CN114156600B - 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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- CN114156600B CN114156600B CN202111519939.5A CN202111519939A CN114156600B CN 114156600 B CN114156600 B CN 114156600B CN 202111519939 A CN202111519939 A CN 202111519939A CN 114156600 B CN114156600 B CN 114156600B
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- solid electrolyte
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- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 239000011533 mixed conductor Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 78
- 239000000463 material Substances 0.000 claims abstract description 63
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 55
- 239000010410 layer Substances 0.000 claims abstract description 33
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- -1 polydimethylsiloxane Polymers 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 23
- 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 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 239000011230 binding 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
- 239000002245 particle 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
- 239000003292 glue Substances 0.000 claims description 9
- 229920000056 polyoxyethylene ether Chemical class 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 239000001768 carboxy methyl cellulose 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
- 238000009210 therapy by ultrasound Methods 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000012528 membrane 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-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
- 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
- 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
- 238000007606 doctor blade method Methods 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 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
- 239000007771 core particle Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 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
- 150000002500 ions Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a diaphragm containing a mixed conductor coating, and 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 core comprises a first component and a second component; the first component is a solid electrolyte material, and the chemical general formula is Li xAyZr2‑ySix‑y‑1P4‑x+yO12, x 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: al, cr, fe, ga, se, Y, in or La; the second component comprises in particular amorphous carbon and/or crystalline carbon; the 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, a lithium battery is used as a novel secondary battery, has the advantages of high energy density, long cycle life and the like, and has an application range which is continuously expanded, and is widely applied to power automobiles, energy storage and portable electric appliances. However, frequent lithium battery safety accidents are increasingly attracting attention, and the performance requirements of the lithium ion batteries are also increasing, so that the lithium batteries are required to have higher capacity and better capacity retention rate, and more importantly, higher safety. The diaphragm is used as an important component of the lithium battery, so that the contact of the positive electrode and the negative electrode can be effectively prevented from being short-circuited, and the safety of the lithium battery is very important to be influenced, so that the high-performance diaphragm has considerable improvement on the electrical performance and the safety of the lithium battery.
The ceramic separator is the most widely used lithium battery separator at present, but the existing ceramic separator on the market has the problems of poor wettability and ion conductivity, poor battery cycle performance, insignificant improvement of heat resistance of the separator and the like, so that the lithium battery separator with excellent performance is required to meet the requirement of battery performance.
Disclosure of Invention
The embodiment of the invention provides a diaphragm containing a mixed conductor coating, a preparation method and application thereof, wherein the diaphragm containing the mixed conductor coating and provided with a novel carbon-coated solid electrolyte material coating replaces the 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 can be reduced.
In a first aspect, embodiments of the present invention provide a separator comprising a mixed conductor coating 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; the core comprises a first component and a second component;
the first component is specifically a solid electrolyte material, and has a chemical general formula of
Li xAyZr2-ySix-y-1P4-x+yO12, x 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: al, cr, fe, ga, se, Y, in or La;
the second component comprises in particular 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 particle 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 are also provided with glue layers; 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 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, including a polyolefin microporous film or a polyimide non-woven fabric; the thickness of the base film is 5-20 mu m, and the porosity is 30-80%.
Preferably, the coating specifically includes: 20 to 80 weight percent of solvent, 10 to 79.95 weight percent of novel carbon-coated solid electrolyte material, 0 to 5 weight percent of wetting agent, 0 to 5 weight percent of dispersing agent, 0.05to 20 weight percent of binder and 0 to 5 weight percent 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, octylphenol polyoxyethylene ether, polyether siloxane, sodium alkylbenzenesulfonate, polyoxyethylene alkylphenol 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, cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
The binder 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 the following components: 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 method for preparing a separator containing a mixed conductor coating according to the first aspect, where the preparation method includes:
According to the required mass parts, the novel carbon-coated solid electrolyte material, the dispersing agent and the solvent are dispersed in a stirring tank at a high speed at a dispersion speed of 2000-3000 rmp;
sanding the dispersed slurry, adding a binder, a wetting agent and an auxiliary agent according to the required parts by mass after sanding, 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 membrane with the novel carbon-coated solid electrolyte material coating;
Wherein, the coating slurry specifically comprises the following components in parts by weight: 20 to 80 weight percent of solvent, 10 to 79.95 weight percent of novel carbon-coated solid electrolyte material, 0 to 5 weight percent of wetting agent, 0 to 5 weight percent of dispersing agent, 0.05 to 20 weight percent of binder and 0 to 5 weight percent of auxiliary agent.
Further preferably, the coating method includes any one of a doctor blade coating method, a gravure roll coating method, and a spray coating method.
In a third aspect, embodiments of the present invention provide a lithium ion battery comprising a separator comprising the mixed conductor coating of the first aspect.
