CN114275776B - Molybdenum sulfide composite material with manganese element loaded on graphene, preparation method and application thereof - Google Patents
Molybdenum sulfide composite material with manganese element loaded on graphene, preparation method and application thereof Download PDFInfo
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Abstract
A molybdenum sulfide composite material with manganese uniformly loaded on graphene, a preparation method and application thereof in modification of lithium-sulfur battery diaphragm belong to the technical field of lithium-sulfur batteries. The graphene oxide is dispersed in water, and (NH) is added 4 ) 6 Mo 7 O 24 Mixing with thiourea, adding manganese salt, and dispersing with ultrasound; and performing hydrothermal reaction for 15-30 hours at 160-220 ℃ in nitrogen atmosphere, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3-5 times, rapidly freezing the centrifugal product in liquid nitrogen, and finally freeze-drying for 20-30 hours under vacuum to obtain the molybdenum sulfide composite material, wherein the composite material can be further applied to a lithium-sulfur battery as a modified diaphragm material, and the modified diaphragm material not only can reduce self impedance of the diaphragm, but also can increase a lithium ion channel on the surface of the diaphragm to accelerate battery reaction, thereby improving the overall performance of the battery.
Description
Technical Field
The application belongs to the technical field of lithium sulfur batteries, and particularly relates to a molybdenum sulfide composite material with manganese uniformly loaded on graphene, a preparation method and application of the molybdenum sulfide composite material in modification of a lithium sulfur battery diaphragm.
Background
Since the human beings put into the electrical age, the electric energy greatly changes our daily life, and the human beings realize the high-speed development of industry through the transmission and application of electric power. However, with the growing population, the rough expansion of industrial processes, the excessive use of fossil fuels, etc., environmental problems have begun to gradually affect our lives and even threaten human survival and development. It is gradually recognized that the development of renewable energy systems mainly comprising new energy sources such as wind energy, solar energy, tidal energy and the like will be an important link in the energy layout of future countries and the world. However, compared with the traditional power generation mode, the new energy is more influenced by many factors such as geography, environment and the like. Therefore, new energy sources are in urgent need of a reasonable and efficient energy storage device to meet the development demands. Lithium ion batteries are widely used as a prominent power storage solution in consumer electronics and power cells. Of course, lithium ion batteries are not applicable to all energy storage fields, and some other types of batteries are also gradually developed under trend.
As the demand for energy storage increases, the energy density of lithium ion batteries cannot meet some of these demands, and the development of new battery systems with high energy density has been delayed. Since Lithium Sulfur Batteries (LSBs) have a higher theoretical specific capacity (1675 mA h g -1 ) And energy density (2600 Wh kg) -1 ) Researchers believe that it has better application prospects than lithium ion batteries in certain fields. Meanwhile, one of the main raw materials of the lithium-sulfur battery has low price and abundant reserves in the nature, and the advantages can greatly reduce the cost required by battery production and are beneficial to popularization and application of the lithium-sulfur battery. However, there are still many bottlenecks in research and development of lithium sulfur batteries. First, the main electrode materials of lithium sulfur batteries have poor conductivity properties, both of elemental sulfur and lithium sulfide, a discharge product, which results in the performance of the battery itself not as good as theoretically expected. Second, the discharge product lithium sulfide and elemental sulfur differ significantly in volume, and the discharge/charge process has about 80% of volume shrinkageExpansion, which may severely damage the cell structure. Finally, lithium polysulfide generated during the charge and discharge of the battery can be dissolved in the electrolyte, and the shuttle effect of polysulfide can affect the utilization ratio of active substances of the lithium-sulfur battery, so that on one hand, the coulomb efficiency is reduced, and on the other hand, the cycle life is shortened.
To overcome these problems, scientists have prepared porous or coarse carbon-based structures and carried pure sulfur onto carbon materials by a hot-melt method, and increase the conductivity of the positive electrode by the carbon materials while buffering the volume change during charge and discharge. In addition, another solution is to increase the physical adsorption and chemical catalytic capacity of the material for polysulfides by designing different polar materials.
