of the separator material, so that the lithium battery can have high safety, lithium ion conductivity and cycling stability at the same time.
In an embodiment of the present application, the separator is polypropylene, polyethylene terephthalate, or a composite material containing the same.
It is noted that if the thickness of the separator is too thick, the energy density of the battery will be reduced. In another embodiment of the present application, the thickness of the separator is preferably 10 to 100 μm, more preferably 10 to 20 μm.
An increase in the thickness of the coating layer increases the rate performance, reversible capacity of the positive electrode, etc., of the battery, but an excessively thick coating layer increases the internal resistance of the battery. In another embodiment of the present application, the thickness of the coating layer is preferably 1-20 μm, more preferably 1-5 μm. Within this range, the thickness of the coating layer can be compatible with the overall performance of the battery, and the overall performance of the battery is better, such as the rate performance of the battery, the reversible capacity of the positive electrode, and the like. If the thickness of the coating layer is too thick, the internal resistance of the battery is obviously increased, and the overall performance of the battery is influenced.
The application also provides a method for preparing the diaphragm material based on any one of the oxide-coated lithium lanthanum zirconium oxide materials or the oxide-coated lithium lanthanum zirconium oxide material obtained by any one of the methods for preparing the oxide-coated lithium lanthanum zirconium oxide material.
In another exemplary embodiment of the present application, a method of preparing a separator material includes the steps of:
s21, mixing the components in a mass ratio of 1: a: b, mixing the oxide-coated lithium lanthanum zirconium oxide material, a polymer and a dispersing solvent to obtain diaphragm slurry; a is more than or equal to 1 and less than or equal to 9; b is more than or equal to 20 and less than or equal to 500;
s22, coating the diaphragm slurry on the surface of the diaphragm to obtain a diaphragm material;
the oxide-coated lithium lanthanum zirconium oxide material is any one of the above oxide-coated lithium lanthanum zirconium oxide materials, or is an oxide-coated lithium lanthanum zirconium oxide material obtained by any one of the above methods for preparing the oxide-coated lithium lanthanum zirconium oxide material.
It should be noted that, the method of this embodiment is a method for preparing a separator material based on the oxide-coated lithium lanthanum zirconium oxide material of this application, or the oxide-coated lithium lanthanum zirconium oxide material obtained by the method for preparing an oxide-coated lithium lanthanum zirconium oxide material of this application, because the oxide coating layer on the surface of the oxide-coated lithium lanthanum zirconium oxide material of this embodiment is very stable, the organic electrolyte of the lithium battery prepared based on the separator material of this embodiment does not form a lithium carbonate layer on the surface of the separator material, so that the lithium battery can have high safety, lithium ion conductivity and cycling stability at the same time; meanwhile, the method of the embodiment has the advantages of simple process, low energy consumption, environmental friendliness (low requirement on environmental pollution or environmental protection process), and easy realization of industrial production.
In one embodiment of the present application, the polymer is preferably one or a mixture of two of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, or a copolymer thereof.
In another embodiment of the present application, the dispersion solvent includes at least one of methanol, ethanol, isopropanol, acetone, butanone, N-dimethylacetamide, N-methylpyrrolidone, and N, N-dimethylformamide.
In another embodiment of the present application, the step S22 specifically includes: and coating the diaphragm slurry on the surface of the diaphragm by a tape casting method, and drying at 80-120 ℃ to obtain the diaphragm material.
Preferably, in said step S22, the casting blade height is 10 to 500. mu.m, more preferably 10 to 100. mu.m.
In another exemplary embodiment of the present application, a lithium battery, in which the separator material is any one of the above separator materials, or a separator material obtained by any one of the above methods for preparing a separator material.
