CN113991241A - Multifunctional film for energy storage device and preparation method thereof - Google Patents
Multifunctional film for energy storage device and preparation method thereof Download PDFInfo
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- CN113991241A CN113991241A CN202111132646.1A CN202111132646A CN113991241A CN 113991241 A CN113991241 A CN 113991241A CN 202111132646 A CN202111132646 A CN 202111132646A CN 113991241 A CN113991241 A CN 113991241A
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- 238000004146 energy storage Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 136
- 239000002243 precursor Substances 0.000 claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 84
- 239000006185 dispersion Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- -1 2-methylimidazole compound Chemical class 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 6
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002356 single layer Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 claims description 3
- QGRVXEOIASZLIL-UHFFFAOYSA-N 3-phenylbenzene-1,2-dithiol Chemical compound SC1=CC=CC(C=2C=CC=CC=2)=C1S QGRVXEOIASZLIL-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 claims description 3
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006193 diazotization reaction Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 230000007547 defect Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 36
- 239000010409 thin film Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000005457 optimization Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000013086 titanium-based metal-organic framework Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000013084 copper-based metal-organic framework Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- YJHVQDZLQLAMFQ-UHFFFAOYSA-N C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O.[Li] Chemical compound C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O.[Li] YJHVQDZLQLAMFQ-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000013094 zinc-based metal-organic framework Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 230000006698 induction Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
-
- 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
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a multifunctional film for an energy storage device and a preparation method thereof, wherein the preparation method comprises the following steps: respectively dispersing precursors of a graphene-based material, a metal-organic framework material or a metal-organic framework material into a solvent to respectively obtain a graphene-based material dispersion liquid, a metal-organic framework material dispersion liquid or a precursor dispersion liquid of the metal-organic framework material; mixing the graphene-based material dispersion liquid with a metal-organic framework material dispersion liquid or a precursor dispersion liquid of a metal-organic framework material to obtain a mixed system; transferring the mixed system to a planar substrate; and removing the solvent to obtain the multifunctional film for the energy storage device. The film prepared by the invention has good multiplying power and cycle performance on the premise of ensuring good wettability, has good tensile strength and puncture resistance, is suitable for new energy storage devices, and overcomes the defects of poor mechanical property, poor electrolyte wettability, complex preparation process and the like of the traditional film.
Description
Technical Field
The invention relates to the technical field of thin film materials, in particular to a multifunctional thin film for an energy storage device and a preparation method thereof.
Background
In each component of the energy storage device, the diaphragm is an electronic insulation and ion conduction thin film material with rich pore channels, plays a role in isolating the positive electrode and the negative electrode and preventing internal short circuit, and is an essential part of the energy storage device. The safety and electrochemical performance (especially rate discharge performance) of the energy storage device are influenced most greatly by the diaphragm. Currently, the most commonly used separators for commercial lithium ion batteries mainly include: the membrane is based on traditional high molecular materials and has the following defects: 1) the membrane is highly flammable, is essentially hydrocarbon, is easy to burn when meeting open fire, is easy to melt when meeting high heat, leads to short circuit of the positive electrode and the negative electrode, and causes potential safety hazards such as combustion and explosion of the battery; 2) the mechanical property is poor, and the tensile strength and the puncture resistance of polyethylene and polypropylene high polymer materials are poor, so that the battery is swelled or is subjected to larger external stress, and the diaphragm is easy to break or be punctured, thereby causing accidents such as internal short circuit and the like; 3) the wetting property of the electrolyte is poor, and the olefin polymer material is difficult to wet with a solvent in an electrode solution because the surface of the olefin polymer material has no polar functional groups; 4) the porosity is insufficient, the pore channel of the diaphragm is a way for ensuring the transmission of the electrolyte, the higher porosity and the proper pore diameter are beneficial to the diffusion of the electrolyte, so that the rate capability of the energy storage device is improved, however, the polyethylene and polypropylene-based diaphragms are the pore channels generated by stretching, and have the defects of low porosity and uneven pore channel size; 5) the diaphragm is applied in the fields of lithium-sulfur batteries and organic batteries, the novel batteries generally have the defect of high solubility of discharge products in electrolyte, and serious shuttle effect exists between a positive electrode and a negative electrode, so that the capacity is reduced, and the charge-discharge efficiency and the cycle performance are deteriorated; 6) finally, the preparation process of the diaphragm involves complicated processes of extrusion, melting, longitudinal/transverse stretching, extraction and the like of raw materials, and the processes are complicated and high in energy consumption. Therefore, it is very urgent to develop a functional thin film with high efficiency for an energy storage device.
