CN110890502B - Preparation method of POSS (polyhedral oligomeric silsesquioxane) grafted carbon nanotube composite lithium-sulfur battery diaphragm - Google Patents
Preparation method of POSS (polyhedral oligomeric silsesquioxane) grafted carbon nanotube composite lithium-sulfur battery diaphragm Download PDFInfo
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- H—ELECTRICITY
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- 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
- 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
- H01M50/411—Organic 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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- 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 POSS grafted carbon nanotube lithium-sulfur battery diaphragm, which comprises the steps of taking a carboxylated carbon nanotube (CNTs-COOH) as a raw material, grafting polyhedral oligomeric silsesquioxane (POSS) onto the surface of the CNTs to obtain a CNTs-POSS material; then preparing the prepared CNTs-POSS, polyether sulfone (PES), a pore-forming agent and an organic solvent into a solution according to a certain mass ratio, heating at a constant temperature, and stirring to form an electrostatic spinning precursor solution in a PES matrix; and (3) uniformly spinning the obtained electrostatic spinning precursor solution on a PE diaphragm to obtain the POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm. The POSS solid electrolyte modified high-strength composite diaphragm with the functions of cutting sulfur and guiding lithium is synthesized by the method, and is used for solving the problems of capacity attenuation caused by shuttle of polysulfide ions in a lithium sulfur battery and safety risks caused by penetration of branch crystals under abnormal working conditions.
Description
Technical Field
The invention relates to a preparation method of a composite diaphragm for a lithium-sulfur battery, in particular to a diaphragm for inhibiting the shuttle effect of the lithium-sulfur battery and a preparation and application method thereof.
Technical Field
The lithium-sulfur battery has the advantages of rich resources, low cost, high biocompatibility of the positive electrode material sulfur, theoretical energy value as high as 2600Wh/kg and the like. As an important component of the lithium-sulfur battery, the diaphragm not only controls the dynamic process of ion transmission in the battery, but also fundamentally determines the working mechanism of the battery, and influences the specific energy, rate capability, cycle life and safety of the battery.
Since the Carbon Nanotubes (CNTs) are discovered in 1991, the unique surface effect, quantum size effect and hollow tubular structure endow the carbon nanotubes with excellent heat conduction, electric conduction, mechanical properties and the like and extremely high length-diameter ratio, so that the Carbon Nanotubes (CNTs) become the object of research on a plurality of polymer-based composite materials. Meanwhile, surface modification and functionalization treatment of the carbon nano tube are also widely researched, and the treated carbon nano tube has good solubility and is beneficial to uniform dispersion and forming processing. POSS (polyhedral oligomeric silsesquioxane) as a novel organic-inorganic nano hybrid material has excellent processability and toughness of an organic material, and keeps heat resistance, oxidation resistance and excellent mechanical properties of an inorganic material, so that POSS becomes one of important means for preparing a performance-improved composite material at present. PES has excellent thermodynamic stability, film forming property and wettability, and has become an important development object of commercial lithium battery diaphragm materials. The prepared CNTs-POSS material is added into PES membrane casting solution, so that the crystallinity of the PES membrane can be reduced, and the porosity of the PES membrane is improved. The higher porosity of the diaphragm can improve the liquid absorption rate of the diaphragm, and further improve the comprehensive properties of the diaphragm, such as ionic conductivity, ion transference number and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm, which can effectively block shuttling of polysulfide in a lithium-sulfur battery so as to improve the capacity performance and the cycle performance of the lithium-sulfur battery, and the diaphragm is prepared by the following specific steps:
1. a preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following specific steps:
(1) Activation of carboxylated carbon nanotubes (CNTs-COOH): weighing a certain amount of carboxylated carbon nanotubes (CNTs-COOH) and placing the CNTs-COOH into a beaker, then adding a certain amount of organic solvent, placing the mixture into an ultrasonic machine for ultrasonic dispersion, pouring the dispersed liquid into a four-mouth bottle, carrying out oil bath at the constant temperature of 60 ℃ in an oil bath pan, then adding a proper amount of activating agent for activation, and stirring and activating the mixture at the temperature of 60 ℃ for 3-5 hours to obtain activated carboxylated carbon nanotubes (CNTs-COOH);