The coating layer of the diaphragm material of lithium cell in this embodiment is the oxide cladding lithium lanthanum zirconium oxygen material of this application, and the relatively poor lithium carbonate layer of lithium lanthanum zirconium oxygen surface lithium ion conductivity has been eliminated to the oxide cladding lithium lanthanum zirconium oxygen material of this application, and its surperficial oxide cladding is very stable, therefore organic electrolyte in the lithium cell of this embodiment can not form the lithium carbonate layer on diaphragm material surface, can have high security, lithium ion conductivity and cycle stability concurrently.
In another exemplary embodiment of the present application, a method for preparing a lithium battery uses any one of the above-mentioned separator materials, or a separator material prepared by any one of the above-mentioned methods for preparing a separator material, as a separator material to prepare a lithium battery.
The preparation method of the lithium battery in the embodiment is based on the diaphragm material or the diaphragm material obtained by the method for preparing the diaphragm material, and because the coating layer of the diaphragm material or the coating layer of the diaphragm material obtained by the method for preparing the diaphragm material is the oxide-coated lithium lanthanum zirconium oxide material, the lithium carbonate layer with poor lithium ion conductivity on the surface of the lithium lanthanum zirconium oxide is eliminated, and the oxide coating layer on the surface of the lithium lanthanum zirconium oxide layer is very stable, the organic electrolyte of the lithium battery prepared in the embodiment can not form the lithium carbonate layer on the surface of the diaphragm material, and the lithium battery can simultaneously have high safety, lithium ion conductivity and cycling stability; in addition, the method of the embodiment has the advantages of simple process, low energy consumption, environmental friendliness (low requirement on environmental pollution or environmental protection process), and easy realization of industrial production.
In one embodiment of the present application, a method of making a lithium battery includes the steps of:
s31, preparing a slurry from the negative electrode material, the conductive agent and the binder and water, and then coating the slurry on a copper foil to prepare a negative electrode;
s32, preparing a slurry from the positive electrode material, a conductive agent and a binder and azomethyl pyrrolidone, and coating the slurry on an aluminum foil to prepare a positive electrode;
s33, preparing the anode, the cathode, the electrolyte and the diaphragm material into a lithium battery; the diaphragm material is any one of the diaphragm materials or the diaphragm material obtained by any one of the methods for preparing the diaphragm material.
It should be noted that, in this embodiment, the negative electrode material may be a carbon-based material, a silicon-based material, or a metal material; the carbon material is a hard carbon material, a soft carbon material or a graphite carbon material; the silicon material is silicon, silicon oxide or a silicon-carbon composite material; the metal material is lithium metal powder, lithium metal foil or a carbon-lithium composite material.
The positive electrode material is preferably a ternary positive electrode material, such as NCM622, NCM523, NCM811, or NCA.
The conductive agent is preferably acetylene black, carbon nanotubes, carbon fibers, graphene or conductive graphite. The binder is preferably sodium carboxymethylcellulose, styrene butadiene rubber, polyvinylidene fluoride, polyacrylonitrile or polyacrylic acid.
The electrolyte can be prepared by the following method: and adding lithium salt into a mixed solvent consisting of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate, and then adding an additive to obtain the electrolyte.
The additive is fluoroethylene carbonate, lithium dioxalate borate, 1, 3-propenyl-sultone, 1, 3-propyl-sultone, succinic anhydride, ethylene carbonate or ethylene carbonate.
Furthermore, the additive is added according to the weight percentage of 1-50% of the electrolyte.
Further, the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate or lithium bis (trifluoromethanesulfonate) imide.
Furthermore, the mixed solvent composed of the ethylene carbonate, the diethyl carbonate and the ethyl methyl carbonate is prepared by mixing the ethylene carbonate, the diethyl carbonate and the ethyl methyl carbonate according to the volume ratio of 4:3: 3.
