CN112018304B - Coating diaphragm for lithium-sulfur battery, preparation method and lithium-sulfur battery - Google Patents
Coating diaphragm for lithium-sulfur battery, preparation method and lithium-sulfur battery Download PDFInfo
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- CN112018304B CN112018304B CN201910459307.0A CN201910459307A CN112018304B CN 112018304 B CN112018304 B CN 112018304B CN 201910459307 A CN201910459307 A CN 201910459307A CN 112018304 B CN112018304 B CN 112018304B
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000000576 coating method Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 31
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006255 coating slurry Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims abstract description 19
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002322 conducting polymer Substances 0.000 claims abstract description 11
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 26
- 239000008247 solid mixture Substances 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 229910021389 graphene Inorganic materials 0.000 claims description 17
- 229920002125 Sokalan® Polymers 0.000 claims description 16
- 239000004584 polyacrylic acid Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- -1 polypropylene Polymers 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 12
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 8
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000289 Polyquaternium Polymers 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000007761 roller coating Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 description 3
- 229960002311 dithranol Drugs 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- MUVQKFGNPGZBII-UHFFFAOYSA-N 1-anthrol Chemical compound C1=CC=C2C=C3C(O)=CC=CC3=CC2=C1 MUVQKFGNPGZBII-UHFFFAOYSA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of a coating diaphragm for a lithium-sulfur battery and the lithium-sulfur battery adopting the coating diaphragm, wherein the preparation method of the coating diaphragm comprises the following steps: dispersing a lithium-conducting polymer in water to obtain first slurry; uniformly mixing the carbon conductor and the anthraquinone, and dispersing the mixture in the absolute ethyl alcohol added with the dispersing agent to obtain second slurry; and (3) mixing the first slurry and the second slurry according to the mass parts (1-8): (2-10) uniformly mixing to obtain a third slurry, uniformly mixing the third slurry with a binder to obtain a coating slurry, coating the coating slurry on the positive electrode side of the polyolefin film, and drying to obtain the coating diaphragm for the lithium-sulfur battery. The lithium-sulfur battery prepared by the method can inhibit the shuttling effect of the lithium-sulfur polymer in the charging and discharging processes of the lithium-sulfur battery, improve the cyclicity and the coulombic efficiency of the lithium-sulfur battery, and prolong the service life of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a coating diaphragm for a lithium-sulfur battery, a preparation method and the lithium-sulfur battery.
Background
The lithium-sulfur battery has higher theoretical specific energy density, and the sulfur anode has low price and is environment-friendly, so that the lithium-sulfur battery is more and more emphasized by people in recent years. The diaphragm is an important component of the lithium-sulfur battery, and mainly has the functions of isolating the positive electrode and the negative electrode of the battery, preventing the internal short circuit of the battery and providing a migration channel for lithium ions in the charging and discharging processes. The traditional lithium-sulfur battery diaphragm mostly adopts a microporous polyethylene or polypropylene film, lithium loses electrons and is changed into lithium ions in the charging and discharging process of the lithium-sulfur battery, the lithium ions react with sulfur at the positive electrode end of the lithium-sulfur battery through the diaphragm to generate a lithium-sulfur polymer, and the lithium-sulfur polymer can shuttle between the positive electrode and the negative electrode through the diaphragm, so that the sulfur positive electrode can be irreversibly damaged, and the cyclicity and the coulombic efficiency of the battery are influenced. The above-mentioned drawbacks still face the challenge of high safety, long life and high specific energy, which are difficult to be combined, and the commercialization process of the lithium-sulfur battery is severely restricted. Therefore, the development of a composite separator having a special function of trapping sulfur and conducting lithium has become one of the important aspects for promoting the development of lithium-sulfur batteries.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a coating diaphragm for a lithium-sulfur battery, which can effectively inhibit the shuttling effect of a lithium-sulfur polymer, improve the cyclicity and the coulombic efficiency of the lithium-sulfur battery, prolong the service life of the battery, and has the advantages of simple preparation process and low cost.
