CN113381121A - 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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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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, carrying out 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 have made significant progress, such as electrode design, membrane modification, electrolyte additives, negative electrode 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 great amount 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 111416090A) and the like, and the electrochemical performance of the lithium-sulfur battery is remarkably improved. However, in lithium-sulphur batteries, the soluble polysulphides belong to the intermediate products of the lithium-sulphur discharge reaction process, and the conversion of polysulphides into solid lithium sulphide is rather slow kinetically. Most polar materials do not accelerate the conversion of polysulfides to lithium sulfide. Thus, an enrichment of polysulphides is caused, even an irresistible shuttling. Researches show that the catalyst modified diaphragm made of nano oxide materials (CN 111370626A), metal nitrides (CN 111864156A) and the like can effectively accelerate shuttling of polysulfide, 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. Electrocatalytic activity of, for example, metal oxides and metal sulfides is severely limited by their poor adsorption properties to polysulfides. Therefore, the high adsorption performance is achieved through the constructionAnd the nano-composite with electrocatalytic activity is an effective method for solving the shuttling of the polysulfide and accelerating the transformation of the polysulfide.
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.
Preparation of modified diaphragm of tungsten oxide/clay mineral nano material
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 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; 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 the 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: 0.3-1: 3.
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 for 12-48 h at 130-200 ℃.
(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 700-1300 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: 1-0.6: 1, 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 20-24 hours at 55-65 ℃.
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.
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 example 1 and a commercial polyethylene diaphragm are selected for comparative analysis, 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. The initial capacity of the lithium-sulfur battery assembled by the modified diaphragm can reach 1076 mA h g at 0.1 DEG C−1. When the discharge rate is increased to 5C, the capacity still reaches 512 mA h g−1. The capacity retention rate is up to 47.6 percent relative to 0.1C. However, the capacity of the comparative example assembled lithium-sulfur battery showed a rapid decrease with increasing rate, with a capacity retention at 5.0C of only 24.8% 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 the 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 of tungsten chloride into 30 mL of deionized water, stirring and carrying out ultrasonic treatment until the tungsten chloride is dissolved; then adding 3mg of halloysite nanoparticles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH =2.6 of the suspension; then transferring the mixture into a reaction kettle, drying the mixture for 24 hours at 180 ℃, washing the mixture for 3 times respectively by deionized water and ethanol, drying and grinding the mixture to obtain a tungsten oxide/halloysite nano 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, N-dimethylformamide is used for adjusting the viscosity of the slurry to 1000 mPs s, and the slurry is stirred to obtain uniform slurry; then coating the slurry on one side of a polyethylene diaphragm by adopting a roller coating method, and drying for 24 hours at the temperature of 60 ℃ to obtain the oxidized polyethylene diaphragmThe tungsten/halloysite nano material modified diaphragm. The thickness of the coating in the diaphragm is 3.5 +/-0.5 mu m;
(3) performance: 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 of hexahydroxy tungsten into 45 mL of ethanol, stirring, and carrying out ultrasonic treatment until the hexahydroxy tungsten is dissolved; then adding 3mg of hectorite nano particles into the solution, stirring and carrying out ultrasonic treatment to obtain a uniform suspension, and adjusting the pH of the solution 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 the tungsten oxide/hectorite nano material, super P and LA133 according to the mass fractions of 65%, 30% and 5%, ball-milling, adding deionized water/isopropanol (v/v =1: 1) to adjust the viscosity of the slurry to be 980 mPs & s, and stirring to obtain uniform slurry; and then coating the slurry on one side of the polyvinylidene fluoride 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 1.5 +/-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 of attapulgite nano particles 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 for 36 hours at 200 ℃, 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 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 mPs & s, 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 for 24 hours at the temperature of 60 ℃ 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) performance: 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 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 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, N-dimethylformamide is used for adjusting the viscosity of the slurry to 880 mPs s, and stirring is carried out 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 of 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 for 30 hours at 190 ℃, 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, N-dimethylformamide is used for adjusting the viscosity of the slurry to 880 mPs s, and stirring is carried out to obtain uniform slurry; and then coating the slurry on one side of a polypropylene diaphragm by adopting a roller coating method, and drying for 24 hours at the temperature of 60 ℃ 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 (10)
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; adding clay mineral nano particles, stirring and carrying out ultrasonic treatment to obtain 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;
(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.
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; the mass ratio of the tungsten source to the clay mineral is 1: 0.3-1: 3.
3. 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 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 the lithium-sulfur battery as claimed in claim 1, wherein: in the step (1), the hydrothermal reaction is carried out for 12-48 h at 130-200 ℃.
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 conductive agent is at least one of super P, acetylene black, graphene, reduced graphene oxide and conductive carbon nanotubes; the mass ratio of the conductive agent to the tungsten oxide/clay mineral nano material is 9: 1-0.6: 1, and the mass percentage content of the conductive agent to the tungsten oxide/clay mineral nano material in the composite coating is 90-97%.
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), at least one of the binders polyvinylidene fluoride, sodium carboxymethylcellulose and LA133 is adopted; the mass percentage of the composite coating is 3% -10%.
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 solvent is at least one of deionized water, isopropanol and N, N-dimethylformamide.
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 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.
9. 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 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.
10. The method for preparing the tungsten oxide/clay mineral nanomaterial modified membrane for the lithium-sulfur battery as claimed in claim 1, wherein: the thermosetting is carried out for 20-24 hours at 55-65 ℃.
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| CN115036592A (en) * | 2022-06-21 | 2022-09-09 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
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| CN114368788A (en) * | 2021-12-21 | 2022-04-19 | 广东省科学院化工研究所 | Composite material and battery composite diaphragm |
| CN114368788B (en) * | 2021-12-21 | 2023-12-05 | 广东省科学院化工研究所 | Composite material and battery composite diaphragm |
| CN115036592A (en) * | 2022-06-21 | 2022-09-09 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
| CN115036592B (en) * | 2022-06-21 | 2023-08-29 | 中国地质大学（武汉） | Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof |
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