Specific example one preparation of Li-Si-O coated pure Li-La-Zr-O coated polypropylene separator Material
At room temperature of 30 ℃, 10g of Li7La3Zr2O12Powder (D)50320nm), adding the mixture into 200g of acetone solvent, stirring the mixture in a stirring kettle in a nitrogen atmosphere for 4 hours at the stirring frequency of 30Hz to obtain uniformly dispersed suspension (first suspension), adding 1.38g of tetraethyl silicate, and stirring the mixture in the stirring kettle in the nitrogen atmosphere for 4 hours at the stirring frequency of 30Hz to obtain uniformly dispersed suspension (second suspension); gradually dropwise adding ammonia water into the suspension, wherein the mass fraction of ammonia in the ammonia water is 25%, the dropwise adding speed is 2mL/h, the dropwise adding time is 10h, and the suspension is stirred in a stirring kettle in nitrogen atmosphere during the whole dropwise adding processThe stirring frequency was 30Hz to obtain a uniformly dispersed suspension (third suspension); carrying out suction filtration on the suspension to obtain suspended particles, repeatedly cleaning the suspended particles by using an acetone solvent, and drying at 80 ℃ to obtain dried suspended particles (modified lithium lanthanum zirconium oxygen); carrying out heat treatment on the dried suspended particles for 4h at 400 ℃ in an air atmosphere to obtain a silicon dioxide coated lithium lanthanum zirconium oxide material; mixing and stirring 5g of Li-Si-O coated lithium lanthanum zirconium oxide material, 0.1g of polyvinylidene fluoride and 20g N-methyl pyrrolidone to prepare uniformly distributed slurry; coating the slurry on the surface of a polypropylene diaphragm by a casting method, wherein the thickness of the polypropylene diaphragm is 12 microns, the height of a casting scraper is 100 microns, and drying at 80 ℃ after coating to obtain the Li-Si-O coated pure lithium lanthanum zirconium oxide coated polypropylene diaphragm material.
Second embodiment preparation of Li-Si-O-coated tantalum-doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material
At room temperature 30 deg.C, 10g Li6.4La3Zr1.4Ta0.6O12Powder (D)50280nm), adding the mixture into 300g of acetone solvent, and stirring the mixture in a stirring kettle in nitrogen atmosphere for 4 hours at the stirring frequency of 50Hz to obtain uniformly dispersed suspension (first suspension); then 0.69g of tetraethyl silicate is added, and the mixture is stirred for 2 hours in a stirring kettle in nitrogen atmosphere, wherein the stirring frequency is 50Hz, and uniformly dispersed suspension (second suspension) is obtained; gradually dropwise adding ammonia water into the suspension, wherein the mass fraction of ammonia in the ammonia water is 25%, the dropwise adding speed is 1mL/h, the dropwise adding time is 20h, the suspension is stirred in a stirring kettle in a nitrogen atmosphere in the whole dropwise adding process, and the stirring frequency is 50Hz, so that uniformly dispersed suspension (third suspension) is obtained; carrying out suction filtration on the suspension to obtain suspended particles, repeatedly cleaning the suspended particles by using an acetone solvent, and drying at 80 ℃ to obtain dried suspended particles (modified lithium lanthanum zirconium oxygen); carrying out heat treatment on the dried suspended particles for 4h at 400 ℃ in an air atmosphere to obtain a Li-Si-O coated tantalum doped lithium lanthanum zirconium oxide material; mixing and stirring 5gLi-Si-O coated tantalum doped lithium lanthanum zirconium oxide material, 0.1g of polyvinylidene fluoride and 20g N-methyl pyrrolidone to prepare uniformly distributed slurry; coating the slurry on the surface of a polyethylene diaphragm by a tape casting method, wherein the thickness of the diaphragm is 12 mu m, and the height of a tape casting scraper is100 mu m, and drying at 80 ℃ after coating to obtain the silicon dioxide coated tantalum doped lithium lanthanum zirconium oxygen coated polyethylene diaphragm material.