Disclosure of Invention
The invention provides a multifunctional film for an energy storage device and a preparation method thereof, aiming at the defects of flammability, poor mechanical property, poor electrolyte wettability, insufficient porosity, unsuitability for novel energy storage devices and complex preparation process of the diaphragm used by the existing energy storage device.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a multifunctional film for an energy storage device comprises the following steps:
s1, respectively dispersing precursors of the graphene-based material, the metal-organic framework material or the metal-organic framework material into a solvent to respectively obtain a graphene-based material dispersion liquid, a metal-organic framework material dispersion liquid or a metal-organic framework material precursor dispersion liquid;
s2, mixing the graphene-based material dispersion liquid obtained in the step S1 with a metal-organic framework material dispersion liquid or a precursor dispersion liquid of a metal-organic framework material to obtain a mixed system;
s3, transferring the mixed system prepared in the S2 to a plane substrate;
and S4, removing the solvent to obtain the multifunctional film for the energy storage device.
As a further optimization of the preparation method of the multifunctional thin film for the energy storage device, in the step S1, the graphene-based material is single-layer graphene oxide, few-layer graphene oxide, graphene modified with amino/carboxyl/mercapto groups on the surface, or a mixture thereof.
As a further optimization of the preparation method of the multifunctional thin film for an energy storage device of the present invention, the metal-organic framework material described in S1 is a metal framework material based on one or more of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium, vanadium, etc.
As a further optimization of the preparation method of the multifunctional film for the energy storage device, the precursor of the metal-organic framework material described in S1 includes a precursor one and a precursor two, where the precursor one is one or more of hydrochloride, sulfate, nitrate and carbonate of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium and vanadium; the precursor II is one or more of polycarboxyl compound, polyamino compound, polyhydroxy compound, multi-thiol compound, imidazole and 2-methylimidazole compound, wherein the polycarboxyl compound comprises p-hydroxybenzoic acid, m-benzoic acid, trimesic acid and biphenyl dicarboxylic acid, the polyamino compound comprises p-phenylenediamine, toluenediamine and biphenyldiamine, the polyhydroxy compound comprises hydroquinone, resorcinol, biphenol and the like, and the multi-thiol compound comprises p-benzenedithiol, m-benzenedithiol and biphenyl dithiol.
As a further optimization of the preparation method of the multifunctional thin film for the energy storage device, the solvent of the dispersed graphene-based material, the metal-organic framework material or the precursor of the metal-organic framework material described in S1 is one or more of water, ethanol, isopropanol, acetone, methanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile.
As a further optimization of the preparation method of the multifunctional thin film for the energy storage device, the concentration of the graphene-based material dispersion liquid in S1 is less than 20 mg/ml.
As a further optimization of the preparation method of the multifunctional film for the energy storage device, the graphene-based material is single-layer graphene oxide, and distilled water is added for ultrasonic dispersion to obtain a graphene-based material dispersion solution; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively zinc nitrate and 2-methylimidazole, and the first precursor and the second precursor are respectively dispersed in water to obtain a first precursor dispersion liquid and a second precursor dispersion liquid; and then adding the precursor primary dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, adding the precursor secondary dispersion liquid, continuing stirring, transferring the mixed solution, performing suction filtration to remove the solvent, and drying to obtain the multifunctional film material.
As a further optimization of the preparation method of the multifunctional film for the energy storage device, the graphene-based material is graphene oxide, para aminobenzoic acid is modified on the surface of the graphene oxide through diazotization to obtain benzoic acid modified graphene oxide, and the benzoic acid modified graphene oxide is ultrasonically dispersed in N, N-dimethylformamide to obtain graphene-based material dispersion liquid; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively copper nitrate and biphenyl dicarboxylic acid, and the first precursor and the second precursor are dispersed in an N, N-dimethylformamide solution to obtain a precursor dispersion liquid; and then adding the precursor dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, then coating the mixed solution on a flat substrate by blade coating, and heating to remove the solvent, thus obtaining the multifunctional film material.