It is another object of the present invention to provide a lithium sulfur battery using the coated separator.
The invention is realized by the following technical scheme:
a preparation method of a coating diaphragm for a lithium-sulfur battery comprises the following steps:
dispersing the lithium-conducting polymer in water according to the solid content of 1-10 wt%, and stirring for 10-50 minutes to obtain a first slurry.
Mixing a carbon conductor and anthraquinone to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with a dispersing agent according to the solid content of 1-10 wt%, wherein the mass of the dispersing agent is 0.1-1% of that of the carbon conductor in the raw material solid mixture, and stirring for 10-50 minutes to obtain a second slurry;
mixing the first slurry and the second slurry according to the mass part of 1-8:2-10, and then introducing the mixture into a sand mill to stir for 20-70 minutes to obtain a third slurry; the third slurry comprises, by mass, 1-5 parts of a lithium conducting polymer, 1-2 parts of a carbon conductor and 1-2 parts of anthraquinone.
Mixing the third slurry with a binder, wherein the amount of the binder is 1-10% of the mass of the third slurry, and stirring for 5-30 minutes to obtain uniformly dispersed coating slurry;
coating the coating slurry on the positive electrode side of a polyolefin film, wherein the thickness of the coating is 1-8 mu m, and drying to obtain the coating diaphragm for the lithium-sulfur battery;
the lithium conducting polymer is at least one of polyacrylic acid, sulfonated polyether sulfone and polymethyl methacrylate;
the adhesive is polyacrylate;
the dispersant is organic ammonium salt substances.
In the technical scheme, the coating slurry is coated on the positive electrode side of the polyolefin membrane in a roll coating mode,
in the above technical scheme, the polyolefin film is a polypropylene film or a polyethylene film.
In the above technical scheme, the anthraquinone substance is one of anthraphenol, oxidized anthraphenol, anthrone, dianthraquinone and dianthraquinone.
In the above technical scheme, the carbon conductor material is one of graphene, natural graphite and artificial graphite.
In the above technical scheme, the carbon-based conductor material is graphene.
In the above technical scheme, the binder is polymethyl acrylate or polyethyl acrylate.
In the technical scheme, the stirring speed in the stirring process is 1000-1200 rpm.
In the technical scheme, the drying temperature is 40-100 ℃, and the drying time is 0.5s.
In the above technical scheme, the dispersant is at least one of polyacrylic acid ammonium salt, trimethylammonium hydrochloride, polyquaternium and polyacrylic acid ammonium salt.
A preparation method of a coating diaphragm for a lithium-sulfur battery comprises the following steps:
uniformly dispersing a lithium-conducting polymer in water according to the solid content of 1-10 wt%, stirring at the speed of 1000-1200 rpm for 10-50 minutes to obtain a first slurry;
mixing a carbon conductor and an anthraquinone substance according to the following parts by weight: 1-2 parts of the carbon conductor and 1-2 parts of the anthraquinone substance to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture in absolute ethyl alcohol added with a dispersing agent according to the solid content of 1-10 wt%, wherein the mass of the dispersing agent is 0.1-1% of that of the carbon conductor in the raw material solid mixture, the stirring speed is 1000-1200 r/m, and the stirring is carried out for 10-50 minutes to obtain a second slurry;
and (2) mixing the first slurry and the second slurry in parts by mass: (1-8) mixing (2-10), and then introducing into a sand mill for stirring to obtain third slurry;
mixing the third slurry with a binder, wherein the amount of the binder is 1-10% of the mass of the third slurry, and stirring for 5-30 minutes to obtain uniformly dispersed coating slurry;
coating the coating slurry on the positive electrode side of a polyolefin film in a roller coating mode, wherein the thickness of the coating is 1-8 mu m, and drying at the drying temperature of 40-100 ℃ for 0.5s to obtain the coating diaphragm for the lithium-sulfur battery;
the lithium conducting polymer is at least one of polyacrylic acid, sulfonated polyether sulfone and polymethyl methacrylate;
the carbon conductor is at least one of graphene, natural graphite and artificial graphite;
the anthraquinone matter is at least one of anthraphenol, oxidized anthraphenol, anthrone, dianthraquinone and dianthradone;
the binder is polymethyl acrylate or polyethyl acrylate;
the dispersant is at least one of polyacrylic acid ammonium salt, trimethylammonium hydrochloride, polyquaternary ammonium salt and polyacrylic acid ammonium salt.