As shown in FIG. 1, in the Li-Si-O-coated tantalum-doped lithium lanthanum zirconium oxide material obtained in the present embodiment, the tantalum-doped lithium lanthanum zirconium oxide D50300nm and the thickness of the Li-Si-O coating layer is 15 nm. As shown in FIG. 2, the thickness of the coating layer in the Li-Si-O coated tantalum-doped lithium lanthanum zirconium oxide coated polyethylene membrane material obtained in the embodiment is 4 μm. As shown in fig. 3, based on the Li-Si-O coated tantalum-doped lithium lanthanum zirconium oxide coated polyethylene separator material obtained in the second embodiment, lithium iron phosphate is used as an anode, and metallic lithium is used as a cathode, and the first charging specific capacity and the first discharging specific capacity of the button cell prepared according to the standard button cell manufacturing method are 147.3mAh/g and 146.7mAh/g respectively, the coulombic efficiency is 99.6%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are 123.5mAh/g and 123.4mAh/g respectively, and the coulombic efficiency is 99.9%. As shown in fig. 4, based on the silicon dioxide coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material obtained in the second embodiment, a 622 type ternary nickel cobalt manganese is used as a positive electrode, a metal lithium is used as a negative electrode, the first charging specific capacity and the first discharging specific capacity of the button battery prepared according to the standard button battery manufacturing method are respectively 166.3mAh/g and 153.4mAh/g, the coulombic efficiency is 92.2%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are respectively 134.3mAh/g and 131.1mAh/g, and the coulombic efficiency is 97.6%.
Third embodiment preparation of Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material
At room temperature 30 deg.C, 10g Li6.4La3Zr1.4Ta0.6O12Powder (D)50280nm), adding the mixture into 300g of acetone solvent, and stirring the mixture in a stirring kettle in nitrogen atmosphere for 4 hours at the stirring frequency of 50Hz to obtain uniformly dispersed suspension (first suspension); then adding 0.85g of tetrabutyl titanate, and stirring for 4 hours in a stirring kettle in nitrogen atmosphere, wherein the stirring frequency is 50Hz, so as to obtain uniformly dispersed suspension (second suspension); ammonia water is gradually dripped into the suspension, the mass fraction of ammonia in the ammonia water is 25 percent, the dripping speed is 1mL/h, and the ammonia water is drippedThe time is 20h, the suspension is stirred in a stirring kettle in nitrogen atmosphere in the whole dripping process, the stirring frequency is 50Hz, and uniformly dispersed suspension (third suspension) is obtained; carrying out suction filtration on the suspension to obtain suspended particles, repeatedly cleaning the suspended particles by using an acetone solvent, and drying at 80 ℃ to obtain dried suspended particles (modified lithium lanthanum zirconium oxygen); carrying out heat treatment on the dried suspended particles for 4h at 400 ℃ in an air atmosphere to obtain a silicon dioxide coated tantalum doped lithium lanthanum zirconium oxide material; mixing and stirring 5g of Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide material, 0.1g of polyvinylidene fluoride and 20g of N-methyl pyrrolidone to prepare uniformly distributed slurry; coating the slurry on the surface of a polyethylene diaphragm by a tape casting method, wherein the thickness of the diaphragm is 12 microns, the height of a tape casting scraper is 100 microns, and drying at 80 ℃ after coating to obtain the silicon dioxide coated tantalum doped lithium lanthanum zirconium oxygen coated polyethylene diaphragm material.
