CN114156600A - Diaphragm containing mixed conductor coating and preparation method and application thereof - Google Patents
Diaphragm containing mixed conductor coating and preparation method and application thereof Download PDFInfo
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- CN114156600A CN114156600A CN202111519939.5A CN202111519939A CN114156600A CN 114156600 A CN114156600 A CN 114156600A CN 202111519939 A CN202111519939 A CN 202111519939A CN 114156600 A CN114156600 A CN 114156600A
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- coating
- solid electrolyte
- carbon
- electrolyte material
- separator
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- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 73
- 239000011533 mixed conductor Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 55
- 239000010410 layer Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- -1 polydimethylsiloxane Polymers 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000080 wetting agent Substances 0.000 claims description 11
- 239000006255 coating slurry Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- YVIGPQSYEAOLAD-UHFFFAOYSA-L disodium;dodecyl phosphate Chemical compound [Na+].[Na+].CCCCCCCCCCCCOP([O-])([O-])=O YVIGPQSYEAOLAD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 239000011118 polyvinyl acetate Substances 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims 1
- 238000007606 doctor blade method Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000007774 anilox coating Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/431—Inorganic material
-
- 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
Abstract
The invention relates to a diaphragm containing a mixed conductor coating, a preparation method and application thereof, wherein the diaphragm containing the mixed conductor coating comprises the following components: a base film, and a coating layer attached to at least one side surface of the base film; the coating comprises a novel carbon-coated solid electrolyte material; the novel carbon-coated solid electrolyte material is of a core-shell structure, and the core-shell structure comprises a core and a shell; the inner core comprises a first component and a second component; the first component is solid electrolyte material with chemical formula of LixAyZr2‑ySix‑y‑1P4‑x+yO12X is more than or equal to 1 and less than or equal to 5, and y is more than 0 and less than or equal to 1; wherein A comprises: one of Al, Cr, Fe, Ga, Se, Y, In or LaOr a plurality thereof; the second component specifically comprises amorphous carbon and/or crystalline carbon; the outer shell is a carbon layer.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a diaphragm containing a mixed conductor coating, and a preparation method and application thereof.
Background
At present, lithium batteries, as novel secondary batteries, have the advantages of high energy density, long cycle life and the like, and the application range of the lithium batteries is continuously expanded, so that the lithium batteries are widely applied to power automobiles, energy storage and portable electrical appliances. However, frequent safety accidents of lithium batteries increasingly attract people's attention, and people have higher and higher performance requirements on lithium batteries, and not only the lithium batteries are required to have higher capacity and better capacity retention rate, but also the lithium batteries are required to have higher safety. The diaphragm is used as an important component of the lithium battery, can effectively prevent the short circuit caused by the contact of the positive electrode and the negative electrode, and has very important influence on the safety of the lithium battery, so that the improvement of the electrical property and the safety performance of the lithium battery by the high-performance diaphragm is considerable.
The ceramic diaphragm is the most widely used diaphragm of the lithium battery at present, but the existing ceramic diaphragm on the market has the problems of poor wettability and ionic conductivity, poor battery cyclicity, insignificant improvement of the heat resistance of the diaphragm and the like, so that the lithium battery diaphragm with excellent performance is required to meet the requirements of the battery performance.
Disclosure of Invention
The embodiment of the invention provides a diaphragm containing a mixed conductor coating, a preparation method and application thereof, and the diaphragm containing the mixed conductor coating and provided with a novel carbon-coated solid electrolyte material coating is used for replacing a traditional ceramic diaphragm, so that the safety performance of a lithium battery can be effectively improved, and the direct-current internal resistance of the battery is reduced.
In a first aspect, embodiments of the present invention provide a separator including a mixed conductor coating, including: a base film, and a coating layer attached to at least one side surface of the base film;
the coating comprises a novel carbon-coated solid electrolyte material; the novel carbon-coated solid electrolyte material is of a core-shell structure, and the core-shell structure comprises a core and a shell; the inner core comprises a first component and a second component;
the first component is a solid electrolyte material with a chemical general formula
LixAyZr2-ySix-y-1P4-x+yO12X is more than or equal to 1 and less than or equal to 5, and y is more than 0 and less than or equal to 1; wherein A comprises: one or more of Al, Cr, Fe, Ga, Se, Y, In or La;
the second component specifically comprises amorphous carbon and/or crystalline carbon;
the shell is a carbon layer.
