CN114606650A - Flexible film and preparation method and application thereof - Google Patents
Flexible film and preparation method and application thereof Download PDFInfo
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- CN114606650A CN114606650A CN202210078712.XA CN202210078712A CN114606650A CN 114606650 A CN114606650 A CN 114606650A CN 202210078712 A CN202210078712 A CN 202210078712A CN 114606650 A CN114606650 A CN 114606650A
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- potassium
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 118
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 81
- 239000011591 potassium Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 9
- 239000004917 carbon fiber Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 111
- 239000002243 precursor Substances 0.000 claims description 65
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- 239000000243 solution Substances 0.000 claims description 63
- 238000009987 spinning Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 24
- 238000010041 electrostatic spinning Methods 0.000 claims description 21
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 230000007613 environmental effect Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000004246 zinc acetate Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 12
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229920000767 polyaniline Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002985 plastic film Substances 0.000 claims description 2
- 229920006255 plastic film Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 claims description 2
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 8
- 239000006183 anode active material Substances 0.000 description 8
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a flexible membrane, which is a flexible membrane material formed by hollow porous carbon fibers, wherein the flexible membrane has a three-dimensional cross-linked structure, and the carbon fibers have uniform particle size. The invention also discloses a preparation method and application of the flexible film. The flexible membrane disclosed by the invention has a three-dimensional cross-linked structure, and the carbon nanofibers in the flexible membrane have a hollow porous structure, so that on one hand, the membrane material has a large specific surface due to the hollow porous structure, the potassium storage capacity is favorably improved, on the other hand, electrolyte and electrons are favorably transmitted in the electrode material due to the hollow porous structure, and the carbon nanofibers have the characteristics of flexibility and conductivity at the same time, so that the electronic conductivity of the material is enhanced, and the electrochemical performance is improved.
Description
Technical Field
The invention relates to the technical field of potassium ion battery cathode materials, in particular to a flexible membrane and a preparation method and application thereof.
Background
Electrostatic spinning is a common method for preparing fiber materials, and the fiber materials prepared by the electrostatic spinning method have the advantages of large specific surface, high void ratio and the like. The fiber material with various structures and functionalization can be obtained by regulating and controlling the spinning solution and the spinning conditions and further processing the spun fiber. Polyacrylonitrile is a common high molecular polymer suitable for electrostatic spinning, and polyacrylonitrile can be well modified by combining polyacrylonitrile with other materials. The MOFs material has various appearances, and when the MOFs material is subjected to high-temperature treatment, a hollow porous carbon material is easily obtained. When the MOFs material is combined with polyacrylonitrile and subjected to high-temperature treatment, a hollow porous flexible membrane material can be obtained.
Flexible devices are becoming more common in today's daily life, such as various intelligent electronic devices in life, and have very important applications in bio-integration, bionics, and the like. In recent years, the development of flexible electrodes has received great attention. Graphene, carbon nanotubes, commercial carbon cloth, nickel foam, and the like are used as flexible substrates, but development is limited due to problems such as excessive cost and complicated preparation process. Therefore, the electrostatic spinning is a simple, convenient, efficient and low-cost method for preparing the flexible membrane electrode. There are three methods of compounding: the first is growing metal oxide on the surface of one-dimensional carbon material (such as carbon nano tube and carbon nano fiber); the second mode is that metal oxide is grown on the surface of a two-dimensional carbon material (such as graphene); in a third mode, for example, the carbon fiber-coated metal oxide flexible electrode for a capacitor and the preparation method disclosed in patent CN201611069056.8, an electrostatic spinning technology is used to prepare a carbon nanofiber (one-dimensional carbon material) cavity-coated metal oxide nanoparticle flexible film. The problems of the technology are as follows: the carbon nanofibers prepared by the electrostatic spinning technology in the technology are in a solid fiber structure, and the electrochemical performance of the membrane material is influenced by the volume effect of the metal oxide.
The potassium ion battery is expected to become a new generation battery main corner due to the advantages of rich raw materials, wide distribution, low cost and the like, however, the current potassium ion battery has a great distance from the application of the potassium ion battery to the field of energy storage, and the development of the potassium ion battery with high energy density and long cycle stability becomes one of the research and development directions of the current potassium ion battery. The electrode material of the potassium ion battery is the core of the current research, and in the aspect of the negative electrode material, the carbon material has good development prospect due to the advantages of high capacity and high cycle.
The current research on carbon materials is mainly focused on powder-like material research, while the research on flexible membranes for potassium ion batteries is less. The flexible membrane is used as the electrode, so that the use of a binder, a conductive agent and a metal current collector is avoided, the improvement of the mass/volume energy density of the whole electrode and the battery is facilitated, and meanwhile, the cycle life of the battery is prolonged. We prepared a flexible membrane by electrospinning and studied its electrochemical performance in a potassium cell. The flexible membrane shows good rate capability and cycle performance in the potassium battery.
Disclosure of Invention
The technical problem to be solved by the invention is how to solve the problem that the electrochemical performance of a membrane material is influenced by the volume effect of a solid carbon fiber structure and a metal oxide in the conventional method for preparing a flexible membrane by compounding a carbon material and the metal oxide.