As shown in FIG. 5, based on the Li-Ti-O coated tantalum-doped lithium lanthanum zirconium oxide material obtained in the third embodiment, tantalum-doped lithium lanthanum zirconium oxide D50The thickness of the Li-Ti-O coating layer is 300nm and 10 nm; as shown in fig. 6, the thickness of the coating layer in the Li-Ti-O coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene separator material obtained according to the third embodiment was 4 μm. As shown in fig. 7, based on the Li-Si-O coated tantalum-doped lithium lanthanum zirconium oxide coated polyethylene separator material obtained in the third embodiment, lithium iron phosphate is used as an anode, and metallic lithium is used as a cathode, and the first charging specific capacity and the first discharging specific capacity of the button cell prepared according to the standard button cell manufacturing method are 153.9mAh/g and 152.5mAh/g, respectively, the coulombic efficiency is 99.1%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are 131.1mAh/g and 129.3mAh/g, respectively, and the coulombic efficiency is still maintained at about 98.6%. As shown in fig. 8, based on the silicon dioxide coated tantalum doped lithium lanthanum zirconium oxide coated polyethylene diaphragm material obtained in the third specific embodiment, with type 622 ternary nickel cobalt manganese as a positive electrode and metal lithium as a negative electrode, the first charging specific capacity and the first discharging specific capacity of the button battery prepared according to the standard button battery manufacturing method are 157.1mAh/g and 157.1mAh/g respectively, the coulombic efficiency is 100.0%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are 117.3mAh/g and 113.0mAh/g respectively, and the coulombic efficiency is bit effective96.4％。
Comparative example I preparation of pure lithium lanthanum zirconium oxide coated polypropylene diaphragm material
5g of lithium lanthanum zirconium oxide material, 0.1g of polyvinylidene fluoride and 20g of N-methyl pyrrolidone are mixed and stirred to prepare uniformly distributed slurry; and coating the slurry on the surface of a polypropylene diaphragm by a casting method, wherein the thickness of the polypropylene diaphragm is 12 microns, the height of a casting scraper is 100 microns, and drying at 80 ℃ after coating to obtain the pure lithium lanthanum zirconium oxygen coated polypropylene diaphragm material.
As shown in FIG. 9, in comparative example, pure lithium lanthanum zirconium oxide, D50300nm without a coating. As shown in fig. 10, the thickness of the coating layer in the pure lithium lanthanum zirconium oxide coated polypropylene separator material obtained in comparative example was 4 μm. As shown in fig. 11, based on the pure lithium lanthanum zirconium oxide coated polypropylene separator material obtained in the first comparative example, lithium iron phosphate is used as the positive electrode, and metallic lithium is used as the negative electrode, the first charging specific capacity and the first discharging specific capacity of the button battery prepared according to the standard button battery manufacturing method are 148.2mAh/g and 135.2mAh/g respectively, the coulombic efficiency is 91.3%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are 118.9mAh/g and 102.5mAh/g respectively, and the coulombic efficiency is about 86.2%. As shown in fig. 12, based on the pure lithium lanthanum zirconium oxygen coated polypropylene separator material obtained in the first comparative example, 622 type ternary nickel cobalt manganese is used as the positive electrode, and metal lithium is used as the negative electrode, the first charge specific capacity and the first discharge specific capacity of the button cell prepared according to the standard button cell manufacturing method are 161.7mAh/g and 150.6mAh/g respectively, and the coulombic efficiency is 93.1%, after 100 times of charging and discharging, the charge specific capacity and the discharge specific capacity are 134.3mAh/g and 120.1mAh/g respectively, and the coulombic efficiency is 89.5%.
Comparative example II preparation of corundum-coated Polypropylene diaphragm Material
Mixing and stirring 10g of corundum material, 0.1g of polyvinylidene fluoride and 20g N-methyl pyrrolidone to prepare uniformly distributed slurry; coating the slurry on the surface of a polypropylene diaphragm by a casting method, wherein the thickness of the polypropylene diaphragm is 12 mu m, the height of a casting scraper is 100 mu m, and the slurry is coated at 80 DEG after coating℃And drying to obtain the corundum coated polypropylene diaphragm material.