Disclosure of Invention
The application aims to provide molybdenum sulfide (MoS) loaded with manganese element on graphene (G) 2 ) Composite materials, methods of preparation and use thereof. The composite material is used for modifying a lithium-sulfur battery system, and the shuttle effect is inhibited by coating the material on a diaphragm modification layer, so that the transformation effect of polysulfide is promoted. The material has the advantages of simple preparation process, easy production and less environmental pollution.
The application is realized by the following technical scheme:
a preparation method of a molybdenum sulfide composite material with manganese loaded on graphene comprises the following steps:
dispersing graphene oxide in water, adding (NH 4 ) 6 Mo 7 O 24 Mixing with thiourea, adding a certain amount of manganese salt, and uniformly dispersing by ultrasonic; the obtained mixed solution is subjected to hydrothermal reaction in a reaction kettle at 160-220 ℃ under nitrogen atmosphere for 15-30 hours, then the reaction solution is taken out and cooled to room temperature, the obtained solid reaction product is centrifugally washed for 3-5 times by deionized water, the centrifugal product is put into liquid nitrogen to be quickly frozen, and finally the obtained product is placed into vacuum (the vacuum degree is less than 10 Pa) to be frozen (-60-35 ℃) and dried for 20-30 hours, so that molybdenum sulfide composite material powder with manganese loaded on graphene is obtained and is marked as G@MoS 2 @Mn。
Preferably, the dispersion concentration of the graphene oxide in water is 2-8 mg/mL;
preferably, (NH) 4 ) 6 Mo 7 O 24 The molar ratio of thiourea to manganese salt is 1: (20-60): (10-30);
preferably, (NH) 4 ) 6 Mo 7 O 24 Mass dosage ratio (3-8) between the graphene oxide and the graphene oxide: 1, a step of;
a molybdenum sulfide composite material with manganese loaded on graphene is prepared by the method.
A preparation method of a modified diaphragm material comprises the following steps:
dispersing a molybdenum sulfide composite material with manganese element loaded on graphene and polyvinylidene fluoride (PVDF) in an N-methyl pyrrolidone (NMP) solution, coating the obtained mixed solution on the surface of a polypropylene diaphragm (PP) facing to the positive electrode side of a lithium-sulfur battery, and drying for 4-8 hours at 50-80 ℃ to obtain a modified diaphragm material; the thickness of the polypropylene diaphragm (PP) before modification is 22-28 mu m, the thickness of the modified diaphragm material after modification is 30-45 mu m, and the loading capacity of the molybdenum sulfide composite material per unit area on the modified diaphragm material is 2-8 mg/cm 2 。
Preferably, the dispersion concentration of the total mass of the molybdenum sulfide composite material and PVDF in NMP solution is 0.05-0.15 g/mL.
Preferably, the mass consumption of the PVDF is 10-20% of the sum of the mass of the molybdenum sulfide composite material and the PVDF; in the N-methyl pyrrolidone (NMP) solution, the concentration of the sum of the molybdenum sulfide composite material and PVDF is 0.05-0.20 mg/mL.
The application provides a molybdenum sulfide composite material with manganese loaded on graphene, which can be further applied to a lithium-sulfur battery as a modified diaphragm material, and has the following advantages:
(1) Compared with MoS 2 And manganese oxide, which is more conductive. The self impedance of the diaphragm can be reduced, and meanwhile, a lithium ion channel on the surface of the diaphragm can be increased, so that the battery reaction is accelerated, and the overall performance of the battery is improved.
(2) The methodThe synthesized material can increase the adsorption effect of the material on polysulfide through the combination of chemical adsorption and physical adsorption, and inhibit the shuttle effect of polysulfide; meanwhile, compared with other graphenes and MoS 2 The composite material and the manganese element can accelerate the oxidation-reduction process in the charge-discharge reaction of the lithium-sulfur battery, and reduce the time for polysulfide to exist in the battery, thereby reducing the energy density loss caused by polysulfide shuttling action.