(2) Grafting POSS: weighing a certain amount of octavinyl lantern type semi-siloxane POSS with amino in a three-neck bottle, adding an organic solvent, and introducing N into the three-neck bottle 2 Discharging air in the bottle, and ultrasonically dispersing for 2-3h, wherein the ultrasonic dispersion is set in the same step (1), so that a well dispersed POSS solution is obtained; adding the dispersed POSS solution into the four-mouth bottle in the step (1), stirring at 60 ℃ and continuously reacting for 12-18h, wherein N is continuously introduced in the reaction process 2 (ii) a After the reaction is finished, carrying out suction filtration, and after the suction filtration, placing a solid sample obtained in the vacuum drying process for 72-96h at the temperature of 60-80 ℃; after drying, grinding the dried solid sample by using a mortar to obtain CNTs-POSS black powder;
(3) Preparing an electrostatic spinning precursor solution: preparing a solution from the prepared CNTs-POSS black powder, polyether sulfone (PES), a pore-forming agent and an organic solvent according to a certain mass ratio, placing the obtained solution in an oil bath pan, heating at a constant temperature of 70 ℃, and stirring until the CNTs-POSS is uniformly dispersed in a PES matrix to form a uniform electrostatic spinning precursor solution;
(4) Preparing a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm: and (3) placing the electrostatic spinning precursor solution obtained in the step (3) in an electrostatic spinning device, opening an electrostatic spinning switch, spinning on a Polyethylene (PE) diaphragm to form a uniform spinning layer of the POSS grafted carbon nano tube on the Polyethylene (PE) diaphragm, then slowly drying for 2 hours at room temperature, after most of water is volatilized, placing in a vacuum drying oven at 40 ℃ for drying for 3 hours, then heating to 60 ℃ for drying for 5 hours, and finally drying at 70 ℃ for 12 hours to obtain the POSS grafted carbon nano tube composite lithium-sulfur battery diaphragm.
2. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the organic solvent in the steps (1) and (2) is one of tetrahydrofuran, toluene and chloroform.
3. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the ultrasonic machine in the step (1) is an ultrasonic cell crusher, wherein the ultrasonic dispersion time is 12-24h, the working time is set to be 60s, the intermittent time is set to be 2s, the ultrasonic frequency is 99 times, and the power is 700W.
4. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: in the four-mouth bottle reaction, a carboxylated carbon nano tube (CNTs-COOH), an activating agent and octavinyl lantern type semi-siloxane POSS with amino are adopted, and the mass ratio of organic solvents is as follows: (4-16): (0.15-2.5): (3-15): 100.
5. a preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the molecular structural formula of the octavinyl lantern type semi-siloxane POSS with amino in the step (2) is as follows:
6. a preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the activating agent in the step (1) is one of N, N' -Carbonyl Diimidazole (CDI), ethylene diamine phosphate, propylene diamine phosphate, xylene, sodium fluosilicate, ammonium sulfate, ammonium chloride, ferrous sulfate and ammonium hydroxide.
7. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the pore-forming additive in the step (3) is one of polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, copovidone, polyvinyl alcohol, polyethylene glycol and sodium nitrate; the organic solvent in the step (3) is one of dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and triethyl phosphate.
8. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the mass ratio of PES, pore-forming additive and organic solvent in the step (3) is 1: (0.1-0.15): (2.5-4.5).
9. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following steps: the spinning layer of the POSS grafted carbon nano tube of the composite lithium-sulfur battery diaphragm of the POSS grafted carbon nano tube in the step (4) is 200-600nm thick, and the PE diaphragm is 9-25 mu m thick.
The invention has the advantages that:
(1) The preparation process is simple, the raw materials are wide in source, and the required experimental instruments are simple, so that the method can be used for large-scale production.
(2) POSS is successfully grafted on the carbon nano tube, so that the advantages of the carbon nano tube and the POSS are complemented. POSS with excellent performance and designable structure is grafted to CNTs, so that the dispersibility and the solubility of the carbon nano tube in the PES matrix can be improved, and the capability of the POSS for adsorbing polysulfide in the PES matrix by virtue of the conductivity of the carbon nano tube can be improved.
(3) The preparation method of the composite lithium-sulfur battery diaphragm of the POSS grafted carbon nanotube has excellent porosity, liquid absorption rate, thermal stability and very high ionic conductivity.
