CN114275776A - Molybdenum sulfide composite material loading manganese element on graphene, preparation method and application thereof - Google Patents
Molybdenum sulfide composite material loading manganese element on graphene, preparation method and application thereof Download PDFInfo
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Abstract
A molybdenum sulfide composite material with a manganese element uniformly loaded on graphene, a preparation method and application of the molybdenum sulfide composite material in modification of a lithium-sulfur battery diaphragm belong to the technical field of lithium-sulfur batteries. It is prepared by dispersing graphene oxide in water, adding (NH)4)6Mo7O24After being mixed with thiourea, manganese salt is added, and the mixture is dispersed uniformly by ultrasonic; carrying out hydrothermal reaction for 15-30 hours at 160-220 ℃ under nitrogen atmosphere, cooling to room temperature, carrying out centrifugal washing on the obtained solid reaction product for 3-5 times by using deionized water, putting the centrifugal product into liquid nitrogen for rapid freezing, and finally carrying out freeze drying for 20-30 hours under vacuum to obtain the molybdenum sulfide composite material,the composite material can be further applied to a lithium-sulfur battery as a modified diaphragm material, the modified diaphragm material can reduce the self impedance of the diaphragm, and can increase the lithium ion channels on the surface of the diaphragm, so that the battery reaction is accelerated, and the overall performance of the battery is improved.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a molybdenum sulfide composite material with manganese elements 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 being has stepped into the electrical age, the electric energy greatly changes our daily life, and the human being realizes the high-speed development of the industry through the transmission and application of electric power. But with the problems of population growth, brute force expansion of industrial processes, excessive use of fossil fuels, and the like, environmental problems have begun to gradually affect our lives and even threaten human survival and development. People gradually recognize that the development of renewable energy systems mainly using new energy sources such as wind energy, solar energy, tidal energy and the like is an important link of energy source layout of the 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 urgently need a reasonable and efficient energy storage device to meet the development requirements of the new energy sources. Lithium ion batteries are widely used as a prominent power storage solution in consumer electronics and power batteries. Of course, lithium ion batteries are not suitable for all energy storage applications, and some other types of batteries are gradually being developed.
With the increasing demand of people for energy storage, the energy density of lithium ion batteries cannot meet part of the demand, and the development of new battery systems with high energy density is not slow. Because the lithium-sulfur batteries (LSBs) have higher theoretical specific capacity (1675mA h g)-1) And energy density (2600Wh kg)-1) The researchers believe that it may be in some fields than the othersThe lithium ion battery has better application prospect. Meanwhile, elemental sulfur, one of the main raw materials of the lithium-sulfur battery, is low in price and abundant in 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 the research and development of lithium sulfur batteries. First, the main electrode material of lithium-sulfur batteries, elemental sulfur, and the discharge product, lithium sulfide, have poor conductivity properties, which results in the performance of the battery itself not being as good as theoretically expected. Second, the volume difference between the discharge product lithium sulfide and elemental sulfur is large, and there is about 80% volume shrinkage/expansion during the discharge/charge process, which may seriously damage the battery structure. Finally, lithium polysulfide generated in the battery charging and discharging process can be dissolved in the electrolyte, and the shuttle effect of the polysulfide can influence the utilization rate of active substances of the lithium-sulfur battery, so that the coulombic efficiency is reduced on one hand, and the cycle life is shortened on the other hand.
In order to overcome these problems, scientists have prepared a porous or rough carbon-based structure, and supported pure sulfur on a carbon material by a hot-melt method, and increased the conductivity of the positive electrode by the carbon material, while buffering the volume change during charge and discharge. In addition, another solution is to increase the physical adsorption and chemical catalytic ability of the material to polysulfides by designing different polar materials.
Disclosure of Invention
The invention aims to provide molybdenum sulfide (MoS) loaded with manganese element on graphene (G)2) Composite material, preparation method and application thereof. The composite material is used for modifying a lithium-sulfur battery system, and the material is coated on a diaphragm modification layer to inhibit the shuttle penetrating effect and promote the conversion effect of polysulfide. The material has the advantages of simple preparation process, easy production and less environmental pollution.