(3) The material is freeze-dried in the synthesis process, and the appearance is mainly flaky. The material introduces graphene so as to increase more active sites and improve the stability of the material. The material has a large number of porous structures, so that the material can bear the problem of volume expansion and shrinkage generated in the charge and discharge processes of the lithium-sulfur battery, thereby prolonging the cycle life of the battery.
Drawings
FIG. 1 is a graph of a molybdenum sulfide composite material G@MoS prepared in example 1 of the present application and having manganese element supported on graphene 2 SEM image of @ Mn.
FIG. 2 is a graph of a molybdenum sulfide composite material G@MoS prepared in example 1 of the present application and carrying a manganese element on graphene 2 TEM image of @ Mn.
FIG. 3 is a graph showing the composite G@MoS prepared in example 1 and comparative example 1 of the present application 2 @Mn and G@MoS 2 Is a XRD pattern of (C).
FIG. 4 is a graph showing the separator material G@MoS prepared in example 1 and comparative example 2 of the present application 2 Multiplying power cycle performance diagram of an assembled lithium sulfur battery of Mn and PP. From the results of example 1 and comparative example 2, it is understood that the present application has excellent battery rate cycle performance.
FIG. 5 is a graph showing the separator material G@MoS prepared in example 1 and comparative example 2 of the present application 2 Test chart of cycling stability of assembled lithium sulfur batteries of Mn and PP. From the results of example 1 and comparative example 2, it is understood that the present application achieves effective improvement in cycle performance of lithium-sulfur batteries.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate further the objects, aspects and advantages of the application. The examples of the application are given below for further illustration of the application and are not intended to limit the application to the specific embodiments thereof.
Example 1
(1) Preparing graphene oxide dispersion liquid: 120mg of graphene oxide powder was weighed and dispersed in 30mL of deionized water, and sonicated for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g (NH) 4 ) 6 Mo 7 O 24 Added into the graphene oxide dispersion liquid prepared in the step (1) and stirred for 10 minutes. Weigh 0.25g MnSO 4 ·H 2 O was added to the stirred solution and sonicated for 5 minutes. Putting the obtained mixed solution into a hydrothermal reaction kettle, filling nitrogen at room temperature, carrying out hydrothermal reaction for 20 hours at 180 ℃, taking out the reaction solution, cooling to the room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, putting the centrifugal product into liquid nitrogen, rapidly freezing, finally drying in a freeze dryer, wherein the freezing temperature is-50 ℃, the vacuum degree is 5Pa during drying, and the freeze drying time is 24 hours, so that the molybdenum sulfide composite material with manganese loaded on graphene is obtained, and the product quality is about 0.5g.
(3) Preparation of modified separator: mixing 27mg of the molybdenum sulfide composite material obtained in the step (2) and 3mg of PVDF according to the mass ratio of 9:1, then adding the mixture into 300mL of NMP solution, and stirring to prepare slurry; the obtained slurry was uniformly coated on one side surface of a PP separator (thickness of 25 μm), and dried at 60 ℃ for 6 hours to obtain a modified separator material (thickness of 35 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm calculated after weighing 2 。
(4) Preparation of sulfur/conductive carbon black (Super-P) composite material
Weighing sulfur and Super-P in a mass ratio of 7:3, mixing and grinding for 40 minutes, putting the ground mixed powder into a reaction kettle, melting for 20 hours at 155 ℃, and cooling to room temperature to obtain the sulfur/Super-P composite material.
The sulfur/Super-P composite material is used as a positive electrode of a lithium sulfur battery, and the metal lithium sheet is used as a negative electrode. The electrolyte is lithium bistrifluoromethylsulfonylimide as an electrolyte and is dissolved in a mixed solvent of 1, 3-Dioxypentacyclic (DOL) and 1, 2-Dimethoxyethane (DME) in a volume ratio of 1:1 (the final concentration of the electrolyte in the mixed solvent is 1.0M), and the solvent contains 1% by mass of lithium nitrate. The lithium sulfur battery is assembled according to the sequence of the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, and the surface of the PP diaphragm, which is provided with the molybdenum sulfide composite material, faces the positive electrode. At a charge-discharge rate of 0.5C, the initial capacity of the battery reaches 1045mAh/g, the capacity of the battery after 100 circles is 877mAh/g, and the capacity of the battery after 150 circles is 857mAh/g.