A lithium-sulfur battery with a coating diaphragm comprises a sulfur positive plate, a metal lithium plate negative electrode and electrolyte, wherein the coating diaphragm obtained by the preparation method in the technical scheme is arranged between the sulfur positive plate and the metal lithium plate negative electrode.
The invention has the advantages and beneficial effects that:
anthraquinone small molecules in the lithium-sulfur battery coating diaphragm can rapidly generate reversible redox reaction with a lithium-sulfur polymer formed at a sulfur positive terminal to form AQ-Li 2 S 4 And (4) precipitating. In the reaction process, an S-O chemical bond is formed between the anthraquinone and the lithium sulfur polymer, so that anthraquinone small molecules have a strong adsorption effect on the soluble lithium sulfur polymer, thereby realizing effective inhibition on loss of active substances, remarkably prolonging the service life of the battery, and having low cost of anthraquinone substances; meanwhile, the slurry of the invention takes ethanol and water as solvents, thereby reducing the cost and being environment-friendly.
Drawings
FIG. 1 is a scanning electron microscope image of a coated separator for a lithium sulfur battery prepared in example 1 of the present invention
For a person skilled in the art, other relevant figures can be obtained from the above figures without inventive effort.
Detailed Description
In order to make the technical solution of the present invention better understood, the technical solution of the present invention is further described below with reference to specific examples.
Main detection equipment used in the embodiments
Example one
Dispersing polyacrylic acid in water according to the solid content of 3wt%, and placing the mixture into a stirrer to be stirred for 30 minutes at the stirring speed of 1000 rpm to obtain first slurry; mixing graphene and anthrol to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with ammonium polyacrylate according to the solid content of 3wt%, wherein the mass of the ammonium polyacrylate is 0.5% of that of the graphene in the raw material solid mixture, placing the mixture into a stirrer, and stirring for 30 minutes at the stirring speed of 1000 rpm to obtain a second slurry; mixing the first slurry and the second slurry according to the mass part of 5:7, and then introducing the mixture into a sand mill to stir for 60 minutes, wherein the rotating speed of the sand mill is 1200 rpm, so as to obtain a third slurry; the third slurry comprises 2 parts by weight of polyacrylic acid, 1 part by weight of graphene and 1 part by weight of anthralin; mixing the third slurry with polymethyl acrylate, wherein the amount of the polymethyl acrylate is 5% of the mass of the third slurry, and stirring in a stirrer for 15 minutes to obtain uniformly dispersed coating slurry; and coating the coating slurry on the positive electrode side of a polypropylene film in a roller coating manner, wherein the thickness of the coating is 2 mu m, and drying at 60 ℃ for 0.5s to obtain the coating diaphragm for the lithium-sulfur battery. Fig. 1 is a scanning electron microscope image of the coated separator for a lithium sulfur battery prepared in example 1, from which it can be seen that the surface of the separator is uniformly coated and has good gas permeability.
And (3) electrochemical performance testing: respectively using a voltage-resistant insulation analyzer to measure the decomposition voltage of the lithium-sulfur battery diaphragm, using a high-temperature test chamber to measure the thermal shrinkage rate of the lithium-sulfur battery diaphragm, and using a chemical composition capacitance cabinet to measure the capacity retention rate and the average coulombic efficiency of the lithium-sulfur battery with the coating diaphragm, wherein the specific test results are as follows: the obtained lithium-sulfur battery separator had a decomposition voltage of 4.7V, a thermal shrinkage of 0.7% at 130 ℃ for 1 hour, and a liquid absorption of 362%. The battery is assembled by adopting sulfur as a positive electrode and a lithium sheet as a negative electrode, the capacity retention rate is 87% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.64% after the battery is cycled for 20 circles.