The invention is realized by the following technical scheme:
a preparation method of a molybdenum sulfide composite material loading manganese elements on graphene comprises the following steps:
dispersing graphene oxide in water, adding (NH)4)6Mo7O24Uniformly mixing the mixture 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 ℃ for 15-30 hours under the atmosphere of nitrogen, taking out the reaction liquid, cooling to room temperature, carrying out centrifugal washing on the obtained solid reaction product with deionized water for 3-5 times, putting the centrifugal product into liquid nitrogen for rapid freezing, and finally freezing under vacuum (the vacuum degree is less than 10Pa) at (-60-35 ℃) for 20-30 hours to obtain molybdenum sulfide composite material powder with manganese element loaded on graphene, wherein the powder is marked as G @ MoS2@Mn。
Preferably, the dispersion concentration of the graphene oxide in water is 2-8 mg/mL;
preferably, (NH)4)6Mo7O24The molar ratio of the thiourea to the manganese salt is 1: (20-60): (10-30);
preferably, (NH)4)6Mo7O24And the mass usage ratio of the graphene oxide to the graphene oxide (3-8): 1;
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 loading manganese elements 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 at 50-80 ℃ for 4-8 hours 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 on the modified diaphragm material in unit area is 2-8 mg/cm2。
Preferably, the dispersion concentration of the total mass of the molybdenum sulfide composite material and PVDF in the NMP solution is 0.05-0.15 g/mL.
Preferably, the mass usage amount of the PVDF is 10-20% of the mass sum of the molybdenum sulfide composite material and the PVDF; in the N-methylpyrrolidone (NMP) solution, the concentration of the sum of the molybdenum sulfide composite material and the PVDF is 0.05-0.20 mg/mL.
The invention provides a molybdenum sulfide composite material loading manganese elements on graphene, which can be further applied to a lithium-sulfur battery as a modified diaphragm material, and the modified diaphragm material has the following advantages:
(1) compared with MoS2And manganese oxide, which is more conductive. The self impedance of the diaphragm can be reduced, and meanwhile, the lithium ion channels on the surface of the diaphragm can be increased, so that the reaction of the battery is accelerated, and the overall performance of the battery is improved.
(2) The material synthesized by the method can increase the adsorption effect of the material on polysulfide by combining chemical adsorption and physical adsorption, and inhibit the shuttling effect of polysulfide; meanwhile, compared with other graphene and MoS2In the composite material, the existence of manganese element can accelerate the oxidation-reduction process in the charge-discharge reaction of the lithium-sulfur battery and reduce the existence time of polysulfide in the battery, thereby reducing the loss of energy density caused by the shuttling effect of the polysulfide.
(3) The material is freeze-dried in the synthesis process, and the shape of the material is mainly flaky. The material introduces graphene, so that more active sites are added, and the stability of the material is improved. The material has a large amount of porous structures, so that the material can bear the problem of volume expansion and contraction generated in the charging and discharging processes of the lithium-sulfur battery, and the cycle life of the battery is prolonged.
Drawings
FIG. 1 shows a molybdenum sulfide composite G @ MoS prepared in example 1 and loaded with manganese on graphene2SEM picture of @ Mn.
FIG. 2 shows a manganese element-loaded molybdenum sulfide composite G @ MoS on graphene prepared in example 1 of the present invention2TEM image of @ Mn.
FIG. 3 shows the composite G @ MoS prepared in example 1 and comparative example 1 of the present invention2@ Mn and G @ MoS2XRD pattern of (a).
FIG. 4 shows the membrane materials G @ MoS prepared in example 1 and comparative example 2 of the present invention2Rate cycle performance of @ Mn and PP assembled lithium-sulfur batteryFigure (a). From the results of example 1 and comparative example 2, it is clear that the present invention has excellent battery rate cycle performance.