Preferably, the carbon layer is specifically a carbon layer film or carbon layer particles; the thickness of the carbon layer is between 1nm and 2 mu m; the coverage rate of the carbon layer on the surface of the inner core is 50% -100%;
the grain size of the inner core is between 30nm and 100 mu m;
the particle size of the novel carbon-coated solid electrolyte material is 31nm-102 mu m;
the mass ratio of the first component to the second component to the carbon layer is 1 (0-0.6): (0.002-0.6).
Preferably, one side or two sides of the coating layer are provided with a glue layer; the material of the glue layer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or polymethyl methacrylate.
Further preferably, the thickness of the coating layer is between 0.5 μm and 10 μm, and the thickness of the glue layer is between 0.2 μm and 5 μm.
Preferably, the base film is an organic base film and comprises a polyolefin microporous film or a polyimide non-woven fabric; the thickness of the basement membrane is 5-20 μm, and the porosity is 30-80%.
Preferably, the coating specifically comprises: 20-80 wt% of solvent, 10-79.95 wt% of novel carbon-coated solid electrolyte material, 0-5 wt% of wetting agent, 0-5 wt% of dispersing agent, 0.05-20 wt% of binder and 0-5 wt% of auxiliary agent; the novel carbon-coated solid electrolyte material in the coating accounts for more than 40% of the total mass of the solid;
the solvent comprises: one or more of deionized water, N-methyl pyrrolidone, alcohol, dimethylformamide, ethyl acetate and isopropanol;
the wetting agent comprises: one or more of polydimethylsiloxane, polyether modified siloxane, polyoxyethylene ether, polyoxyethylene octylphenol ether, polyether siloxane, sodium alkyl benzene sulfonate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether or sodium lauryl sulfate;
the dispersant comprises: one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyacrylamide, polyvinyl acetate or polyurethane;
the auxiliary agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty alcohol sulfate, polyglycol ether, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene alkylamine, polyoxyethylene amide, titanate coupling agent or aluminate coupling agent.
In a second aspect, an embodiment of the present invention provides a preparation method of the separator containing the mixed conductor coating layer according to the first aspect, where the preparation method includes:
dispersing the novel carbon-coated solid electrolyte material, the dispersing agent and the solvent in a stirring tank at a high speed at a dispersion speed of 2000-3000 rmp in parts by mass;
sanding the dispersed slurry, taking out the slurry by sanding, adding the binder, the wetting agent and the auxiliary agent according to the required mass part, fully stirring and carrying out ultrasonic treatment to obtain the coating slurry;
uniformly coating the coating slurry on at least one surface of a base film and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating;
the coating slurry specifically comprises the following components in parts by weight: 20-80 wt% of solvent, 10-79.95 wt% of novel carbon-coated solid electrolyte material, 0-5 wt% of wetting agent, 0-5 wt% of dispersing agent, 0.05-20 wt% of binder and 0-5 wt% of auxiliary agent.
Further preferably, the coating method includes any one of a blade coating method, a gravure roll coating method, and a spray coating method.
In a third aspect, an embodiment of the present invention provides a lithium ion battery including the separator including the mixed conductor coating layer according to the first aspect.
In a fourth aspect, embodiments of the present invention provide a use of the mixed conductor coating-containing separator described in the first aspect, where the mixed conductor coating-containing separator described in the first aspect is used for a battery separator of a secondary battery.
The diaphragm containing the mixed conductor coating provided by the embodiment of the invention has the advantages that the novel carbon-coated solid electrolyte material is introduced, so that the diaphragm not only has the thermal stability of the traditional ceramic diaphragm, but also is different from the condition that lithium ions do not have the migration capability in the traditional ceramic, the lithium ions have the migration capability in the novel carbon-coated solid electrolyte material in the diaphragm, the unique core-shell structure can effectively improve the conductivity of lithium ions and the interface compatibility of electrolyte/electrode, the moisture content of the diaphragm can be effectively reduced, and the cycle performance and the safety performance of a battery can be effectively improved.
