CN113381121B - Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery - Google Patents
Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery Download PDFInfo
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a tungsten oxide/clay mineral nano material modified diaphragm for a lithium-sulfur battery, which comprises the steps of mixing a tungsten oxide/clay mineral nano material, a conductive agent and a binder, ball-milling, adding a solvent to adjust the viscosity of slurry to 700-1300 mPa.s, and uniformly stirring to obtain the slurry; then coating the slurry on one side of a commercial diaphragm by adopting a roller coating method, and performing thermocuring to obtain a modified diaphragm, wherein the tungsten oxide/clay mineral nano material has strong electro-catalytic activity and high adsorption performance, and can effectively accelerate the catalytic conversion reaction of polysulfide; the highly electron conductive carbon material facilitates rapid transfer of electrons during catalytic conversion. The prepared modified diaphragm can effectively inhibit the problems of low battery capacity, low active substance utilization, slow kinetics, poor rate performance and stable circulation caused by polysulfide shuttling in the lithium-sulfur battery, thereby obviously improving the electrochemical performance of the battery.
Description
Technical Field
The invention relates to a preparation method of a tungsten oxide/clay mineral nano material modified diaphragm for a lithium-sulfur battery, belonging to the technical field of lithium batteries.
Background
The lithium-sulfur battery has high mass energy density (2600 Wh kg) −1 ) And high volumetric energy density (2800 Wh L) −1 ) And is considered one of the most promising high specific energy storage systems. However, the development of high energy density lithium-sulfur batteries is severely restricted by problems such as shuttle of soluble polysulfides. Various strategies have been used to solve the above scientific problems and to achieveSignificant advances have been made, such as electrode design, membrane modification, electrolyte additives, negative protection, intercalation, and the like. Compared with other strategies, the diaphragm modification has the advantages of simplicity, high efficiency, difficulty in increasing the volume and the quality of the battery, easiness in industrial popularization and the like. However, the inherent drawbacks of commercial separators have hindered their use in lithium-sulfur batteries, such as large and irregular pore size structures, non-polar surfaces, and the like. Therefore, separator surface modification is one of the main approaches to addressing polysulfide shuttling in lithium-sulfur batteries. At present, a large number of carbon materials and other nano-materials are used for modifying the diaphragm, and are applied to the lithium-sulfur battery, such as boron nitride (CN 110707269A), perovskite (CN 11141 6090A) and the like, so that the electrochemical performance of the lithium-sulfur battery is remarkably improved. However, in lithium-sulphur batteries, soluble polysulphides are intermediate products during the lithium-sulphur discharge reaction, and the conversion of polysulphides into solid lithium sulphide is rather slow in kinetics. Most polar materials do not accelerate the conversion of polysulfide to lithium sulfide. Thus, an enrichment of polysulphides is caused, which may not even stop shuttling. Researches show that catalyst modified diaphragms of nano oxide materials (CN 111370626A), metal nitrides (CN 111864156A) and the like can effectively accelerate shuttling of polysulfides, and dynamics, capacity, cycling stability and the like of the lithium-sulfur battery are obviously improved. However, the single catalyst described above is not effective in exerting the optimum electrocatalytic activity. The electrocatalytic activity of e.g. metal oxides and metal sulfides is severely limited by their poor adsorption properties to polysulfides. Therefore, an effective method for solving polysulfide shuttling and accelerating polysulfide conversion is achieved by constructing nano-composite with high adsorption performance and electrocatalytic activity.
Disclosure of Invention
The invention aims to solve the technical defects of the existing commercial diaphragm in the application of a lithium-sulfur battery, and provides a preparation method of a tungsten oxide/clay mineral nano material modified diaphragm suitable for the lithium-sulfur battery so as to promote the development of the next generation of high-energy density lithium-sulfur battery.
1. Preparation of tungsten oxide/clay mineral nano material modified diaphragm
The invention relates to a preparation method of a tungsten oxide/clay mineral nano material modified diaphragm for a lithium-sulfur battery, which comprises the following steps:
(1) Preparing tungsten oxide/clay mineral nano material: adding a tungsten source into a strong polar solvent, stirring, and performing ultrasonic treatment until the tungsten source is dissolved; adding clay mineral nano particles, stirring and carrying out ultrasonic treatment to obtain uniform suspension; and (3) adjusting the pH value of the suspension to 1~3, transferring the suspension to a reaction kettle for hydrothermal reaction, washing, drying and grinding a product to obtain the tungsten oxide/clay mineral nano material.