In a fourth aspect, an embodiment of the present invention provides a use of the separator containing a mixed conductor coating layer according to the first aspect, where the separator containing a mixed conductor coating layer according to the first aspect is used for a battery separator of a secondary battery.
The separator containing the mixed conductor coating provided by the embodiment of the invention not only has the thermal stability of the traditional ceramic separator because the novel carbon-coated solid electrolyte material is introduced, but also has migration capability in the novel carbon-coated solid electrolyte material of the separator unlike the situation that lithium ions do not have migration capability in the traditional ceramic, and the unique core-shell structure of the separator can effectively improve the lithium ion conductivity and the interfacial compatibility of electrolyte/electrode, can effectively reduce the moisture of the separator, and can effectively improve the cycle performance and the safety performance of a battery.
Drawings
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
FIG. 1 is a flow chart of a method for preparing a separator containing a mixed conductor coating according to an embodiment of the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a separator comprising a mixed conductor coating provided in example 1 of the present invention;
Fig. 3 is a graph showing the comparison of the internal resistance of the separator containing the mixed conductor coating provided in example 1 of the present invention and the internal resistance of the separator of comparative example 1 and the separator of comparative example 2.
Detailed Description
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
The invention provides a diaphragm containing a mixed conductor coating, which comprises the following components: 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 base film is 5-20 mu m, and the porosity is 30-80%.
The coating includes a novel carbon-coated solid electrolyte material.
The novel carbon-coated solid electrolyte material is in a core-shell structure and comprises an inner core and an outer shell, and the particle size of the novel carbon-coated solid electrolyte material is 31nm-102 mu m.
The core comprises a first component and a second component, and the particle size of the core is between 30nm and 100 mu m. The first component is a solid electrolyte material, and the chemical general formula is Li xAyZr2-ySix-y-1P4-x+yO12, x 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: al, cr, fe, ga, se, Y, in or La. The second component comprises in particular amorphous carbon and/or crystalline carbon.
The shell is a carbon layer and comprises 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 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 Li xAyZr2-ySix-y-1P4-x+yO12/C-C, wherein x is more than or equal to 1 and less than or equal to 5, and y is more than or equal to 0 and less than or equal to 1.
In addition to the novel carbon-coated solid electrolyte materials described above, the coating also includes other components. The composition of the coating may specifically include: 20 to 80 weight percent of solvent, 10 to 79.95 weight percent of novel carbon-coated solid electrolyte material, 0to 5 weight percent of wetting agent, 0to 5 weight percent of dispersing agent, 0.05 to 20 weight percent of binder and 0to 5 weight percent 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 agent comprises: one or more of polydimethylsiloxane, polyether modified siloxane, polyoxyethylene ether, octylphenol polyoxyethylene ether, polyether siloxane, sodium alkylbenzenesulfonate, polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether or sodium lauryl sulfate;
The dispersing agent comprises: one or more of polyethylene glycol, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
The binder 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 two sides of the coating 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 mu m and 5 mu m.
The above separator containing the mixed conductor coating can be obtained by the following preparation method. The specific method steps are shown in fig. 1, and comprise the following steps:
Step 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 according to the required parts by weight;
Step 120, sanding the dispersed slurry, adding a binder according to the required mass parts after sanding, fully stirring a wetting agent and an auxiliary agent, and performing ultrasonic treatment to obtain coating slurry;
and 130, uniformly coating the coating slurry on at least one surface of the base film and drying to obtain the membrane with the novel carbon-coated solid electrolyte material coating.
Specifically, the coating method includes any one of a doctor blade coating method, a gravure roll coating method, and a spray coating method.
In the above method steps, the selection and mass parts of each component material are consistent with the specific materials and numerical ranges in the above battery separator embodiments, and are not described herein.
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, for example, can be used in a lithium ion battery together with a positive electrode, a negative electrode and electrolyte.
For better understanding of the technical solution provided by the present invention, the following description will respectively illustrate specific processes for preparing a separator containing a mixed conductor coating layer using several methods provided in the above embodiments of the present invention, and methods and battery characteristics for applying the same to a secondary battery, in a plurality of specific examples.
Example 1
The embodiment provides a preparation method of a diaphragm containing a mixed conductor coating.
40G of polyethylene glycol, 20g of sodium carboxymethylcellulose and 8kg of deionized water were added to a pre-stirring tank and dispersed at a dispersion speed of 3000rpm for 1 hour to obtain a first slurry.
1800G of the novel carbon-coated solid electrolyte material Li 2Al0.5Zr1.5Si0.5P2.5O12/C-C (the ratio is 1:0.55:0.05) was added to the first slurry, dispersed at a dispersion speed of 2500rpm for 1.5 hours, and the dispersed slurry was added to a sand mill for sand milling for 0.5 hour to obtain a 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 30rpm.