Drawings
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method for preparing a separator including a mixed conductor coating according to an embodiment of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a separator containing a mixed conductor coating provided in example 1 of the present invention;
fig. 3 is a graph comparing the dc internal resistance of the mixed conductor coating-containing separator provided in example 1 of the present invention with the separators of comparative example 1 and comparative example 2.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The invention provides a diaphragm containing a mixed conductor coating, which comprises: a base film, and a coating layer attached to at least one side surface of the base film.
The base film is an organic base film and comprises a polyolefin microporous film or polyimide non-woven fabric; the thickness of the basement membrane is 5-20 μm, and the porosity is 30-80%.
The coating comprises a novel carbon-coated solid electrolyte material.
The novel carbon-coated solid electrolyte material is of a core-shell structure and comprises a core layer and a shell layer, and the particle size of the novel carbon-coated solid electrolyte material is 31nm-102 mu m.
The inner core comprises a first component and a second component, and the particle size of the inner core is 30nm-100 μm. The first component is solid electrolyte material with chemical formula of LixAyZr2-ySix-y-1P4-x+yO12X is more than or equal to 1 and less than or equal to 5, and y is more than 0 and less than or equal to 1; wherein A comprises: one or more of Al, Cr, Fe, Ga, Se, Y, In or La. The second component specifically comprises amorphous carbon and/or crystalline carbon.
The shell is a carbon layer and comprises carbon layer films or carbon layer particles; the thickness of the carbon layer is between 1nm and 2 mu m; the coverage of the carbon layer to the surface of the core is 50% -100%.
The mass ratio of the first component to the second component to the carbon layer is 1 (0-0.6): (0.002-0.6).
The novel carbon-coated solid electrolyte material is represented as LixAyZr2-ySix-y-1P4-x+yO12The ratio of x to y is more than or equal to 1 and less than or equal to 5, and y is more than 0 and less than or equal to 1.
In addition to the above-described novel carbon-coated solid electrolyte material, the coating layer includes other components. The composition of the coating may specifically include: 20-80 wt% of solvent, 10-79.95 wt% of novel carbon-coated solid electrolyte material, 0-5 wt% of wetting agent, 0-5 wt% of dispersing agent, 0.05-20 wt% of binder and 0-5 wt% of auxiliary agent; the novel carbon-coated solid electrolyte material in the coating accounts for more than 40% of the total mass of the solid; the thickness of the coating is between 0.5 μm and 10 μm.
Wherein, the solvent comprises: one or more of deionized water, N-methyl pyrrolidone, alcohol, dimethylformamide, ethyl acetate and isopropanol;
the wetting agents include: one or more of polydimethylsiloxane, polyether modified siloxane, polyoxyethylene ether, polyoxyethylene octylphenol ether, polyether siloxane, sodium alkyl benzene sulfonate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether or sodium lauryl sulfate;
the dispersant comprises: one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyacrylamide, polyvinyl acetate or polyurethane;
the auxiliary agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty alcohol sulfate, polyglycol ether, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene alkylamine, polyoxyethylene amide, titanate coupling agent or aluminate coupling agent.
In addition, one side or both sides of the coating layer can be provided with a glue layer, the material of the glue layer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or polymethyl methacrylate, and the thickness of the glue layer is between 0.2 and 5 mu m.
The above separator containing the mixed conductor coating layer can be obtained by the following production method. The specific method steps are shown in fig. 1 and comprise:
110, dispersing the novel carbon-coated solid electrolyte material, the dispersing agent and the solvent in a stirring tank at a high speed at a dispersion speed of 2000-3000 rmp in parts by mass;
and step 130, uniformly coating the coating slurry on at least one surface of the base film and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating.
Specifically, the coating method includes any one of a blade coating method, a gravure roll coating method, and a spray coating method.
In the above method steps, the selection and the parts by mass of each component material are consistent with the specific materials and the numerical range in the above battery separator embodiment, and are not described herein again.
The separator containing the mixed conductor coating provided by the embodiment of the invention can be used for a battery separator of a secondary battery, such as a lithium ion battery together with a positive electrode, a negative electrode and an electrolyte.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the specific processes for preparing the separator containing the mixed conductor coating by using the methods provided by the above embodiments of the invention, and the methods and battery characteristics for applying the same to the secondary battery.
Example 1
This example provides a method for preparing a separator with a mixed conductor coating.