FIG. 5 shows the G @ MoS separator materials prepared in example 1 and comparative example 2 of the present invention2@ Mn and PP assemble the cycle stability test chart of the lithium-sulfur battery. From the results of example 1 and comparative example 2, it is understood that the present invention 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, are included to further illustrate the objects, aspects and advantages of the invention. The following examples of the present invention are given to further illustrate the present invention and are not intended to limit the embodiments of the present invention.
Example 1
(1) Preparing a graphene oxide dispersion liquid: 120mg of graphene oxide powder is weighed and dispersed in 30mL of deionized water, and ultrasonic treatment is carried out for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g of (NH) were weighed out4)6Mo7O24Adding the graphene oxide dispersion liquid prepared in the step (1) and stirring for 10 minutes. Weigh 0.25g MnSO4·H2O is added to the stirred solution and sonicated for 5 minutes. And placing the obtained mixed solution in a hydrothermal reaction kettle, introducing nitrogen at room temperature, performing hydrothermal reaction at 180 ℃ for 20 hours, taking out the reaction liquid, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, placing the centrifuged product in liquid nitrogen for rapid freezing, and finally placing the product in a freeze dryer for drying, wherein the freezing temperature is-50 ℃, the vacuum degree during drying is 5Pa, and the freeze drying time is 24 hours, so that the molybdenum sulfide composite material loaded with the manganese element on the graphene is obtained, and the mass of the product is about 0.5 g.
(3) Preparing a modified diaphragm: 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 mixture into 300mL of NMP solution, and stirring to prepare slurry; the resulting slurry was uniformly coated on one surface of a PP separator (thickness of 25 μm), and dried at 60 ℃And 6 hours, thus obtaining the modified diaphragm material (the thickness is 35 mu m). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm through calculation after weighing2。
(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 the positive electrode of the lithium-sulfur battery, and the metal lithium sheet is used as the negative electrode. The electrolyte is prepared by dissolving lithium bis (trifluoromethyl) sulfonyl imide serving as an electrolyte into a mixed solvent of 1, 3-Dioxolane (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 sequentially assembled according to a positive electrode shell, a positive electrode, electrolyte, a diaphragm, the electrolyte, a negative electrode and a negative electrode shell, wherein one surface of the PP diaphragm, on which the molybdenum sulfide composite material is prepared, faces the positive electrode. Under the charge and 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 857 mAh/g.
Example 2
(1) Preparing a graphene oxide dispersion liquid: 120mg of graphene oxide powder is weighed and dispersed in 30mL of deionized water, and ultrasonic treatment is carried out for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g of (NH) were weighed out4)6Mo7O24Adding the graphene oxide dispersion liquid prepared in the step (1) and stirring for 10 minutes. Weigh 0.25g MnSO4·H2O is added to the stirred solution and sonicated for 5 minutes. Placing the obtained mixed solution in a hydrothermal reaction kettle, introducing nitrogen at room temperature, performing hydrothermal reaction at 200 ℃ for 20 hours, taking out the reaction solution, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, rapidly freezing the centrifuged product in liquid nitrogen, and finally drying in a freeze dryer at the freezing temperature of-50 ℃ and the vacuum degree of 5Pa during dryingAnd drying for 24 hours to obtain the molybdenum sulfide composite material loaded with the manganese element on the graphene, wherein the mass of the product is about 0.5 g.
(3) Preparing a modified diaphragm: 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 mixture into 300mL of NMP solution, and stirring to prepare slurry; the obtained slurry was uniformly coated on a PP separator (thickness of 25 μm), and dried at 60 ℃ for 6 hours to obtain a modified separator (thickness of 35 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm through calculation after weighing2。
(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 a metal lithium sheet is used as a negative electrode. The electrolyte is prepared by dissolving lithium bis (trifluoromethyl) sulfonyl imide serving as an electrolyte into a mixed solvent of 1, 3-Dioxolane (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 sequentially assembled according to the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, wherein the side, on which the molybdenum sulfide composite material is prepared, of the PP diaphragm faces the positive electrode. Under the charge and 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 865 mAh/g.