The third slurry was sonicated for 0.5 hours at an ultrasonic frequency of 5kHz.
And carrying out vacuum defoaming on the ultrasonic slurry for 0.5 hour.
And filtering the slurry subjected to vacuum deaeration through 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 tape speed is 15m/min, and the coating thickness is 2 mu m. The base film was a 12 μm polyethylene microporous film (wet process) with a base film porosity of 40%.
Fig. 2 is an SEM image of a separator containing a mixed conductor coating prepared in the embodiment of the invention, and as can be seen from fig. 2, the particle diameter distribution of the mixed conductor coating is uniform, and the gaps between the particles are smaller, so that the performance stability of the material is higher, and the thermal stability of the separator can be effectively improved.
Example 2
The embodiment provides a preparation method of a diaphragm containing a mixed conductor coating.
1900G of novel carbon-coated solid electrolyte material Li 2Ga0.5Zr1.5Si0.5P2.5O12/C-C (ratio 1:0.4:0.03), 20g of sodium dodecyl benzene sulfonate, 20g of sodium hexametaphosphate, 200g of polyvinyl alcohol, 20g of polydimethylsiloxane and 8kg of deionized water are added into a stirring tank, and dispersed and stirred for 3 hours at 2500 rmp.
The dispersed slurry was sanded, taken out and subjected to ultrasonic treatment, and the process parameters were the same as in example 1, to obtain a slurry having a novel carbon-coated solid electrolyte material.
And uniformly coating the slurry with the novel carbon-coated solid electrolyte material on the inner and outer side surfaces of the 9 mu m polyethylene microporous membrane by using an anilox roller, and drying to obtain the double-sided coated membrane with the novel carbon-coated solid electrolyte material coating.
Example 3
The embodiment provides a preparation method of a diaphragm containing a mixed conductor coating.
2000G of the novel carbon-coated solid electrolyte material Li 2La0.5Zr1.5Si0.5P2.5O12/C-C (ratio 1:0.56:0.1), 40g of polyvinylpyrrolidone, 200g of polyvinylidene fluoride and 8kg of N-methylpyrrolidone are added into a stirring tank, and dispersed and stirred for 2 hours at 2500 rmp.
And (3) sanding the dispersed slurry, taking out, and performing ultrasonic treatment, wherein the technological parameters are the same as those of the embodiment 1, so as to obtain the slurry with the novel carbon-coated solid electrolyte material.
And uniformly coating the sizing agent 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 travelling speed is 12m/min, the coating thickness is 1.5 mu m, and the base film is 20 mu m polyimide non-woven fabric.
Example 4
The embodiment provides a preparation method of a diaphragm containing a mixed conductor coating.
2000G of the novel carbon-coated solid electrolyte material Li 2Al0.5Zr1.5Si0.5P2.5O12/C-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 are added into a stirring tank, and dispersed and stirred for 3 hours at 2500 rmp.
And (3) sanding the dispersed slurry, taking out, and performing ultrasonic treatment, wherein the technological parameters are the same as those of the embodiment 1, so as to obtain the novel carbon-coated solid electrolyte material coating slurry.
The sizing agent is uniformly coated on the surface of a base film by an anilox roller and is dried, the drying temperature is 50 ℃, the base film travelling speed is 15m/min, and the coating thickness is 2 mu m. The base film is a 12 μm polyethylene microporous film, and the porosity of the base film is 40%.
And (3) adding a layer of aqueous polyvinylidene fluoride (PVDF) slurry on the coated coating of the 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 tape speed is 15m/min, and the coating thickness is 1 mu m.
Example 5
The embodiment provides a preparation method of a diaphragm containing a mixed conductor coating.
2000G of novel carbon-coated solid electrolyte material Li 2Fe0.5Zr1.5Si0.5P2.5O12/C-C (the ratio is 1:0.4:0.2), 40g of polyvinylpyrrolidone, 200g of polyvinylidene fluoride and 8kg of N-methyl pyrrolidone are added into a stirring tank, dispersed and stirred for 3 hours under 2500rmp, and the dispersed slurry is sanded, taken out and then subjected to ultrasonic treatment, so that the required novel carbon-coated solid electrolyte material coating slurry is obtained.
The sizing agent is uniformly coated on the surface of a base film by an anilox roller and is dried, the drying temperature is 60 ℃, the base film tape speed is 12m/min, and the coating thickness is 2 mu m. The base film is 20 μm polyimide nonwoven fabric.
And (3) adding a layer of PVDF slurry on the coated coating of the base film, and drying to obtain the membrane with the novel carbon-coated solid electrolyte material coating. Wherein the drying temperature is 65 ℃, the base film tape speed is 10m/min, and the coating thickness is 1 mu m.