40g of polyethylene glycol, 20g of sodium carboxymethylcellulose and 8kg of deionized water were charged into a preliminary stirring tank, and dispersed at a dispersion speed of 3000rpm for 1 hour to obtain a first slurry.
1800g of novel carbon-coated solid electrolyte material Li2Al0.5Zr1.5Si0.5P2.5O12adding/C-C (the ratio is 1: 0.55: 0.05) into the first slurry, dispersing at the dispersion speed of 2500rpm for 1.5 hours, adding the dispersed slurry into a sand mill, and sanding for 0.5 hour to obtain second slurry.
Adding 200g of styrene-butadiene rubber and 20g of polyether modified siloxane into the second slurry, and fully stirring to obtain a third slurry; wherein the stirring speed was 30 rpm.
And carrying out ultrasonic treatment on the third slurry for 0.5 hour at the ultrasonic frequency of 5 kHz.
And (4) defoaming the slurry subjected to ultrasonic treatment in vacuum for 0.5 hour.
And filtering the slurry subjected to vacuum defoaming by using a 170-mesh screen to obtain the required slurry with the novel carbon-coated solid electrolyte material.
And uniformly coating the slurry with the novel carbon-coated solid electrolyte material on the surface of a base film by using an anilox roller and drying to form the required diaphragm. Wherein the drying temperature is 50 ℃, the base film moving speed is 15m/min, and the coating thickness is 2 μm. The base film is a 12-micron polyethylene microporous film (wet method), and the porosity of the base film is 40%.
Fig. 2 is an SEM image of the separator including the mixed conductor coating layer prepared in the embodiment of the present invention, and as can be seen from fig. 2, the diameter distribution of the particles of the mixed conductor coating layer is uniform, and the gaps between the particles are small, so that the material performance stability is high, and the thermal stability of the separator can be effectively improved.
Example 2
This example provides a method for preparing a separator with a mixed conductor coating.
1900g of a novel carbon-coated solid electrolyte material Li2Ga0.5Zr1.5Si0.5P2.5O12C-C (ratio: 1: 0.4: 0.03), 20g of sodium dodecylbenzenesulfonate, 20g of sodium hexametaphosphate, 200g of polyvinyl alcohol, 20g of polydimethylsiloxane and 8kg of deionized water were added to a stirring tank, and dispersed and stirred at 2500rmp for 3 hours.
And (3) sanding the dispersed slurry, taking out, and then carrying out ultrasonic treatment, wherein the technological parameters are the same as those in example 1, so that the slurry with the novel carbon-coated solid electrolyte material is obtained.
And uniformly coating the slurry with the novel carbon-coated solid electrolyte material on the inner and outer side surfaces of a 9-micron polyethylene microporous membrane by using an anilox roller, and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating and coated on both sides.
Example 3
This example provides a method for preparing a separator with a mixed conductor coating.
2000g of a novel carbon-coated solid electrolyte material Li2La0.5Zr1.5Si0.5P2.5O12The mixture of/C-C (ratio: 1: 0.56:0.1), 40g of polyvinylpyrrolidone, 200g of polyvinylidene fluoride and 8kg of N-methylpyrrolidone was placed in a stirring vessel and dispersed and stirred at 2500rmp for 2 hours.
And (3) sanding the dispersed slurry, taking out, and then carrying out ultrasonic treatment, wherein the technological parameters are the same as those in example 1, so that the slurry with the novel carbon-coated solid electrolyte material is obtained.
And uniformly coating the slurry on the surface of a base film by using an anilox roller and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating. Wherein the drying temperature is 60 ℃, the base film moving speed is 12m/min, the coating thickness is 1.5 μm, and the base film is 20 μm polyimide non-woven fabric.
Example 4
This example provides a method for preparing a separator with a mixed conductor coating.
2000g of a novel carbon-coated solid electrolyte material Li2Al0.5Zr1.5Si0.5P2.5O12C-C (ratio: 1: 0.3: 0.1), 40g of polyethylene glycol, 20g of sodium carboxymethylcellulose, 200g of styrene-butadiene rubber, 20g of polyoxyethylene alkylphenol ether and 8kg of deionized water were added to a stirring tank, and dispersed and stirred at 2500rmp for 3 hours.