As a further optimization of the preparation method of the multifunctional film for the energy storage device, the graphene-based material is graphene oxide, and the graphene oxide is ultrasonically dispersed in ethanol to obtain graphene-based material dispersion liquid; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively tetrabutyl titanate and terephthalic acid, and the first precursor and the second precursor are dispersed in an ethanol/N, N-dimethylformamide mixed solution to obtain a precursor dispersion solution; and then adding the precursor dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, transferring and coating the mixed solution on an aluminum foil, heating in an oven to remove the solvent, and stripping to obtain the multifunctional film material.
The multifunctional film for the energy storage device is prepared according to the preparation method, the mass percent of the graphene-based material in the multifunctional film is 1-90%, the mass percent of the metal-organic framework material or the precursor of the metal-organic framework material is more than 10%, and the thickness of the film is 3-200 μm.
Advantageous effects
The multifunctional film for the energy storage device and the preparation method thereof disclosed by the invention have the following advantages:
the film prepared by mixing the dispersion liquid of the graphene-based material and the dispersion liquid of the metal-organic framework material or the precursor thereof can prevent the shuttle effect of a discharge product which is easy to dissolve in the electrolyte between a positive electrode and a negative electrode on the premise of ensuring good wettability, has an induction effect on the deposition and dissolution reaction of a lithium metal negative electrode, has good multiplying power and cycle performance, has good tensile strength and puncture resistance, is particularly suitable for new energy storage devices, and overcomes the defects of flammability, poor mechanical property, poor wettability of the electrolyte, insufficient porosity, unsuitability for new energy storage devices and complex preparation process of the film used in the traditional energy storage devices.
Mixing the graphene-based material and the metal-organic framework material dispersion liquid or the precursor dispersion liquid of the metal-organic framework material to form dispersion liquid respectively, and then mixing and preparing the film, wherein the graphene-based material has larger sheet diameter and extremely thin thickness, and stronger accumulation acting force exists between sheet layers, so that the graphene-based material is easy to stack or agglomerate, and the intrinsic characteristic of graphene is lost, therefore, the graphene-based material is mixed with a solvent to form a stable dispersion solution, and the graphene is prevented from stacking or agglomerating; the situation that if the graphene-based material and the metal-organic framework material or the precursor of the metal-organic framework material are dispersed together, metal ions can coordinate with oxygen-containing functional groups on the surface of the graphene-based material to further initiate agglomeration is avoided, and finally the prepared film is uniform in texture, stable in performance and high in quality.
The graphene-based material is used as one of the components of the multifunctional film, so that the film has a two-dimensional layered structure, has a high specific surface area, and can be modified with various functional groups on the surface, so that the graphene-based material is easily combined with other materials to form a composite film material; meanwhile, the graphene-based material has excellent mechanical properties and flexibility, so that the prepared film material has better tensile strength and puncture resistance. The metal-organic framework material has a high specific surface area and rich interpenetration pore channels, plays a role in organizing the agglomeration of the graphene-based material, and is beneficial to the transmission of electrolyte. The combination of polar functional groups on the surface of the graphene-based material, organic bridging parts of the metal-organic framework material and metal nodes enables the film to have good wettability to polar electrolyte.
The mixed dispersion system is directly transferred to a substrate in a certain mode, so that the method is suitable for large-scale commercial production; the invention can conveniently obtain the film materials with different components by controlling the proportion of the components of the film material; by controlling the concentration or amount of the components, the thickness of the film material can be easily controlled.