Example two
Dispersing sulfonated polyether sulfone in water according to the solid content of 5wt%, and placing the sulfonated polyether sulfone in a stirrer to stir for 40 minutes at the stirring speed of 1000 rpm to obtain first slurry; mixing graphene and anthralin oxide to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with trimethylammonium hydrochloride according to the solid content of 5wt%, wherein the mass of the trimethylammonium hydrochloride is 0.3% of that of the graphene in the raw material solid mixture, placing the raw material solid mixture into a stirrer, and stirring for 40 minutes at the stirring speed of 1000 revolutions per minute to obtain a second slurry; mixing the first slurry and the second slurry according to the mass part of 4:6, and then introducing the mixture into a sand mill to stir for 45 minutes, wherein the rotating speed of the sand mill is 1200 rpm, so as to obtain a third slurry; the third slurry comprises 2 parts by mass of sulfonated polyether sulfone, 1 part by mass of graphene and 1 part by mass of anthralin oxide; mixing the third slurry with polymethyl acrylate, wherein the amount of the polymethyl acrylate is 6% of the mass of the third slurry, and stirring in a stirrer for 20 minutes to obtain uniformly dispersed coating slurry; and coating the coating slurry on the positive electrode side of a polyethylene film in a roller coating manner, wherein the thickness of the coating is 2.5 mu m, and drying at 70 ℃ for 0.5s to obtain the coating diaphragm for the lithium-sulfur battery.
And (3) electrochemical performance testing: respectively using a voltage-resistant insulation analyzer to measure the decomposition voltage of the lithium-sulfur battery diaphragm, using a high-temperature test chamber to measure the thermal shrinkage rate of the lithium-sulfur battery diaphragm, and using a chemical composition capacitance cabinet to measure the capacity retention rate and the average coulombic efficiency of the lithium-sulfur battery with the coating diaphragm, wherein the specific test results are as follows: the decomposition voltage of the obtained lithium-sulfur battery separator was 4.8V, the thermal shrinkage at 130 ℃ for 1 hour was 1.2%, and the liquid absorption rate was 403%. The battery is assembled by adopting sulfur as a positive electrode and a lithium sheet as a negative electrode, the capacity retention rate is 82.2% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.83% after the battery is cycled for 20 circles.
EXAMPLE III
Dispersing polymethyl methacrylate in water according to the solid content of 7wt%, placing the mixture in a stirrer, and stirring for 50 minutes at the stirring speed of 1000 rpm to obtain first slurry; mixing graphene and anthrone to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into anhydrous ethanol added with polyquaternium according to the solid content of 7wt%, wherein the mass of the polyquaternium is 0.7% of the mass of the graphene in the raw material solid mixture, placing the mixture into a stirrer, and stirring for 45 minutes at the stirring speed of 1000 rpm to obtain a second slurry; mixing the first slurry and the second slurry according to the mass part of 1:1, and then introducing the mixture into a sand mill to stir for 50 minutes, wherein the rotating speed of the sand mill is 1200 rpm, so as to obtain a third slurry;
the third slurry comprises, by mass, 3 parts of polymethyl methacrylate, 2 parts of graphene and 1 part of anthrone; mixing the third slurry with polyethylacrylate, wherein the amount of the polyethylacrylate is 7% of the mass of the third slurry, and stirring in a stirrer for 25 minutes to obtain uniformly dispersed coating slurry; and coating the coating slurry on the positive electrode side of a polypropylene film in a roller coating manner, wherein the thickness of the coating is 3 mu m, and drying the coating for 0.5s at 55 ℃ to obtain the coating diaphragm for the lithium-sulfur battery.