As shown in FIG. 13, the corundum material used in comparative example No. D50100nm without coating. As shown in fig. 14, the thickness of the coating layer in the corundum-coated polypropylene separator material obtained in the comparative example was 4 μm. As shown in fig. 15, based on the corundum-coated polypropylene separator material obtained in the comparative example, the first charge specific capacity and the first discharge specific capacity of the button cell prepared according to the standard button cell manufacturing method with lithium iron phosphate as the positive electrode and lithium metal as the negative electrode were 144.4mAh/g and 136.7mAh/g, respectively, and the coulombic efficiency was 94.7%, and after 100 charges and discharges, the charge specific capacity and the discharge specific capacity were 117.4mAh/g and 107.0mAh/g, respectively, and the coulombic efficiency was 91.1%. As shown in fig. 16, based on the corundum-coated polypropylene separator material obtained in the comparative example, 622 type ternary nickel-cobalt-manganese alloy is used as the positive electrode, metal lithium is used as the negative electrode, the first charging specific capacity and the first discharging specific capacity of the button battery prepared according to the standard button battery manufacturing method are 141.7mAh/g and 131.6mAh/g respectively, the coulombic efficiency is 92.8%, after 100 times of charging and discharging, the charging specific capacity and the discharging specific capacity are 66.8mAh/g and 54.4mAh/g respectively, and the coulombic efficiency is reduced to about 81.5%.
It should be noted that, comparing the above-mentioned specific examples and comparative examples, the batteries obtained according to the first specific example (data not provided, similar to data of other specific examples), the second specific example and the third specific example are different from the batteries obtained according to the first specific example and the second specific example mainly in that the separator material is different, and mainly the substance coated on the separator is different, the performance of the battery prepared by the oxide-coated lithium lanthanum zirconium oxide material in the present application is obviously improved compared with that in the comparative examples, and particularly after 100 times of charge and discharge cycling, the decline of the battery performance is obviously reduced, and the battery has higher cycling stability.
Although the present application has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application, and all changes, substitutions and alterations that fall within the spirit and scope of the application are to be understood as being included within the following description of the preferred embodiment.
Claims (10)
1. The oxide-coated lithium lanthanum zirconium oxide material is characterized by being of a core-shell structure and comprising lithium lanthanum zirconium oxide and an oxide coating layer coated on the surface of the lithium lanthanum zirconium oxide.
2. The oxide-coated lithium lanthanum zirconium oxide material of claim 1,
the lithium lanthanum zirconium oxide is a pure lithium lanthanum zirconium oxide material or a lithium lanthanum zirconium oxide material doped with at least one element of tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium and barium;
the oxide is MOxX is a natural number, and M is at least one selected from silicon, aluminum, titanium, zirconium and niobium;
d of the lithium lanthanum zirconium oxide50Is 50-500 nm; preferably, D of the lithium lanthanum zirconium oxide50Is 100-300 nm;
the thickness of the oxide coating layer is 5-100 nm; preferably, the thickness of the oxide coating layer is 5-20 nm.
3. A method of preparing an oxide coated lithium lanthanum zirconium oxide material, comprising the steps of:
s11, forming an oxide coating layer on the surface of the lithium lanthanum zirconium oxide by a coprecipitation method to obtain modified lithium lanthanum zirconium oxide;
s12, carrying out heat treatment on the modified lithium lanthanum zirconium oxide, wherein the heat treatment temperature is 200-600 ℃, and obtaining the oxide-coated lithium lanthanum zirconium oxide material.