(4) In the composite lithium-sulfur battery diaphragm of the POSS grafted carbon nano tube prepared by the invention, the functions of each layer are different but are mutually supplemented, the porous Polyethylene (PE) diaphragm matrix has high mechanical strength, the porous Polyethylene (PE) diaphragm matrix has high thermal stability with a polyether sulfone (PES) matrix, and the CNTs-POSS doped into the PES matrix has a high-efficiency sulfur-cutting and lithium-conducting effect, so that the chemical performance of the lithium-sulfur battery is further improved.
Detailed Description
The present invention provides a preparation method of a composite lithium-sulfur battery diaphragm of POSS grafted carbon nanotubes, and the following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Weighing 2g of carboxylated carbon nanotubes (CNTs-COOH) in a 500mL beaker, adding 200mL of Tetrahydrofuran (THF), placing in an ultrasonic cell crusher, and performing ultrasonic dispersion for 12h, wherein the working time is set to be 60s, the pause time is set to be 2s, the ultrasonic frequency is set to be 99 times, and the power is set to be 700W; pouring the dispersed liquid into a four-mouth bottle, performing oil bath at the constant temperature of 60 ℃ in an oil bath pan, adding 0.2g of N, N-Carbonyl Diimidazole (CDI) for activation, and stirring and activating at 60 ℃ for 3 hours;
(2) Weighing 2.5g of POSS in a beaker, adding 60mL of tetrahydrofuran, and ultrasonically dispersing for 1h (the same step (1) is set); introducing N into the four-mouth bottle 2 Discharging the air in the bottle, adding the dispersed liquid into a four-mouth bottle, stirring at 60 ℃ and continuing to react for 12h (continuously introducing N in the reaction process) 2 ) (ii) a After the reaction is finished, carrying out suction filtration to obtain a CNTs-POSS solid sample, and placing the obtained CNTs-POSS solid sample at 60 ℃ for vacuum drying for 72h; after drying, grinding the solid sample by using a mortar to obtain CNTs-POSS black powder;
(3) Preparing 0.5g of CNTs-POSS, 8g of Polyethersulfone (PES), 1.5g of PVP and 40g of NMP into a solution in a four-opening bottle, placing the obtained solution in an oil bath pan, heating at a constant temperature of 70 ℃, and stirring until the CNTs-POSS is uniformly dispersed in a PES matrix to form a uniform electrostatic spinning precursor solution;
(4) Preparing a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm: and (4) placing the electrospinning precursor solution obtained in the step (3) in an electrostatic spinning device, turning on an electrostatic spinning switch, spinning on a Polyethylene (PE) diaphragm, forming a uniform POSS grafted carbon nanotube spinning layer on the Polyethylene (PE) diaphragm, then slowly drying for 2 hours at room temperature, after most of water is volatilized, placing in a vacuum drying oven for drying at 40 ℃ for 3 hours, then heating to 60 ℃ for drying for 5 hours, and finally drying at 70 ℃ for 12 hours to obtain the POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm.
Example 2
(1) Weighing 2.5g of carboxylated carbon nanotubes (CNTs-COOH) in a 500mL beaker, adding 200mL of toluene, placing the beaker in an ultrasonic cell crusher for ultrasonic dispersion for 12 hours, and setting the working time to be 60s, the pause time to be 2s, the ultrasonic frequency to be 99 times and the power to be 700W; pouring the dispersed liquid into a four-mouth bottle, performing oil bath at the constant temperature of 60 ℃ in an oil bath pot, adding 0.3g of ethylenediamine phosphate for activation, and stirring and activating at 60 ℃ for 3 hours;
(2) Weighing 3g of POSS in a beaker, adding 60mL of toluene, and ultrasonically dispersing for 1h (the same step (1)); introducing N into the four-mouth bottle 2 Discharging the air in the bottle, adding the dispersed liquid into a four-mouth bottle, stirring at 60 ℃ and continuing to react for 12h (continuously introducing N in the reaction process) 2 ) (ii) a After the reaction is finished, carrying out suction filtration to obtain a CNTs-POSS solid sample, and placing the obtained CNTs-POSS solid sample at 60 ℃ for vacuum drying for 72h; after drying, grinding the solid sample by using a mortar to obtain CNTs-POSS black powder;
(3) Preparing a solution from 0.6g of CNTs-POSS, 8g of Polyethersulfone (PES), 1.5g of PVP and 39.5g of NMP in a four-mouth bottle, placing the obtained solution in an oil bath pan, heating at a constant temperature of 70 ℃, and stirring until the CNTs-POSS is uniformly dispersed in a PES matrix to form a uniform electrostatic spinning precursor solution;
(4) Preparing a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm: and (4) placing the electrospinning precursor solution obtained in the step (3) in an electrostatic spinning device, turning on an electrostatic spinning switch, spinning on a Polyethylene (PE) diaphragm, forming a uniform POSS grafted carbon nanotube spinning layer on the Polyethylene (PE) diaphragm, then slowly drying for 2 hours at room temperature, after most of water is volatilized, placing in a vacuum drying oven for drying at 40 ℃ for 3 hours, then heating to 60 ℃ for drying for 5 hours, and finally drying at 70 ℃ for 12 hours to obtain the POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm.