The tungsten source is one of tungsten chloride, sodium tungstate, tungsten hexacarbonyl and ammonium metatungstate, and the clay mineral nanosheet is at least one of hectorite, calcium-based montmorillonite, attapulgite and halloysite; the mass ratio of the tungsten source to the clay mineral is 1.
The strong polar solvent is at least one of deionized water, ethanol, isopropanol and amide in N, N-dimethylformamide.
The hydrothermal reaction is carried out at 130-200 ℃ for 12-48 h.
(2) Preparing a tungsten oxide/clay mineral nano material modified diaphragm: mixing and ball-milling the tungsten oxide/clay mineral nano material, the conductive agent and the binder, adding a solvent to adjust the viscosity of the slurry to 700-1300 mPa.s, and uniformly stirring to obtain the slurry; and then coating the slurry on one side of a commercial diaphragm by adopting a roller coating method, and performing thermocuring to obtain the tungsten oxide/clay mineral nano material modified diaphragm for the lithium-sulfur battery.
The conductive agent is at least one of super P, acetylene black, graphene, reduced graphene oxide and conductive carbon nano tubes; the mass ratio of the conductive agent to the tungsten oxide/clay mineral nano material is 9 to 0.6, and the mass percentage content of the conductive agent to the tungsten oxide/clay mineral nano material in the composite coating is 90-97%.
At least one of the binders polyvinylidene fluoride, sodium carboxymethylcellulose and LA 133; the mass percentage of the composite coating is 3% -10%.
The solvent is at least one of deionized water, isopropanol and N, N-dimethylformamide.
The commercial diaphragm is one of a polypropylene diaphragm, a polyethylene/polypropylene mixed diaphragm, a polyimide diaphragm, a polyvinylidene fluoride diaphragm and a glass fiber diaphragm.
The thermosetting is carried out for 20 to 24 hours at the temperature of 55 to 65 ℃.
The thickness of the tungsten oxide/clay mineral nano material coating in the tungsten oxide/clay mineral nano material modified diaphragm is 1~4 +/-0.5 mu m. The coating comprises tungsten oxide/clay mineral nano material with strong electro-catalytic activity and high adsorption performance, carbon material with high electronic conductivity and binder; the tungsten oxide/clay mineral nano material can effectively accelerate catalytic conversion reaction of polysulfide, and the conductive carbon material is beneficial to rapid transfer of electrons in the catalytic conversion process.
3. Performance of tungsten oxide/clay mineral nano material modified diaphragm
The lithium-sulfur battery is assembled by adopting the tungsten oxide/clay mineral nano material modified diaphragm, and the modified diaphragm is directed at the sulfur positive electrode side in the assembling process. Various performances of the tungsten oxide/clay mineral nano material modified diaphragm prepared in the embodiment 1 and a commercial polyethylene diaphragm are compared and analyzed, and the structure and the performance of the modified diaphragm are illustrated.
1. Mechanical Properties
The modified diaphragm prepared in example 1 is repeatedly folded and bent and then opened, and the diaphragm is free from powder falling, which shows that the diaphragm of the invention has excellent mechanical stability.
2. Wettability of electrolyte
Fig. 1 is a contact angle of an ether-based electrolyte on the surfaces of a modified separator (right) prepared in example 1 and a commercial polyethylene separator (left, thickness of 25 μm, porosity of 41%). It was shown that the contact angle of the ether-based electrolyte on the surface of the modified separator was 0 °, and the contact angle on the surface of the commercial polyethylene separator was 44.6 °. This shows that the tungsten oxide/clay mineral nano material modified diaphragm has better wettability to the electrolyte and is easy to be wetted by the electrolyte.
3. Electrocatalytic activity towards polysulphides
FIG. 2 is a CV curve of a symmetric battery assembled by the tungsten oxide/clay mineral nanomaterial modified membrane prepared by the method. The tungsten oxide/clay mineral nano material is used for preparing a working electrode, and the symmetrical battery is assembled by the ether-based electrolyte containing the polysulfide, so that the higher the peak current density of the CV curve is, the higher the electrocatalytic activity of the material on the polysulfide is. It can be easily found that the tungsten oxide/clay mineral nano material prepared by the invention has good electrocatalytic activity on polysulfide.