And (3) sanding the dispersed slurry, taking out the slurry, and then carrying out ultrasonic treatment, wherein the technological parameters are the same as those in example 1, so that the required novel carbon-coated solid electrolyte material coating slurry is obtained.
Uniformly coating the slurry on the surface of a base film by using an anilox roller, and drying, wherein the drying temperature is 50 ℃, the tape moving speed of the base film is 15m/min, and the coating thickness is 2 mu m. The basal membrane is a polyethylene microporous membrane with the diameter of 12 mu m, and the porosity of the basal membrane is 40 percent.
And (3) coating a layer of water-based polyvinylidene fluoride (PVDF) slurry on the coating of the coated base film, and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating. Wherein the drying temperature is 60 ℃, the base film moving speed is 15m/min, and the coating thickness is 1 μm.
Example 5
This example provides a method for preparing a separator with a mixed conductor coating.
2000g of a novel carbon-coated solid electrolyte material Li2Fe0.5Zr1.5Si0.5P2.5O12Adding 40g of polyvinylpyrrolidone, 200g of polyvinylidene fluoride and 8kg of N-methyl pyrrolidone into a stirring tank at a ratio of 1: 0.4: 0.2, dispersing and stirring for 3 hours at 2500rmp, sanding the dispersed slurry, taking out, and performing ultrasonic treatment to obtain the required novel carbon-coated solid electrolyte material coating slurry.
Uniformly coating the slurry on the surface of a base film by using an anilox roller, and drying, wherein the drying temperature is 60 ℃, the tape moving speed of the base film is 12m/min, and the coating thickness is 2 mu m. The base film is 20 μm polyimide non-woven fabric.
And (3) coating a layer of PVDF slurry on the coating of the coated base film, and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating. Wherein the drying temperature is 65 ℃, the base film moving speed is 10m/min, and the coating thickness is 1 μm.
To better illustrate the effects of the examples of the present invention, pouch cells were respectively assembled using the separators of example 1, comparative example 1, and comparative example 2 under the same conditions, and comparative tests were performed.
Comparative example 1
With Li2Zr2Si1P2O12C-C (ratio 1: 0.55: 0.05) undoped carbon-coated solid electrolyte material in place of Li in example 12Al0.5Zr1.5Si0.5P2.5O12a/C-C novel carbon-coated solid electrolyte material, a coating layer was prepared and a separator was coated under the same conditions as in example 1.
Comparative example 2
With Li2Al0.5Zr1.5Si0.5P2.5O12Solid electrolyte material not coated with carbon layer instead of Li in example 12Al0.5Zr1.5Si0.5P2.5O12a/C-C novel carbon-coated solid electrolyte material, a coating layer was prepared and a separator was coated under the same conditions as in example 1.
The physical properties and electrochemical properties of the separator prepared in example 1 were compared with those of comparative example 1 and comparative example 2.
TABLE 1
Table 1 shows the physical property comparison data of the separator of example 1 with the separators of comparative examples 1 and 2, and it can be seen from the data of table 1 that the separator coated with the carbon-coated material of the present invention is significantly better in physical strength and moisture than the separator of the material not coated with carbon, and the safety of the battery is effectively improved.
| Numbering | Capacity retention after 100 weeks | Capacity retention after 150 weeks | Capacity retention after 200 weeks |
| Example 1 | ＞95％ | ＞95％ | ＞90％ |
| Comparative example 1 | ＞95％ | 90％-95％ | ＜85％ |
| Comparative example 2 | ＞95％ | ＜85％ | ＜85％ |
TABLE 2
Table 2 shows comparison data of the cycle capacities of the pouch battery assembled with the separator of example 1 and the pouch batteries assembled with the separators of comparative examples 1 and 2, and it can be seen from the data of table 2 and fig. 3 that the pouch battery assembled with the separator coated with the novel carbon-coated solid electrolyte material of the present invention is significantly better in capacity retention rate and internal resistance after cycling than the pouch battery assembled with the separator not coated with carbon, which indicates that the separator including the mixed conductor coating of the present invention can effectively prolong the service life of the battery.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A mixed conductor coating-containing separator, comprising: a base film, and a coating layer attached to at least one side surface of the base film;
the coating comprises a novel carbon-coated solid electrolyte material; the novel carbon-coated solid electrolyte material is of a core-shell structure, and the core-shell structure comprises a core and a shell; wherein the inner core comprises a first component and a second component;
the first component is a solid electrolyte material with a chemical general formula
LixAyZr2-ySix-y-1P4-x+yO12X is more than or equal to 1 and less than or equal to 5, and y is more than 0 and less than or equal to 1; wherein A comprises: one or more of Al, Cr, Fe, Ga, Se, Y, In or La;
the second component specifically comprises amorphous carbon and/or crystalline carbon;
the shell is a carbon layer.