Example 3
(1) Weighing 3g of carboxylated carbon nanotubes (CNTs-COOH) in a 500mL beaker, adding 200mL of chloroform, placing the beaker in an ultrasonic cell crusher for ultrasonic dispersion for 12h, setting the working time to be 60s, the intermittent time to be 2s, the ultrasonic frequency to be 99 times and the power to be 700W; pouring the dispersed liquid into a four-mouth bottle, performing oil bath at the constant temperature of 60 ℃ in an oil bath pan, adding 0.5g of N, N-Carbonyldiimidazole (CDI) for activation, and stirring and activating at 60 ℃ for 3 hours;
(2) Weighing a proper amount of POSS (polyhedral oligomeric silsesquioxane) in a beaker, adding 60mL of chloroform, and ultrasonically dispersing for 1h (the same step (1)); introducing N into the four-mouth bottle 2 Discharging the air in the bottle, adding the dispersed liquid into a four-mouth bottle, stirring at 60 ℃ and continuing to react for 12 hours (continuously introducing N in the reaction process) 2 ) (ii) a After the reaction is finished, carrying out suction filtration to obtain a CNTs-POSS solid sample, and placing the obtained CNTs-POSS solid sample at 60 ℃ for vacuum drying for 72h; after drying, grinding the solid sample by using a mortar to obtain CNTs-POSS black powder;
(3) 0.5g of CNTs-POSS, 8g of Polyethersulfone (PES), 1.5g of PVP and 40g of NMP are prepared into a solution in a four-mouth bottle, and the obtained solution is placed in an oil bath pan to be heated at a constant temperature of 70 ℃ and stirred until the CNTs-POSS is uniformly dispersed in a PES matrix to form a uniform electrostatic spinning precursor solution;
(4) Preparing a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm: and (3) placing the electrospinning precursor solution obtained in the step (3) in an electrostatic spinning device, opening an electrostatic spinning switch, spinning on a Polyethylene (PE) diaphragm, forming a uniform spinning layer of the POSS grafted carbon nano tube on the Polyethylene (PE) diaphragm, then slowly drying for 2 hours at room temperature, after most of water is volatilized, placing in a vacuum drying oven at 40 ℃ for drying for 3 hours, then heating to 60 ℃ for drying for 5 hours, and finally drying at 70 ℃ for 12 hours to obtain the POSS grafted carbon nano tube composite lithium-sulfur battery diaphragm.
And (3) carrying out physical and electrochemical performance tests on the obtained diaphragm: the method mainly comprises the tests of porosity, puncture resistance, rupture temperature, ionic conductivity, ion migration number and the like, and all indexes are shown in the table I. The resulting separator sheet was then loaded into a lithium sulfur battery for battery performance testing. The cells were tested for cycling performance at room temperature at a current density of 0.5C (1c = 1675ma/g), with cycling performance as shown in table two. And (3) testing the rate performance of the battery by cycling for 100 circles under different current densities of 0.5C, 1C, 2C and the like, wherein the rate performance of the lithium-sulfur battery is shown in the third table.