4. Electrochemical performance in lithium symmetric cells
FIG. 3 is a comparison of electrochemical performance of the modified separator prepared in example 1 and a polyethylene separator (comparative example: 25 μm in thickness and 41% in porosity) in lithium-sulfur. Under the condition of 0.1C, the initial capacity of the lithium-sulfur battery assembled by the modified diaphragm can reach 1076 mA h g −1 . When the discharge rate is increased to 5C, the capacity still reaches 512 mA h g −1 . Compared with 0.1C, the capacity retention rate is up to 47.6%. However, the capacity of the comparative example assembled lithium-sulfur cell showed a rapid drop with increasing rate, with a capacity retention of only 24.8% at 5.0C relative to 0.1C. This demonstrates that the modified oxygen separators are effective in inhibiting polysulfide shuttling in lithium-sulfur cells, thereby significantly improving the electrochemical performance of the cells.
In conclusion, the tungsten oxide/clay mineral nano material, the conductive agent and the binder are mixed and ball-milled, then the solvent is added to adjust the viscosity of the slurry to 700-1300 mPa.s, and the slurry is obtained after uniform stirring; then coating the slurry on one side of a commercial diaphragm by adopting a roller coating method, and performing thermocuring to obtain a modified diaphragm, wherein the tungsten oxide/clay mineral nano material has strong electro-catalytic activity and high adsorption performance, and can effectively accelerate the catalytic conversion reaction of polysulfide; the highly electron conductive carbon material facilitates rapid transfer of electrons during catalytic conversion. The prepared modified diaphragm can effectively inhibit the problems of low battery capacity, low active substance utilization, slow kinetics, poor rate performance and stable circulation caused by polysulfide shuttling in a lithium-sulfur battery, thereby obviously improving the electrochemical performance of the battery.
Drawings
Fig. 1 is a comparison of electrolyte wettability of the separator in the composite separator of the invention of example 1 and the polyethylene separator.
Fig. 2 is a CV curve of a symmetrical cell assembled by tungsten oxide/clay mineral nanomaterial invented in each example.
Fig. 3 is a comparison of the performance of a lithium-sulfur battery assembled with the separator in the composite separator of example 1 and a polyethylene separator.
Detailed Description
The preparation and performance of the tungsten oxide/clay mineral nano material composite modified diaphragm of the invention are further explained by the specific examples.
Example 1
(1) Preparing a tungsten oxide/clay mineral nano material: adding 3mg tungsten chloride into 30 mL deionized water, stirring and carrying out ultrasonic treatment until the tungsten chloride is dissolved; then adding 3mg halloysite nanoparticles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH of the suspension to be =2.6; then transferring the tungsten oxide/halloysite nanometer material to a reaction kettle, drying 24h at 180 ℃, washing 3 times respectively by deionized water and ethanol, drying and grinding to obtain the tungsten oxide/halloysite nanometer material;
(2) Preparing a modified diaphragm: mixing tungsten oxide/halloysite nano material, acetylene black and polyvinylidene fluoride according to the mass fractions of 75%, 15% and 10%, ball-milling, and addingN, NAdjusting the viscosity of the slurry to 1000 mPas by using dimethylformamide, and stirring to obtain uniform slurry; and then coating the slurry on one side of a polyethylene diaphragm by adopting a roller coating method, and drying the polyethylene diaphragm at 60 ℃ for 24h to obtain the tungsten oxide/halloysite nano material modified diaphragm. The thickness of the coating in the diaphragm is 3.5 +/-0.5 mu m;
(3) The performance is as follows: the tungsten oxide/halloysite nano material modified diaphragm is used for assembling the lithium-sulfur battery by facing a sulfur anode, CV curves of symmetrical batteries are shown in figures 2 and 3, the tungsten oxide/halloysite nano material has good electrocatalytic performance on polysulfide, and the rate capability of the lithium-sulfur battery is obviously improved by the modified diaphragm.