To better illustrate the effect of the examples of the present invention, comparative tests were performed by assembling the pouch cells with the separators of example 1, comparative example 1 and comparative example 2, respectively, under the same conditions.
Comparative example 1
A coating layer and a separator were prepared and coated under the same conditions as in example 1, except that the novel carbon-coated solid electrolyte material of Li 2Al0.5Zr1.5Si0.5P2.5O12/C-C in example 1 was replaced with a carbon-coated solid electrolyte material of Li 2Zr2Si1P2O12/C-C (ratio of 1:0.55:0.05) which was not doped.
Comparative example 2
The novel Li 2Al0.5Zr1.5Si0.5P2.5O12/C-C carbon-coated solid electrolyte material of example 1 was replaced with a solid electrolyte material in which Li 2Al0.5Zr1.5Si0.5P2.5O12 was not coated with a carbon layer, and a coating layer was prepared and a separator was coated under the same conditions as in example 1.
The separator prepared in this example 1 was compared with the separator of comparative example 1 and the separator of comparative example 2 in terms of physical properties and electrochemical properties.
TABLE 1
Table 1 shows that the physical properties of the separator of example 1 and the separator of comparative examples 1 and 2 are significantly better than those of the separator of the material without carbon coating in physical strength and moisture, and the safety of the battery is effectively improved as shown in table 1.
| Numbering device | 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 is the cycle capacity comparison data of the separator-assembled soft pack battery of example 1 and the separator-assembled soft pack batteries of comparative examples 1 and 2, and it can be seen from the data of table 2 and fig. 3 that the separator-assembled soft pack battery coated with the novel carbon-coated solid electrolyte material of the present invention is also significantly better in terms of capacity retention rate and internal resistance after cycle than the separator-assembled soft pack battery without carbon coating, which indicates that the separator containing the mixed conductor coating of the present invention can effectively improve the service life of the battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A separator comprising a mixed conductor coating, the mixed conductor coating 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 core comprises a first component and a second component;
the first component is specifically a solid electrolyte material, and has a chemical general formula of
Li xAyZr2-ySi x-y-1P4-x+yO12, x 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: al, cr, fe,
Ga. One or more of Se, Y, in or La;
the second component comprises in particular amorphous carbon and/or crystalline carbon;
The shell is a carbon layer;
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%.
2. The mixed conductor coated separator of claim 1 wherein the core particle size is between 30nm and 100 μm;
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 separator with mixed conductor coating according to claim 1, wherein one or both sides of the coating further have a glue layer; the material of the glue layer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer or polymethyl methacrylate.
4. A separator with mixed conductor coating according to claim 3, wherein 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 mixed conductor coated separator of claim 1, wherein the base film is an organic base film comprising a polyolefin microporous film or a polyimide nonwoven fabric; the thickness of the base film is 5-20 mu m, and the porosity is 30-80%.
6. The separator with mixed conductor coating according to claim 1, characterized in that said coating comprises in particular: 20 to 80 weight percent of solvent, 10 to 79.95 weight percent of novel carbon-coated solid electrolyte material, 0 to 5 weight percent of wetting agent, 0 to 5 weight percent of dispersing agent, 0.05 to 20 weight percent of binder and 0 to 5 weight percent 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, octylphenol polyoxyethylene ether, polyether siloxane, sodium alkylbenzenesulfonate, polyoxyethylene alkylphenol 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, cetyltrimethylammonium bromide, polyvinylpyrrolidone, sodium polyacrylate or polymethacrylate;
The binder 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 the following components: 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 of preparing a separator comprising a mixed conductor coating according to any one of claims 1-6, comprising:
According to the required mass parts, the novel carbon-coated solid electrolyte material, the dispersing agent and the solvent are dispersed in a stirring tank at a high speed at a dispersion speed of 2000-3000 rmp;
sanding the dispersed slurry, adding a binder, a wetting agent and an auxiliary agent according to the required parts by mass after sanding, 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 membrane with the novel carbon-coated solid electrolyte material coating and the mixed conductor coating;
Wherein, the coating slurry specifically comprises the following components in parts by weight: 20 to 80 weight percent of solvent, 10 to 79.95 weight percent of novel carbon-coated solid electrolyte material, 0 to 5 weight percent of wetting agent, 0 to 5 weight percent of dispersing agent, 0.05 to 20 weight percent of binder and 0 to 5 weight percent of auxiliary agent.
8. The method for producing a separator containing 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 a separator comprising a mixed conductor coating according to any of the preceding claims 1-6.
10. Use of the separator containing mixed conductor coating according to any one of the preceding claims 1-6, characterized in that the separator containing mixed conductor coating is used for a battery separator of a secondary battery.
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