And (3) electrochemical performance testing: respectively using a voltage-resistant insulation analyzer to measure the decomposition voltage of the lithium-sulfur battery diaphragm, using a high-temperature test chamber to measure the thermal shrinkage rate of the lithium-sulfur battery diaphragm, and using a chemical composition capacitance cabinet to measure the capacity retention rate and the average coulombic efficiency of the lithium-sulfur battery with the coating diaphragm, wherein the specific test results are as follows: the obtained lithium-sulfur battery separator had a decomposition voltage of 4.7V, a heat shrinkage of 1 hour at 130 ℃ of 1% and a liquid absorption of 347%. The battery is assembled by adopting sulfur as a positive electrode and a lithium sheet as a negative electrode, the capacity retention rate is 86% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.2% after the battery is cycled for 20 circles.
Example four
Dispersing polyacrylic acid in water according to the solid content of 8wt%, and placing the mixture into a stirrer to be stirred for 20 minutes at the stirring speed of 1000 rpm to obtain first slurry; mixing graphene and anthraquinone to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with polyacrylic acid ammonium salt according to the solid content of 8wt%, wherein the mass of the polyacrylic acid ammonium salt is 0.6% of the mass of the graphene in the raw material solid mixture, placing the raw material solid mixture into a stirrer, and stirring for 20 minutes at the stirring speed of 1000 rpm to obtain a second slurry; mixing the first slurry and the second slurry according to the mass part of 3:8, and then introducing the mixture into a sand mill to stir for 35 minutes, wherein the rotating speed of the sand mill is 1200 rpm, so as to obtain a third slurry; the third slurry comprises 4 parts by mass of polyacrylic acid, 1 part by mass of graphene and 1 part by mass of anthraquinone; mixing the third slurry with polyethylacrylate, wherein the amount of the polyethylacrylate is 8% of the mass of the third slurry, and stirring in a stirrer for 20 minutes to obtain uniformly dispersed coating slurry; and coating the coating slurry on the positive electrode side of a polypropylene film in a roller coating manner, wherein the thickness of the coating is 4 mu m, and drying the coating for 0.5s at 65 ℃ to obtain the coating diaphragm for the lithium-sulfur battery.
And (3) electrochemical performance testing: respectively using a voltage-resistant insulation analyzer to measure the decomposition voltage of the lithium-sulfur battery diaphragm, using a high-temperature test chamber to measure the thermal shrinkage rate of the lithium-sulfur battery diaphragm, and using a chemical composition capacitance cabinet to measure the capacity retention rate and the average coulombic efficiency of the lithium-sulfur battery with the coating diaphragm, wherein the specific test results are as follows: the obtained lithium-sulfur battery separator had a decomposition voltage of 4.7V, a thermal shrinkage of 0.9% at 130 ℃ for 1 hour, and a liquid absorption of 385%. The battery is assembled by adopting sulfur as a positive electrode and a lithium sheet as a negative electrode, the capacity retention rate is 85% after the battery is cycled for 100 circles under the multiplying power of 0.5C, and the average coulombic efficiency is 99.8% after the battery is cycled for 20 circles.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (8)
1. A preparation method of a coating diaphragm for a lithium-sulfur battery is characterized by comprising the following steps: the method comprises the following steps:
uniformly dispersing a lithium conducting polymer in water according to the solid content of 1-10 wt% to obtain a first slurry;
mixing a carbon conductor and an anthraquinone substance to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with a dispersing agent according to the solid content of 1-10wt%, wherein the mass of the dispersing agent is 0.1-1% of that of the carbon conductor in the raw material solid mixture, and obtaining a second slurry;
and (2) mixing the first slurry and the second slurry according to the mass parts: mixing (1~8) parts by weight, and introducing into a sand mill for stirring to obtain a third slurry; the third slurry comprises 3236 parts by mass of a lithium conducting polymer, 3236 parts by mass of a carbon conductor and 3262 parts by mass of an anthraquinone substance, 5262 parts by mass of a carbon conductor and 3763 parts by mass of an anthraquinone substance;
mixing the third slurry with a binder, wherein the using amount of the binder is 1-10% of the mass of the third slurry, and stirring for 5-30 minutes to obtain a uniformly dispersed coating slurry;
coating the coating slurry on the positive electrode side of a polyolefin film, wherein the thickness of the coating is 1~8μm, and drying to obtain the coating diaphragm for the lithium-sulfur battery;
the lithium conducting polymer is at least one of polyacrylic acid, sulfonated polyether sulfone and polymethyl methacrylate;
the carbon conductor is at least one of graphene, natural graphite and artificial graphite;
the anthraquinone matter is at least one of anthraphenol, oxidized anthraphenol, anthrone, dianthraquinone and dianthranone;
the binder is polyacrylate;
the dispersant is organic ammonium salt.