Example 2
(1) Preparing a tungsten oxide/clay mineral nano material: adding 6 mg hexahydroxytungsten into 45 mL ethanol, stirring, and performing ultrasonic treatment until the hexahydroxytungsten is dissolved; then 3mg hectorite nano particles are added into the solution, stirring and ultrasonic treatment are carried out to obtain uniform suspension, and the pH of the solution is adjusted to be =1.2; then transferring the mixture into a reaction kettle, drying the mixture for 48 hours at 160 ℃, washing the mixture for 3 times respectively by deionized water and ethanol, drying and grinding the mixture to obtain the tungsten oxide/hectorite nano material;
(2) Preparing a modified diaphragm: mixing and ball-milling the tungsten oxide/hectorite nano material, super P and LA133 according to the mass fractions of 65%, 30% and 5%, adding deionized water/isopropanol (v/v = 1:1) to adjust the viscosity of the slurry to 980 mPas & s, and stirring to obtain uniform slurry; and then coating the slurry on one side of the polyvinylidene fluoride membrane by adopting a roller coating method, and drying the polyvinylidene fluoride membrane at 60 ℃ for 24h to obtain the tungsten oxide/hectorite nano material modified membrane. The thickness of the coating in the diaphragm is 1.5 +/-0.5 mu m;
(3) Performance: the modified diaphragm is used for assembling the lithium-sulfur battery by facing a sulfur positive electrode, the CV curve of a symmetrical battery is shown in figure 2, the tungsten oxide/hectorite nano material has good electrocatalytic performance on polysulfide, and the rate capability of the lithium-sulfur battery is obviously improved by the modified diaphragm.
Example 3
(1) Preparing a tungsten oxide/clay mineral nano material: adding 4.5mg of sodium tungstate into 15mL of deionized water, stirring and carrying out ultrasonic treatment until the sodium tungstate is dissolved; adding 8.4 mg attapulgite nanoparticles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH of the solution to be =3; then transferring the mixture into a reaction kettle, drying the mixture at 200 ℃ for 36 h, washing the mixture for 3 times respectively by deionized water and ethanol, drying and grinding the mixture to obtain the tungsten oxide/attapulgite nano material;
(2) Preparing a diaphragm: mixing and ball-milling the tungsten oxide/attapulgite nano material, graphene and LA133 according to the mass fractions of 80%, 17% and 3%, adding deionized water/isopropanol (v/v = 1:1) to adjust the viscosity of the slurry to 1280 mPas, and stirring to obtain uniform slurry; and then coating the slurry on one side of the polyimide diaphragm by adopting a roller coating method, and drying the polyimide diaphragm at 60 ℃ by using 24h to obtain the tungsten oxide/attapulgite nano material modified diaphragm. The thickness of the coating in the diaphragm is 3 +/-0.5 mu m;
(3) The performance is as follows: the modified diaphragm is used for assembling the lithium-sulfur battery by facing a sulfur anode, the CV curve of the symmetrical battery is shown in figure 2, the tungsten oxide/attapulgite nano material has good electrocatalytic performance on polysulfide, and the rate capability of the lithium-sulfur battery is obviously improved by the modified diaphragm.
Example 4
(1) Preparing a tungsten oxide/clay mineral nano material: adding 3mg of metatungstic acid amine into 5mL of deionized water, stirring, and carrying out ultrasonic treatment until the metatungstic acid amine is dissolved; then adding 4.5mg of hectorite nanoparticles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH of the solution to be =2.6; then transferring the mixture to a reaction kettle, drying 48h at 160 ℃, washing 3 times by deionized water and ethanol respectively, drying and grinding to obtain a tungsten oxide/hectorite nano material;
(2) Preparing a diaphragm: mixing tungsten oxide/hectorite nano material, reduced graphene oxide and polyvinylidene fluoride according to the mass fractions of 42%, 51% and 7%, ball-milling, and addingN, NAdjusting the viscosity of the slurry to 880 mPas & s by using dimethylformamide, and stirring to obtain uniform slurry; and then coating the slurry on one side of the glass fiber diaphragm by adopting a roller coating method, and drying for 24 hours at the temperature of 60 ℃ to obtain the tungsten oxide/hectorite nano material modified diaphragm. The thickness of the coating in the diaphragm is 1 +/-0.5 mu m;
(3) Performance: the modified diaphragm is used for assembling the lithium-sulfur battery by facing a sulfur positive electrode, the CV curve of a symmetrical battery is shown in figure 2, the tungsten oxide/hectorite nano material has good electrocatalytic performance on polysulfide, and the rate capability of the lithium-sulfur battery is obviously improved by the modified diaphragm.