Example 3
(1) Preparing a graphene oxide dispersion liquid: 120mg of graphene oxide powder is weighed and dispersed in 30mL of deionized water, and ultrasonic treatment is carried out for 1 hour.
(2) Preparing a molybdenum sulfide composite material with manganese element loaded on graphene: 0.91g of thiourea and 0.49g of (NH) were weighed out4)6Mo7O24Adding the graphene oxide dispersion liquid prepared in the step (1) and stirring for 10 minutes. Weigh 0.42g MnSO4·H2Adding O to the stirredIn solution, sonicate for 5 minutes. And placing the obtained mixed solution in a hydrothermal reaction kettle, introducing nitrogen at room temperature, performing hydrothermal reaction at 200 ℃ for 20 hours, taking out the reaction solution, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, placing the centrifuged product in liquid nitrogen for rapid freezing, and finally placing the product in a freeze dryer for drying, wherein the freezing temperature is-50 ℃, the vacuum degree during drying is 5Pa, and the freeze drying time is 24 hours, so that the molybdenum sulfide composite material loaded with the manganese element on the graphene is obtained, and the mass of the product is about 0.6 g.
(3) Preparing a modified diaphragm: 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 mixture into 300mL of NMP solution, and stirring to prepare slurry; the resulting slurry was uniformly coated on a PP separator (thickness of 25 μm), and dried at 60 ℃ for 6 hours to obtain a modified separator (thickness of 33 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm through calculation after weighing2。
(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 a metal lithium sheet is used as a negative electrode. The electrolyte is prepared by dissolving lithium bis (trifluoromethyl) sulfonyl imide serving as an electrolyte into a mixed solvent of 1, 3-Dioxolane (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 sequentially assembled according to the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, wherein the side, on which the molybdenum sulfide composite material is prepared, of the PP diaphragm faces the positive electrode. Under the charge and 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 860 mAh/g.
Comparative example 1
(1) Preparing a graphene oxide dispersion liquid: 120mg of graphene oxide powder is weighed and dispersed in 30mL of deionized water, and ultrasonic treatment is carried out for 1 hour.
(2) Preparing a graphene and molybdenum sulfide composite material: 0.91g of thiourea and 0.49g of (NH) were weighed out4)6Mo7O24Adding the graphene oxide dispersion liquid prepared in the step (1) and stirring for 10 minutes. Placing the obtained mixed solution in a hydrothermal reaction kettle, filling nitrogen at room temperature, performing hydrothermal reaction at 180 ℃ for 20 hours, taking out the reaction liquid, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3 times, placing the centrifuged product in liquid nitrogen for rapid freezing, and finally placing the product in a freeze dryer for drying, wherein the freezing temperature is-50 ℃, the vacuum degree during drying is 5Pa, and the freeze drying time is 24 hours, so that the graphene and molybdenum sulfide composite material (G @ MoS) is obtained2) The mass of the product was about 0.4 g.
(3) Preparing a modified diaphragm: 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 powder into 300mL of NMP solution, and stirring to prepare slurry; the resulting slurry was uniformly coated on a PP separator (thickness of 25 μm), and dried at 60 ℃ for 6 hours to obtain a modified separator (thickness of 37 μm). The load capacity of the molybdenum sulfide composite material in the step (2) on the diaphragm is 3mg/cm through calculation after weighing2。
(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/conductive carbon black (Super-P) composite material.
The sulfur/Super-P composite material is used as a positive electrode, and a metal lithium sheet is used as a negative electrode. The electrolyte is prepared by dissolving lithium bis (trifluoromethyl) sulfonyl imide serving as an electrolyte into a mixed solvent of 1, 3-Dioxolane (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 sequentially assembled according to the positive electrode shell, the positive electrode, the electrolyte, the diaphragm, the electrolyte, the negative electrode and the negative electrode shell, wherein the side, on which the molybdenum sulfide composite material is prepared, of the PP diaphragm faces the positive electrode. Under the charge-discharge rate of 0.5C, the initial capacity of the battery reaches 987mAh/g, the capacity of the battery after 100 circles is 765mAh/g, and the capacity of the battery after 150 circles is 640 mAh/g.