Example 2
(1) Preparing graphene oxide dispersion liquid: 120mg of graphene oxide powder was weighed and dispersed in 30mL of deionized water, and sonicated for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g (NH) 4 ) 6 Mo 7 O 24 Added into the graphene oxide dispersion liquid prepared in the step (1) and stirred for 10 minutes. Weigh 0.25g MnSO 4 ·H 2 O was added to the stirred solution and sonicated for 5 minutes. Putting the obtained mixed solution into a hydrothermal reaction kettle, filling nitrogen at room temperature, carrying out hydrothermal reaction for 20 hours at 200 ℃, taking out the reaction solution, cooling to the room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, putting the centrifugal product into liquid nitrogen, rapidly freezing, finally drying in a freeze dryer, wherein the freezing temperature is-50 ℃, the vacuum degree is 5Pa during drying, and the freeze drying time is 24 hours, so that the molybdenum sulfide composite material with manganese loaded on graphene is obtained, and the product quality is about 0.5g.
(3) Preparation of modified separator: mixing 27mg of the molybdenum sulfide composite material obtained in the step (2) and 3mg of PVDF according to the mass ratio of 9:1, then adding the mixture into 300mL of NMP solution, and stirring to prepare slurry; the obtained slurry was uniformly coated on a PP separator (thickness: 25 μm) and dried at 60℃for 6 hours to obtain a modified separator (thickness: 35 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm calculated after weighing 2 。
(4) Preparation of sulfur/conductive carbon black (Super-P) composite material
Weighing sulfur and Super-P in a mass ratio of 7:3, mixing and grinding for 40 minutes, putting the ground mixed powder into a reaction kettle, melting for 20 hours at 155 ℃, and cooling to room temperature to obtain the sulfur/Super-P composite material.
The sulfur/Super-P composite material is used as a positive electrode, and the metal lithium sheet is used as a negative electrode. The electrolyte is lithium bis (trifluoromethylsulfonyl) imide as an electrolyte and is dissolved in a mixed solvent of 1, 3-Dioxypentacyclic (DOL) and 1, 2-Dimethoxyethane (DME) in a volume ratio of 1:1 (the final concentration of the electrolyte in the mixed solvent is 1.0M), and the solvent contains 1% by mass of lithium nitrate. The battery is assembled according to the sequence of the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, and the surface of the PP diaphragm, which is provided with the molybdenum sulfide composite material, faces the positive electrode. At a charge-discharge rate of 0.5C, the initial capacity of the battery reaches 1105mAh/g, the capacity of the battery after 100 circles is 892mAh/g, and the capacity of the battery after 160 circles is 865mAh/g.
Example 3
(1) Preparing graphene oxide dispersion liquid: 120mg of graphene oxide powder was weighed and dispersed in 30mL of deionized water, and sonicated for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g (NH) 4 ) 6 Mo 7 O 24 Added into the graphene oxide dispersion liquid prepared in the step (1) and stirred for 10 minutes. Weigh 0.42g MnSO 4 ·H 2 O was added to the stirred solution and sonicated for 5 minutes. Putting the obtained mixed solution into a hydrothermal reaction kettle, filling nitrogen at room temperature, carrying out hydrothermal reaction for 20 hours at 200 ℃, taking out the reaction solution, cooling to the room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, putting the centrifugal product into liquid nitrogen, rapidly freezing, finally drying in a freeze dryer, wherein the freezing temperature is-50 ℃, the vacuum degree is 5Pa during drying, and the freeze drying time is 24 hours, so that the molybdenum sulfide composite material with manganese loaded on graphene is obtained, and the product quality is about 0.6g.