Drawings
FIG. 1 is a graph comparing the rate capability of lithium iron phosphate batteries of GO/Zn-MOFs membranes and commercial PE membranes obtained in example 1 of the present invention;
FIG. 2 is a graph comparing the rate performance of lithium-sulfur batteries with GO-COOH/Cu-MOFs separator and commercial PP separator obtained in example 2 of the present invention;
FIG. 3 is a graph comparing the cycle performance of lithium-sulfur batteries with GO-COOH/Cu-MOFs separator and commercial PP separators obtained in example 2 of the present invention;
FIG. 4 is an SEM image of the GO/Ti-MOFs membrane obtained in example 3 of the present invention;
FIG. 5 is a graph comparing the rate performance of lithium-anthraquinone organic batteries of GO/Ti-MOFs separator obtained in example 3 of the present invention and commercial PE separator.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
A preparation method of a multifunctional film for an energy storage device comprises the following steps:
s1, respectively dispersing precursors of the graphene-based material, the metal-organic framework material or the metal-organic framework material into a solvent to respectively obtain a graphene-based material dispersion liquid, a metal-organic framework material dispersion liquid or a metal-organic framework material precursor dispersion liquid;
s2, mixing the graphene-based material dispersion liquid obtained in the step S1 with a metal-organic framework material dispersion liquid or a precursor dispersion liquid of a metal-organic framework material to obtain a mixed system;
s3, transferring the mixed system prepared in the S2 to a plane substrate;
and S4, removing the solvent to obtain the multifunctional film for the energy storage device.
The graphene-based material of S1 is a single-layer graphene oxide, an oligo-layer graphene oxide, a graphene with a surface modified with amino/carboxyl/mercapto, or a mixture thereof. The metal-organic framework material of S1 is a metal framework material based on one or more of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium, vanadium, and the like. S1, wherein the precursor of the metal-organic framework material comprises a first precursor and a second precursor, and the first precursor is one or more of hydrochloride, sulfate, nitrate and carbonate of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium and vanadium; the precursor II is one or more of polycarboxyl compound, polyamino compound, polyhydroxy compound, multi-thiol compound, imidazole and 2-methylimidazole compound, wherein the polycarboxyl compound comprises p-hydroxybenzoic acid, m-benzoic acid, trimesic acid and biphenyl dicarboxylic acid, the polyamino compound comprises p-phenylenediamine, toluenediamine and biphenyldiamine, the polyhydroxy compound comprises hydroquinone, resorcinol, biphenol and the like, and the multi-thiol compound comprises p-benzenedithiol, m-benzenedithiol and biphenyl dithiol. The solvent of the dispersed graphene-based material, the metal-organic framework material or the precursor of the metal-organic framework material described in S1 is one or more of water, ethanol, isopropanol, acetone, methanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile. The concentration of the graphene-based material dispersion liquid of S1 is less than 20 mg/ml.
In a preferred embodiment of the present invention, the dispersing in S1 is performed by one or more of mechanical stirring, magnetic stirring, ultrasonic, ball milling, and high-speed shearing. S3, the transfer is carried out in one or any combination of spin coating, drop coating, blade coating, suction filtration, printing and transfer coating. S4, the solvent is removed by one or more of heating drying, infrared drying and normal temperature evaporation.
The multifunctional film for the energy storage device is prepared according to the preparation method, the mass percent of the graphene-based material in the multifunctional film is 1-90%, the mass percent of the metal-organic framework material or the precursor of the metal-organic framework material is more than 10%, and the thickness of the film is 3-200 μm.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments and the accompanying drawings.
Example 1
Weighing 20mg of single-layer graphene oxide, adding distilled water, and performing ultrasonic dispersion for 1 hour to prepare a solution of 2mg/ml, wherein the obtained graphene-based material is a solution A; weighing 1.8g of 2-methylimidazole, and dissolving in 30ml of water to obtain a solution B; 1.2g of zinc nitrate was weighed and dissolved in 20ml of water with stirring to obtain solution C. Adding the solution B into the solution A, stirring for 30min, performing ultrasonic treatment for 30min, adding the solution C, and continuing stirring for 2 h. And removing the solvent from the mixed solution through suction filtration, and drying the obtained filter membrane for 3 hours in vacuum to finally obtain the composite film material with the thickness of 20 mu m.
The lithium ion battery is assembled by taking the thin film material as a diaphragm (GO/Zn-MOFs), taking commercial lithium iron phosphate as a positive electrode material and a lithium sheet as a negative electrode and a counter electrode, and the electrochemical performance of the lithium ion battery is evaluated and compared with the commercial polyethylene diaphragm (PE). The comparative result is shown in figure 1, the battery taking GO/Zn-MOFs as the diaphragm has the discharge specific capacity of 170mAh/g at 0.3C, is close to the theoretical specific capacity of lithium iron phosphate, and has the discharge specific capacity of 150mAh/g at 5C high rate, which is far superior to the lithium battery taking the commercial diaphragm, mainly because the diaphragm has good electrolyte wettability and conductivity.