Comparative example 2
In the comparative example, the positive and negative electrode materials were all the same as those described above, except that the separator was a pp separator made of an unmodified molybdenum sulfide composite material, and the lithium-sulfur battery was prepared in the same manner as in example 1.
Under the charge and discharge rate of 0.5C, the initial capacity of the battery reaches 749mAh/g, and the capacity of the battery after 100 circles is 520 mAh/g.
According to the results of the examples 1 to 3 and the comparative examples 1 to 2, the cycle performance of the lithium-sulfur battery is effectively improved, and the lithium-sulfur battery has excellent rate cycle performance.
The above embodiments are chosen by the inventors, but the embodiments of the invention are not limited to the above embodiments. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application.
Claims (9)
1. A preparation method of a molybdenum sulfide composite material loading manganese elements on graphene is characterized by comprising the following steps: dispersing graphene oxide in water, adding (NH)4)6Mo7O24Uniformly mixing the mixture 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 a nitrogen atmosphere for 15-30 hours, taking out the reaction liquid, cooling to room temperature, centrifugally washing the obtained solid reaction product with deionized water for 3-5 times, rapidly freezing the centrifuged product in liquid nitrogen, and finally freeze-drying in vacuum to obtain molybdenum sulfide composite material powder with manganese element loaded on graphene, wherein the powder is marked as G @ MoS2@Mn。
2. The preparation method of the molybdenum sulfide composite material loaded with manganese element on graphene according to claim 1, wherein the preparation method is characterized in that: the dispersion concentration of the graphene oxide in water is 2-8 mg/mL (NH)4)6Mo7O24The molar ratio of the thiourea to the manganese salt is 1: (20-60): (10 to 30), (NH)4)6Mo7O24The mass and dosage ratio of the graphene oxide to the graphene oxide is (3-8): 1.
3. the preparation method of the molybdenum sulfide composite material loading manganese element on the graphene according to claim 1, characterized by comprising the following steps: the vacuum degree of the freeze drying under vacuum is less than 10Pa, the freezing temperature is-60 to-35 ℃, and the drying time is 20 to 30 hours.
4. A molybdenum sulfide composite material loading manganese element on graphene is characterized in that: is prepared by the method of any one of claims 1 to 3.
5. The application of the molybdenum sulfide composite material loaded with manganese on graphene according to claim 4 in modification of a lithium-sulfur battery diaphragm.
6. The application of the molybdenum sulfide composite material with the manganese element loaded on the graphene in the modification of the lithium-sulfur battery diaphragm as claimed in claim 5 is characterized in that: the preparation method comprises the steps of dispersing a molybdenum sulfide composite material loading manganese elements on graphene and polyvinylidene fluoride in an N-methyl pyrrolidone solution, coating the obtained mixed solution on the surface of the polypropylene diaphragm facing the positive electrode side of the lithium-sulfur battery, and drying at 50-80 ℃ for 4-8 hours to obtain the modified diaphragm material.
7. The application of the molybdenum sulfide composite material with the manganese element loaded on the graphene in the modification of the lithium-sulfur battery diaphragm as claimed in claim 6, 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 loading capacity of the molybdenum sulfide composite material on the modified diaphragm material in unit area is 2-8 mg/cm2。
8. The application of the molybdenum sulfide composite material with the manganese element loaded on the graphene in the modification of the lithium-sulfur battery diaphragm as claimed in claim 5 is characterized in that: the total mass of the molybdenum sulfide composite material and the polyvinylidene fluoride is dispersed in the N-methyl pyrrolidone solution at a concentration of 0.05-0.15 g/mL.
9. The application of the molybdenum sulfide composite material with the manganese element loaded on the graphene in the modification of the lithium-sulfur battery diaphragm as claimed in claim 5 is characterized in that: the mass usage of the polyvinylidene fluoride is 10-20% of the mass sum 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 the polyvinylidene fluoride is 0.05-0.20 mg/mL.
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