(3) Preparation of modified separator: 27mg of the extract obtained in step (2)The obtained molybdenum sulfide composite material and 3mg PVDF are mixed according to the mass ratio of 9:1, and then added into 300mL of NMP solution, and stirred to prepare slurry; the obtained slurry was uniformly coated on a PP separator (thickness: 25 μm) and dried at 60℃for 6 hours to obtain a modified separator (thickness: 33 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm calculated after weighing 2 。
(4) Preparation of sulfur/conductive carbon black (Super-P) composite material
Weighing sulfur and Super-P in a mass ratio of 7:3, mixing and grinding for 40 minutes, putting the ground mixed powder into a reaction kettle, melting for 20 hours at 155 ℃, and cooling to room temperature to obtain the sulfur/Super-P composite material.
The sulfur/Super-P composite material is used as a positive electrode, and the metal lithium sheet is used as a negative electrode. The electrolyte is lithium bis (trifluoromethylsulfonyl) imide as an electrolyte and is dissolved in a mixed solvent of 1, 3-Dioxypentacyclic (DOL) and 1, 2-Dimethoxyethane (DME) in a volume ratio of 1:1 (the final concentration of the electrolyte in the mixed solvent is 1.0M), and the solvent contains 1% by mass of lithium nitrate. The battery is assembled according to the sequence of the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, and the surface of the PP diaphragm, which is provided with the molybdenum sulfide composite material, faces the positive electrode. At a charge-discharge rate of 0.5C, the initial capacity of the battery reaches 1089mAh/g, the capacity of the battery after 100 circles is 886mAh/g, and the capacity of the battery after 150 circles is 860mAh/g.
Comparative example 1
(1) Preparing graphene oxide dispersion liquid: 120mg of graphene oxide powder was weighed and dispersed in 30mL of deionized water, and sonicated for 1 hour.
(2) Preparing a graphene and molybdenum sulfide composite material: 0.91g of thiourea and 0.49g (NH) 4 ) 6 Mo 7 O 24 Added into the graphene oxide dispersion liquid prepared in the step (1) and stirred for 10 minutes. Putting the obtained mixed solution into a hydrothermal reaction kettle, filling nitrogen at room temperature, performing hydrothermal reaction for 20 hours at 180 ℃, taking out the reaction solution, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, putting the centrifugal product into liquid nitrogen, rapidly freezing, and finally putting the solid reaction product into freezingDrying in a dryer at-50deg.C under vacuum degree of 5Pa for 24 hr to obtain graphene and molybdenum sulfide composite material (G@MoS) 2 ) The product mass was about 0.4g.
(3) Preparation of modified separator: mixing 27mg of the molybdenum sulfide composite material obtained in the step (2) and 3mg of PVDF according to the mass ratio of 9:1, adding the mixed powder into 300mL of NMP solution, and stirring to prepare slurry; the obtained slurry was uniformly coated on a PP separator (thickness: 25 μm) and dried at 60℃for 6 hours to obtain a modified separator (thickness: 37 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm calculated after weighing 2 。
(4) Preparation of sulfur/conductive carbon black (Super-P) composite material
And (3) weighing sulfur and Super-P in a mass ratio of 7:3, mixing and grinding for 40 minutes, putting the ground mixed powder into a reaction kettle, melting for 20 hours at 155 ℃, and cooling to room temperature to obtain the sulfur/conductive carbon black (Super-P) composite material.
The sulfur/Super-P composite material is used as a positive electrode, and the metal lithium sheet is used as a negative electrode. The electrolyte is lithium bis (trifluoromethylsulfonyl) imide as an electrolyte and is dissolved in a mixed solvent of 1, 3-Dioxypentacyclic (DOL) and 1, 2-Dimethoxyethane (DME) in a volume ratio of 1:1 (the final concentration of the electrolyte in the mixed solvent is 1.0M), and the solvent contains 1% by mass of lithium nitrate. The battery is assembled according to the sequence of the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, and the surface of the PP diaphragm, which is provided with the molybdenum sulfide composite material, faces the positive electrode. At a charge-discharge rate of 0.5C, the initial capacity of the battery reaches 987mAh/g, the battery capacity after 100 circles is 765mAh/g, and the battery capacity after 150 circles is 640mAh/g.