4. The method of preparing an oxide coated lithium lanthanum zirconium oxide material of claim 3, wherein the lithium lanthanum zirconium oxide is a pure lithium lanthanum zirconium oxide material or a lithium lanthanum zirconium oxide material doped with at least one element of tantalum, niobium, aluminum, gallium, tungsten, calcium, strontium, and barium;
d of the lithium lanthanum zirconium oxide50Is 50-500 nm; preferably, D of the lithium lanthanum zirconium oxide50Is 100-300 nm;
the heat treatment temperature of the step S12 is 200-400 ℃;
the heat treatment time of the step S12 is 2-6 hours;
the heat treatment of step S12 is performed under air atmosphere conditions;
the step S11 includes the steps of:
s111, sequentially adding a dispersion solvent and lithium lanthanum zirconium oxide into a reaction container according to the mass ratio of 10-20:1, and stirring for 1-4 hours to obtain a first suspension;
s112, press MOxCalculating equivalent, mixing the M source with the mass fraction ratio of 1:100-1000 and the first suspension, and stirring for 1-4 hours to obtain a second suspension; the X is a natural number, and the M source comprises a methyl ester compound M (OCH) of M3)2xEthyl ester compound M (OC)2H5)2xPropyl ester compound M (OC)3H7)2xAnd butyl ester compound M (OC)4H9)2xAt least one of; the M is selected from at least one of silicon, aluminum, titanium, zirconium and niobium;
s113, ammonia water is dripped into the second suspension, and the mass ratio of the total mass of the ammonia in the ammonia water dripped into the second suspension to the mass of the lithium lanthanum zirconium oxide required for obtaining the second suspension is 1-5:1, so that a third suspension is obtained;
s114, filtering the third suspension to obtain suspended particles;
and S115, washing the suspended particles by using a dispersing solvent, and drying the suspended particles to obtain the modified lithium lanthanum zirconium oxide.
5. The method of preparing an oxide-coated lithium lanthanum zirconium oxide material as claimed in claim 4, wherein the steps S111 and/or S112 are performed under a protective atmosphere; the protective atmosphere is nitrogen, argon, helium or any combination thereof;
the stirring frequency in the steps S111 and S112 is 30-50 Hz;
the dispersing solvent comprises at least one of methanol, ethanol, isopropanol, acetone, butanone, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide;
the dropping speed of the ammonia water is 1-5 mL/h;
the mass fraction of ammonia in the ammonia water is 10-25%;
the drying temperature in the step S115 is 80-120 ℃.
6. The membrane material is characterized by comprising a membrane and a coating layer coated on the membrane, wherein the coating layer is an oxide-coated lithium lanthanum zirconium oxide material; the oxide-coated lithium lanthanum zirconium oxide material is the oxide-coated lithium lanthanum zirconium oxide material described in claim 1 or 2, or the oxide-coated lithium lanthanum zirconium oxide material obtained by the method for preparing the oxide-coated lithium lanthanum zirconium oxide material described in any one of claims 3 to 5.
7. The separator material according to claim 6, wherein the separator is polypropylene, polyethylene terephthalate, or a composite material containing them;
the thickness of the diaphragm is 10-100 μm; preferably, the thickness of the separator is 10 to 20 μm;
the thickness of the coating layer is 1-20 μm; preferably, the thickness of the coating layer is 1 to 5 μm.
8. A method of making a separator material, comprising the steps of:
s21, mixing the components in a mass ratio of 1: a: b, mixing the oxide-coated lithium lanthanum zirconium oxide material, a polymer and a dispersing solvent to obtain diaphragm slurry; a is more than or equal to 1 and less than or equal to 9, and b is more than or equal to 20 and less than or equal to 500;
s22, coating the diaphragm slurry on the surface of the diaphragm to obtain a diaphragm material;
the oxide-coated lithium lanthanum zirconium oxide material is the oxide-coated lithium lanthanum zirconium oxide material described in claim 1 or 2, or the oxide-coated lithium lanthanum zirconium oxide material prepared by the method for preparing the oxide-coated lithium lanthanum zirconium oxide material described in any one of claims 3 to 5.
9. The method for preparing the membrane material according to claim 8, wherein the polymer is at least one of polyethylene oxide, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, or a copolymer thereof;
the dispersing solvent comprises at least one of methanol, ethanol, isopropanol, acetone, butanone, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide;
the step S22 specifically includes: and coating the diaphragm slurry on the surface of the diaphragm by a tape casting method, and drying at 80-120 ℃ to obtain the diaphragm material.
10. A lithium battery, characterized in that the separator material in the lithium battery is the separator material described in claim 6 or 7, or the separator material obtained by the method for preparing a separator material described in claim 8 or 9.
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