2. The separator with a mixed conductor coating according to claim 1, characterized in that the carbon layer is in particular a carbon layer film or carbon layer particles; the thickness of the carbon layer is between 1nm and 2 mu m; the coverage rate of the carbon layer on the surface of the inner core is 50% -100%;
the grain size of the inner core is between 30nm and 100 mu m;
the particle size of the novel carbon-coated solid electrolyte material is 31nm-102 mu m;
the mass ratio of the first component to the second component to the carbon layer is 1 (0-0.6): (0.002-0.6).
3. The hybrid conductor coating-containing separator according to claim 1, wherein the coating further has a subbing layer on one or both sides; the material of the glue layer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or polymethyl methacrylate.
4. The separator with a mixed conductor coating according to claim 3, characterized in that the thickness of the coating is between 0.5 μm and 10 μm and the thickness of the glue layer is between 0.2 μm and 5 μm.
5. The separator with the mixed conductor coating according to claim 1, wherein the base film is an organic base film comprising a polyolefin microporous film or a polyimide non-woven fabric; the thickness of the basement membrane is 5-20 μm, and the porosity is 30-80%.
6. The separator comprising a mixed conductor coating according to claim 1, characterized in that said coating comprises in particular: 20-80 wt% of solvent, 10-79.95 wt% of novel carbon-coated solid electrolyte material, 0-5 wt% of wetting agent, 0-5 wt% of dispersing agent, 0.05-20 wt% of binder and 0-5 wt% of auxiliary agent;
the novel carbon-coated solid electrolyte material in the coating accounts for more than 40% of the total mass of the solid;
the solvent comprises: one or more of deionized water, N-methyl pyrrolidone, alcohol, dimethylformamide, ethyl acetate and isopropanol;
the wetting agent comprises: one or more of polydimethylsiloxane, polyether modified siloxane, polyoxyethylene ether, polyoxyethylene octylphenol ether, polyether siloxane, sodium alkyl benzene sulfonate, polyoxyethylene alkyl phenol ether, polyoxyethylene fatty alcohol ether or sodium lauryl sulfate;
the dispersant comprises: one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylic acid, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyacrylamide, polyvinyl acetate or polyurethane;
the auxiliary agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine (alcohol), polyoxyethylene fatty alcohol sulfate, polyglycol ether, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene alkylamine, polyoxyethylene amide, titanate coupling agent or aluminate coupling agent.
7. A method for preparing a separator comprising a mixed conductor coating according to any of claims 1 to 6, wherein the method comprises:
dispersing the novel carbon-coated solid electrolyte material, the dispersing agent and the solvent in a stirring tank at a high speed at a dispersion speed of 2000-3000 rmp in parts by mass;
sanding the dispersed slurry, taking out the slurry by sanding, adding the binder, the wetting agent and the auxiliary agent according to the required mass part, fully stirring and carrying out ultrasonic treatment to obtain the coating slurry;
uniformly coating the coating slurry on at least one surface of a base film and drying to obtain the diaphragm with the novel carbon-coated solid electrolyte material coating and the mixed conductor coating;
the coating slurry specifically comprises the following components in parts by weight: 20-80 wt% of solvent, 10-79.95 wt% of novel carbon-coated solid electrolyte material, 0-5 wt% of wetting agent, 0-5 wt% of dispersing agent, 0.05-20 wt% of binder and 0-5 wt% of auxiliary agent.
8. The method of preparing a separator comprising a mixed conductor coating according to claim 7, wherein the coating method comprises any one of a doctor blade coating method, a gravure roll coating method, and a spray coating method.
9. A lithium ion battery comprising the separator with a mixed conductor coating according to any of claims 1 to 6.
10. Use of the mixed conductor coating-containing separator according to any one of claims 1 to 6 for a battery separator for a secondary battery.
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