Comparative example 2
The positive and negative electrode materials in the comparative example are both the materials described above, except that the separator is a pp separator of an unmodified molybdenum sulfide composite material, and the lithium-sulfur battery was prepared in the same manner as in example 1.
At a charge-discharge rate of 0.5C, the initial capacity of the battery reaches 749mAh/g, and after 100 circles, the capacity of the battery is 520mAh/g.
From the results of examples 1 to 3 and comparative examples 1 to 2 described above, it is apparent that the present application achieves effective improvement of cycle performance of lithium sulfur batteries and has excellent cycle performance of battery rate.
The above examples are selected by the inventor, but the embodiments of the present application are not limited by the above examples. Therefore, the application is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the application should be also included in the scope of the claims of the application.
Claims (7)
1. A preparation method of a molybdenum sulfide composite material with manganese loaded on graphene is characterized by comprising the following steps: dispersing graphene oxide in water, adding (NH 4 ) 6 Mo 7 O 24 Mixing with thiourea, adding a certain amount of manganese salt, and uniformly dispersing by ultrasonic; carrying out hydrothermal reaction on the obtained mixed solution in a reaction kettle at 160-220 ℃ under nitrogen atmosphere for 15-30 hours, taking out the reaction solution, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3-5 times, putting the centrifugal product into liquid nitrogen for rapid freezing, and finally, putting the centrifugal product into vacuum for freeze drying to obtain molybdenum sulfide composite material powder loaded with manganese element on graphene, wherein G@MoS is marked 2 @Mn; wherein the dispersion concentration of graphene oxide in water is 2-8 mg/mL, (NH) 4 ) 6 Mo 7 O 24 The molar ratio of thiourea to manganese salt is 1: 20-60: 10 to 30, (NH) 4 ) 6 Mo 7 O 24 The mass dosage ratio between the graphene oxide and the graphene oxide is 3-8: 1.
2. the method for preparing the molybdenum sulfide composite material with manganese loaded on graphene according to claim 1, which is characterized in that: the vacuum degree of freeze drying under vacuum is less than 10Pa, the freezing temperature is-60 to-35 ℃, and the drying time is 20-30 hours.
3. A molybdenum sulfide composite material for loading manganese element on graphene is characterized in that: is prepared by the method of claim 1 or 2.
4. The use of a molybdenum sulfide composite material loaded with manganese element on graphene in modification of lithium-sulfur battery diaphragm according to claim 3.
5. The application of the molybdenum sulfide composite material with manganese loaded on graphene in modification of lithium-sulfur battery diaphragm, according to claim 4, is characterized in that: dispersing a molybdenum sulfide composite material with manganese element loaded on graphene and polyvinylidene fluoride in an N-methyl pyrrolidone solution, coating the obtained mixed solution on the surface of a polypropylene diaphragm facing to the positive electrode of a lithium-sulfur battery, and drying for 4-8 hours at 50-80 ℃ to obtain the modified diaphragm material.
6. The application of the molybdenum sulfide composite material with manganese loaded on graphene in modification of lithium-sulfur battery diaphragm, according to claim 5, is characterized in that: the thickness of the polypropylene diaphragm before modification is 22-28 mu m, the thickness of the modified diaphragm material after modification is 30-45 mu m, and the load capacity of the molybdenum sulfide composite material per unit area on the modified diaphragm material is 2-8 mg/cm 2 。
7. The application of the molybdenum sulfide composite material with manganese loaded on graphene in modification of lithium-sulfur battery diaphragm, according to claim 5, is characterized in that: the mass dosage of the polyvinylidene fluoride is 10-20% of the sum of the mass of the molybdenum sulfide composite material and the polyvinylidene fluoride; in the N-methyl pyrrolidone solution, the concentration of the sum of the molybdenum sulfide composite material and polyvinylidene fluoride is 0.05-0.20 mg/mL.
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