Example 5
(1) Preparing a tungsten oxide/clay mineral nano material: adding 8mg of hexahydroxy tungsten into 6mL of ethanol, stirring, and carrying out ultrasonic treatment until the hexahydroxy tungsten is dissolved; then adding 12 mg calcium-based montmorillonite nanoparticles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH of the solution to be =2.6; then transferring the mixture into a reaction kettle, drying the mixture at 190 ℃ for 30 h, washing the mixture for 3 times respectively by deionized water and ethanol, drying and grinding the mixture to obtain the tungsten oxide/calcium-based montmorillonite nano material;
(2) Preparing a modified diaphragm: mixing tungsten oxide/calcium-based montmorillonite nanometer material, conductive carbon nanotube and sodium carboxymethylcellulose in the mass fractions of 88%, 10% and 2%, ball-milling, addingN, NAdjusting the viscosity of the slurry to 880 mPas by using dimethylformamide, and stirring to obtain uniform slurry; and then coating the slurry on one side of a polypropylene diaphragm by adopting a roller coating method, and drying the polypropylene diaphragm at 60 ℃ for 24h to obtain the tungsten oxide/calcium-based montmorillonite nano material composite modified diaphragm. The thickness of the coating in the diaphragm is 2.6 +/-0.5 mu m;
(3) Performance: the modified diaphragm is used for assembling the lithium-sulfur battery by facing a sulfur positive electrode, the CV curve of a symmetrical battery is shown in figure 2, the tungsten oxide/calcium-based montmorillonite nano material has good electrocatalytic performance on polysulfide, and the rate capability of the lithium-sulfur battery is obviously improved by the modified diaphragm.
Claims (8)
1. A preparation method of a tungsten oxide/clay mineral nano material modified diaphragm for a lithium-sulfur battery comprises the following steps:
(1) Preparing a tungsten oxide/clay mineral nano material: adding a tungsten source into a strong polar solvent, stirring and carrying out ultrasonic treatment until the tungsten source is dissolved; then adding clay mineral nano particles, stirring and carrying out ultrasonic treatment to obtain a uniform suspension; adjusting the pH value of the suspension to 1~3, transferring the suspension to a reaction kettle for hydrothermal reaction, washing, drying and grinding a product to obtain a tungsten oxide/clay mineral nano material; the mass ratio of the tungsten source to the clay mineral nano particles is 1:0.3 to 1; the hydrothermal reaction is carried out for 12 to 48 hours at a temperature of between 130 and 200 ℃;
(2) Preparing a tungsten oxide/clay mineral nano material modified diaphragm: mixing and ball-milling the tungsten oxide/clay mineral nano material, the conductive agent and the binder, adding a solvent to adjust the viscosity of the slurry to 700 to 1300 mPa.s, and uniformly stirring to obtain the slurry; coating the slurry on one side of a commercial diaphragm by adopting a roller coating method, and performing thermocuring to obtain a tungsten oxide/clay mineral nano material modified diaphragm for the lithium-sulfur battery; the mass ratio of the conductive agent to the tungsten oxide/clay mineral nano material is 9 to 0.6, and the mass percentage of the conductive agent to the tungsten oxide/clay mineral nano material in the composite coating is 90-97%; the thickness of the tungsten oxide/clay mineral nano material coating is 1~4 +/-0.5 mu m.
2. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: in the step (1), the tungsten source is one of tungsten chloride, sodium tungstate, tungsten hexacarbonyl and ammonium metatungstate, and the clay mineral nanosheets are at least one of hectorite, calcium-based montmorillonite, attapulgite and halloysite.
3. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for lithium-sulfur battery as claimed in claim 1, wherein: in the step (1), the strong polar solvent is at least one of deionized water, ethanol, isopropanol and amide in N, N-dimethylformamide.
4. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for lithium-sulfur battery as claimed in claim 1, wherein: in the step (2), the conductive agent is at least one of super P, acetylene black, graphene, reduced graphene oxide and conductive carbon nanotubes.
5. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: in the step (2), the binder is at least one of polyvinylidene fluoride, sodium carboxymethylcellulose and LA133, and the mass percentage of the binder in the composite coating is 3% -10%.
6. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: in the step (2), the solvent is at least one of deionized water, isopropanol and N, N-dimethylformamide.
7. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: in the step (2), the commercial diaphragm is one of a polypropylene diaphragm, a polyethylene/polypropylene mixed diaphragm, a polyimide diaphragm, a polyvinylidene fluoride diaphragm and a glass fiber diaphragm.
8. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: in the step (2), the thermosetting is carried out for 20 to 24 hours at the temperature of 55 to 65 ℃.
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