2. The method of preparing a coated separator for a lithium sulfur battery according to claim 1, wherein: the coating slurry is coated on the positive electrode side of the polyolefin film in a roll coating mode.
3. The method of preparing a coated separator for a lithium sulfur battery according to claim 1, wherein: the polyolefin film is a polypropylene film or a polyethylene film.
4. The method of preparing a coated separator for a lithium sulfur battery according to claim 1, wherein: the polyacrylate is polymethyl acrylate or polyethyl acrylate.
5. The method of preparing a coated separator for a lithium sulfur battery according to claim 1, wherein: the drying temperature is 40 to 100 ℃, and the drying time is 0.5s.
6. The method of preparing a coated separator for a lithium sulfur battery according to claim 1, wherein: the organic ammonium salt is at least one of polyacrylic acid ammonium salt, trimethylammonium hydrochloride and polyquaternary ammonium salt.
7. A preparation method of a coating diaphragm for a lithium-sulfur battery is characterized by comprising the following steps: the method comprises the following steps:
uniformly dispersing a lithium conducting polymer in water according to the solid content of 1-10 wt%, stirring at the speed of 1000-1200 rpm for 10-50 minutes to obtain a first slurry;
mixing a carbon conductor and an anthraquinone substance according to the following parts by mass: 1~2 parts of the carbon conductor and 1~2 parts of the anthraquinone material to obtain a raw material solid mixture, uniformly dispersing the raw material solid mixture into absolute ethyl alcohol added with a dispersing agent according to the solid content of 1-10wt%, wherein the mass of the dispersing agent is 0.1-1% of that of the carbon conductor in the raw material solid mixture, stirring at the speed of 1000-1200 rpm, and stirring for 10-50 minutes to obtain a second slurry;
and (2) mixing the first slurry and the second slurry according to the mass parts: mixing (1~8) parts by weight, and introducing into a sand mill for stirring to obtain a third slurry;
mixing the third slurry with a binder, wherein the using amount of the binder is 1-10% of the mass of the third slurry, and stirring for 5-30 minutes to obtain a uniformly dispersed coating slurry;
coating the coating slurry on the positive electrode side of a polyolefin film in a roll coating mode, wherein the coating thickness is 1~8μm, and drying at the drying temperature of 40-100 ℃ for 0.5s to obtain the coating diaphragm for the lithium-sulfur battery;
the lithium conducting polymer is at least one of polyacrylic acid, sulfonated polyether sulfone and polymethyl methacrylate;
the carbon conductor is at least one of graphene, natural graphite and artificial graphite;
the anthraquinone matter is at least one of anthraphenol, oxidized anthraphenol, anthrone, dianthraquinone and dianthranone;
the binder is polymethyl acrylate or polyethyl acrylate;
the dispersant is at least one of polyacrylic acid ammonium salt, trimethylammonium hydrochloride and polyquaternium.
8. A lithium-sulfur battery with a coating diaphragm, which comprises a sulfur positive plate, a metal lithium plate negative electrode and an electrolyte, and is characterized in that the coating diaphragm obtained by the preparation method of any one of the 1~7 is arranged between the sulfur positive plate and the metal lithium plate negative electrode.
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