Table one: physical and chemical property test indexes of the separators of the respective examples
A second table: cycling Performance of the lithium-sulfur batteries of the examples
A third table: rate performance of lithium sulfur battery of each example
| Serial number | 0.5C | 1C | 2C |
| Example 1 | 678mAh/g | 550mAh/g | 510mAh/g |
| Example 2 | 680mAh/g | 557mAh/g | 523mAh/g |
| Example 3 | 743mAh/g | 565mAh/g | 530mAh/g |
Claims (9)
1. A preparation method of a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm is characterized by comprising the following specific steps:
(1) Activation of carboxylated carbon nanotubes (CNTs-COOH): weighing a certain amount of carboxylated carbon nanotubes (CNTs-COOH) and placing the CNTs-COOH into a beaker, then adding a certain amount of organic solvent, placing the mixture into an ultrasonic machine for ultrasonic dispersion, pouring the dispersed liquid into a four-mouth bottle, carrying out oil bath at the constant temperature of 60 ℃ in an oil bath pan, then adding a proper amount of activating agent for activation, and stirring and activating the mixture at the temperature of 60 ℃ for 3-5 hours to obtain activated carboxylated carbon nanotubes (CNTs-COOH);
(2) Grafting POSS: weighing a certain amount of octavinyl lantern type semi-siloxane POSS with amino in a three-neck bottle, adding an organic solvent, and introducing N into the three-neck bottle 2 Discharging air in the bottle, and ultrasonically dispersing for 2-3h, wherein the ultrasonic dispersion is set in the same step (1), so that a well dispersed POSS solution is obtained; adding the dispersed POSS solution into the four-mouth bottle in the step (1), stirring at 60 ℃ to continue reacting for 12-18h, and continuously introducing N in the reaction process 2 (ii) a After the reaction is finished, carrying out suction filtration, and placing a solid sample obtained after suction filtration at 60-80 DEG CVacuum drying for 72-96h; after drying, grinding the dried solid sample by using a mortar to obtain CNTs-POSS black powder;
(3) Preparing an electrostatic spinning precursor solution: preparing a solution from the prepared CNTs-POSS black powder, polyether sulfone (PES), a pore-forming agent and an organic solvent according to a certain mass ratio, placing the obtained solution in an oil bath pan, heating at a constant temperature of 70 ℃, and stirring until the CNTs-POSS is uniformly dispersed in a polyether sulfone matrix to form a uniform electrostatic spinning precursor solution;
(4) Preparing a POSS grafted carbon nanotube composite lithium-sulfur battery diaphragm: and (3) placing the electrostatic spinning precursor solution obtained in the step (3) in an electrostatic spinning device, opening an electrostatic spinning switch, spinning on a Polyethylene (PE) diaphragm to form a uniform spinning layer of the POSS grafted carbon nano tube on the Polyethylene (PE) diaphragm, then slowly drying for 2 hours at room temperature, after most of water is volatilized, placing in a vacuum drying oven at 40 ℃ for drying for 3 hours, then heating to 60 ℃ for drying for 5 hours, and finally drying at 70 ℃ for 12 hours to obtain the POSS grafted carbon nano tube composite lithium-sulfur battery diaphragm.
2. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the organic solvent in the steps (1) and (2) is one of tetrahydrofuran, toluene and chloroform.
3. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the ultrasonic machine in the step (1) is an ultrasonic cell crusher, wherein the ultrasonic dispersion time is 12-24h, the working time is set to be 60s, the intermittent time is set to be 2s, the ultrasonic frequency is 99 times, and the power is 700W.
4. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: in the four-mouth bottle reaction, a carboxylated carbon nanotube (CNTs-COOH), an activating agent and octavinyl lantern type semi-siloxane POSS with amino are adopted, and the mass ratio of organic solvents is as follows: (4-16): (0.15-2.5): (3-15): 100.
5. the method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator as claimed in claim 1, wherein the POSS grafted carbon nanotube composite lithium-sulfur battery separator comprises the following steps: the molecular structural formula of the octavinyl lantern type semi-siloxane POSS with amino in the step (2) is as follows:
6. the method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the activating agent in the step (1) is one of N, N' -Carbonyl Diimidazole (CDI), ethylenediamine phosphate, propylenediamine phosphate, xylene, sodium fluosilicate, ammonium sulfate, ammonium chloride, ferrous sulfate and ammonium hydroxide.
7. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the pore-forming additive in the step (3) is one of polyvinylpyrrolidone, carboxymethyl cellulose, methyl cellulose, copovidone, polyvinyl alcohol, polyethylene glycol and sodium nitrate; the organic solvent in the step (3) is one of dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and triethyl phosphate.
8. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the mass ratio of the polyether sulfone, the pore-forming additive and the organic solvent in the step (3) is 1: (0.1-0.15): (2.5-4.5).
9. The method for preparing the POSS grafted carbon nanotube composite lithium-sulfur battery separator according to claim 1, wherein the method comprises the following steps: the spinning layer of the POSS grafted carbon nano tube of the composite lithium-sulfur battery diaphragm of the POSS grafted carbon nano tube in the step (4) is 200-600nm thick, and the PE diaphragm is 9-25 mu m thick.
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