Example 2
Weighing 100mg of graphene oxide, modifying p-aminobenzoic acid on the surface of the graphene oxide through diazotization to obtain benzoic acid modified graphene oxide, and dispersing the benzoic acid modified graphene oxide to 50ml of N, N-dimethylformamide through ultrasound to obtain a solution of 2mg/ml, which is a solution A; the solution B was prepared by dissolving 2g of biphenyldicarboxylic acid and 2.5 g of copper nitrate in 50ml of N, N-dimethylformamide under stirring. Adding the solution B into the solution A, stirring for 20min, then performing ultrasonic treatment for 1h, and finally stirring for 4 h. And (3) blade-coating the mixed solution on a flat substrate, heating at 150 ℃ for 5h, and removing the solvent to obtain the composite film material with the thickness of 25 mu m.
The electrochemical performance of the lithium-sulfur battery is evaluated by assembling the lithium-sulfur battery by taking the thin film material as a diaphragm (GO-COOH/Cu-MOFs), taking sulfur/carbon as a positive electrode material and taking a lithium sheet as a negative electrode and a counter electrode, and comparing the electrochemical performance with a commercial polypropylene diaphragm (PP). As shown in fig. 2, the rate performance of the lithium-sulfur battery using GO-COOH/Cu-MOFs as the separator is far superior to that of the lithium-sulfur battery using the commercial separator at each discharge rate; and the cycle performance was also superior to that of a PP separator-based lithium-sulfur battery (see fig. 3). The GO-COOH/Cu-MOFs diaphragm disclosed by the invention can prevent the shuttle effect of a discharge product (polysulfide compound) which is easily dissolved in electrolyte between a positive electrode and a negative electrode on the premise of ensuring good wettability, and has an induction effect on deposition and dissolution reactions of a lithium metal negative electrode, so that good multiplying power and cycle performance are obtained.
Example 3
Weighing 100mg of graphene oxide, and dispersing the graphene oxide into 100ml of ethanol by ultrasonic treatment for 2 hours to obtain a solution of 1mg/ml, namely a solution A; 1.5g of terephthalic acid was dissolved in 50ml of a mixed solution of ethanol/N, N-dimethylformamide (volume ratio: 1) with stirring, and 2.4g of tetrabutyl titanate was added and dissolved with stirring to obtain a solution B. And adding the solution B into the solution A, stirring for 1 hour, then carrying out ultrasonic treatment for 2 hours, and finally stirring for 5.5 hours. And transferring and coating the mixed solution on an aluminum foil, heating the aluminum foil in an oven at 180 ℃ for 2h to remove the solvent, and stripping the film from the aluminum foil to obtain the composite film material with the thickness of 30 mu m.
The lithium-anthraquinone organic lithium battery is assembled by taking the thin film material as a diaphragm (GO/Ti-MOFs), anthraquinone as a positive electrode material and a lithium sheet as a negative electrode and a counter electrode, and the electrochemical performance of the lithium-anthraquinone organic lithium battery is evaluated and compared with a commercial polypropylene diaphragm (PE). As shown in fig. 4, an SEM of the obtained composite thin film shows that Ti-MOFs is deposited on the surface of graphene oxide, and effectively prevents stacking of graphene oxide, and more importantly, the thin film material disclosed by the present invention has rich channels. As shown in fig. 5, the lithium-anthraquinone organic batteries based on GO/Ti-MOFs separator showed superior specific capacity and rate performance compared to commercial PE-based separator, mainly due to the following points: 1) the abundant and interconnected pore channels ensure the efficient and rapid transmission of the electrolyte; 2) the functional groups and Ti-MOFs on the surface of the graphene oxide have good wettability to the electrolyte; 3) the Ti-MOFs prevents the discharge product of the anthraquinone from reciprocating between the anode and the cathode, thereby improving the electrochemical performance.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a multifunctional film for an energy storage device is characterized by comprising the following steps: the method comprises the following steps:
s1, respectively dispersing precursors of the graphene-based material, the metal-organic framework material or the metal-organic framework material into a solvent to respectively obtain a graphene-based material dispersion liquid, a metal-organic framework material dispersion liquid or a metal-organic framework material precursor dispersion liquid;
s2, mixing the graphene-based material dispersion liquid obtained in the step S1 with a metal-organic framework material dispersion liquid or a precursor dispersion liquid of a metal-organic framework material to obtain a mixed system;
s3, transferring the mixed system prepared in the S2 to a plane substrate;
and S4, removing the solvent to obtain the multifunctional film for the energy storage device.
2. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the graphene-based material of S1 is a single-layer graphene oxide, an oligo-layer graphene oxide, a graphene with a surface modified with amino/carboxyl/mercapto, or a mixture thereof.
3. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the metal-organic framework material of S1 is a metal framework material based on one or more of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium, vanadium, and the like.
4. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: s1, wherein the precursor of the metal-organic framework material comprises a first precursor and a second precursor, and the first precursor is one or more of hydrochloride, sulfate, nitrate and carbonate of cobalt, copper, iron, nickel, titanium, niobium, manganese, zinc, chromium and vanadium; the precursor II is one or more of polycarboxyl compound, polyamino compound, polyhydroxy compound, multi-thiol compound, imidazole and 2-methylimidazole compound, wherein the polycarboxyl compound comprises p-hydroxybenzoic acid, m-benzoic acid, trimesic acid and biphenyl dicarboxylic acid, the polyamino compound comprises p-phenylenediamine, toluenediamine and biphenyldiamine, the polyhydroxy compound comprises hydroquinone, resorcinol, biphenol and the like, and the multi-thiol compound comprises p-benzenedithiol, m-benzenedithiol and biphenyl dithiol.
5. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the solvent of the dispersed graphene-based material, the metal-organic framework material or the precursor of the metal-organic framework material described in S1 is one or more of water, ethanol, isopropanol, acetone, methanol, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile.
6. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the concentration of the graphene-based material dispersion liquid of S1 is less than 20 mg/ml.
7. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the graphene-based material is single-layer graphene oxide, and distilled water is added for ultrasonic dispersion to obtain graphene-based material dispersion liquid; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively zinc nitrate and 2-methylimidazole, and the first precursor and the second precursor are respectively dispersed in water to obtain a first precursor dispersion liquid and a second precursor dispersion liquid; and then adding the precursor primary dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, adding the precursor secondary dispersion liquid, continuing stirring, transferring the mixed solution, performing suction filtration to remove the solvent, and drying to obtain the multifunctional film material.
8. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the graphene-based material is graphene oxide, para aminobenzoic acid is modified on the surface of the graphene oxide through diazotization reaction to obtain benzoic acid modified graphene oxide, and the benzoic acid modified graphene oxide is dispersed in N, N-dimethylformamide through ultrasound to obtain graphene-based material dispersion liquid; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively copper nitrate and biphenyl dicarboxylic acid, and the first precursor and the second precursor are dispersed in an N, N-dimethylformamide solution to obtain a precursor dispersion liquid; and then adding the precursor dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, then coating the mixed solution on a flat substrate by blade coating, and heating to remove the solvent, thus obtaining the multifunctional film material.
9. The method of claim 1 for preparing a multifunctional film for an energy storage device, wherein: the graphene-based material is graphene oxide, and the graphene-based material is ultrasonically dispersed into ethanol to obtain graphene-based material dispersion liquid; the precursor of the metal-organic framework material comprises a first precursor and a second precursor, wherein the first precursor and the second precursor are respectively tetrabutyl titanate and terephthalic acid, and the first precursor and the second precursor are dispersed in an ethanol/N, N-dimethylformamide mixed solution to obtain a precursor dispersion solution; and then adding the precursor dispersion liquid into the graphene-based material dispersion liquid, stirring, performing ultrasonic dispersion, transferring and coating the mixed solution on an aluminum foil, heating in an oven to remove the solvent, and stripping to obtain the multifunctional film material.
10. The multifunctional film for an energy storage device prepared by the preparation method according to any one of claims 1, 7, 8 and 9, wherein: the mass percentage of the graphene-based material in the multifunctional film is 1-90%, the mass percentage of the metal-organic framework material or the precursor of the metal-organic framework material is more than 10%, and the thickness of the film is 3-200 mu m.
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