The invention solves the technical problems through the following technical means:
the flexible membrane is a flexible membrane material formed by hollow porous carbon fibers, has a three-dimensional cross-linked structure, and is uniform in carbon fiber particle size.
The flexible membrane disclosed by the invention has a three-dimensional cross-linked structure, and the carbon nanofibers in the flexible membrane have a hollow porous structure, so that on one hand, the membrane material has a large specific surface due to the hollow porous structure, the potassium storage capacity is favorably improved, on the other hand, electrolyte and electrons are favorably transmitted in the electrode material due to the hollow porous structure, and the carbon nanofibers have the characteristics of flexibility and conductivity at the same time, so that the electronic conductivity of the material is enhanced, and the electrochemical performance is improved.
The invention also provides a method for preparing the flexible film, which comprises the following steps:
(1) dispersing the additive into the N, N-dimethylformamide solution according to the mass ratio of 0-0.05:4.6 to form a mixed solution I;
(2) dissolving acetate in the mixed solution I obtained in the step (1), and stirring to form a mixed solution II, wherein the addition amount of the acetate is 0.01-1g based on the addition amount of N, N-dimethylformamide;
(3) dispersing polyacrylonitrile in the mixed solution II obtained in the step (2), and stirring for 2-24h at 20-60 ℃ to obtain a uniformly dispersed mixed solution III, wherein the adding amount of the polyacrylonitrile is 0.3-1g based on the adding amount of the N, N-dimethylformamide;
(4) spinning the mixed solution tee obtained in the step (3) into a precursor film I through industrialized electrostatic spinning equipment;
(5) dissolving a proper amount of dimethyl imidazole in methanol to obtain a mixed solution IV, placing the precursor membrane I obtained in the step (4) with the size of 12cm x 12cm in the solution IV, washing for three times by using methanol at the temperature of 20-80 ℃ for 20-24h, and drying at the temperature of 60 ℃ to obtain a membrane II, wherein the addition amount of the dimethyl imidazole is 0.2-5g by taking the addition amount of the N, N-dimethylformamide as a reference;
(6) calcining the second membrane material obtained in the step (5) in an inert atmosphere to obtain a third membrane, wherein the calcining temperature is 500-950 ℃, the heating speed is 3-15 ℃/min, and the calcining time is 0.5-24 h;
(7) and (4) calcining the membrane III obtained in the step (6) in an ammonia atmosphere to obtain a membrane IV material, wherein the calcining temperature is 400-900 ℃, the calcining time is 0.5-24h, and the heating speed is 3-15 ℃/min.
(8) And (3) placing the membrane IV obtained in the step (7) in a mixed acid solution, treating for 1-3h at 20-120 ℃, washing and drying to obtain the final flexible membrane material, wherein the volume of the mixed acid solution is 0-100 ml.
Preferably, the additive in step (1) includes one or more of polyvinylpyrrolidone, reduced graphene oxide, polyaniline, melamine and urea.
Preferably, the acetate in step (2) includes one of zinc acetate, iron, cobalt and nickel.
Preferably, the spinning conditions in the step (4) are: the voltage is 14-40kV, the moving speed of the solution is 20-500cm/s, and the aperture is 0.6-0.9 mm; the environmental humidity is 20-45%, and the spinning temperature is 20-50 ℃.
Preferably, the inert atmosphere in step (6) comprises nitrogen or argon.
Preferably, the mixed acid in the step (8) comprises hydrochloric acid/nitric acid or hydrochloric acid/sulfuric acid, and the volume ratio of the mixed acid to the mixed acid is 0-100% to 0-100%.
A potassium battery comprises a positive plate, a negative plate, electrolyte, a diaphragm and a shell; the positive plate adopts the flexible membrane;
the negative plate is metal potassium;
the diaphragm comprises a composite diaphragm made of one or more of polyethylene, polypropylene microporous membranes, glass fiber diaphragms and non-woven fabrics diaphragms.
Further, the electrolyte is obtained by dissolving potassium salt in an organic solvent; the potassium salt comprises one or more of potassium bis (fluorosulfonyl) imide, potassium perchlorate, potassium hexafluorophosphate, potassium trifluoromethanesulfonate and potassium bis (trifluoromethanesulfonyl) imide; the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, tetraethylene glycol dimethyl ether, fluoroethylene carbonate, diglyme, 1, 3-cyclopentanediol, ethylene glycol dimethyl ether and triglyme.
Further, the outer shell of the battery is made of one or more of an aluminum shell, an aluminum plastic film and stainless steel; the shape of the battery comprises a button type, a column type or a square type.
The invention has the following beneficial effects:
1. the flexible membrane disclosed by the invention has a three-dimensional cross-linked structure and does not contain metal oxide, and the carbon nano-fiber in the flexible membrane has a hollow porous structure, so that on one hand, the membrane material has a large specific surface due to the hollow porous structure, and the potassium storage capacity is favorably improved, on the other hand, the electrolyte and electrons are favorably transmitted in the electrode material due to the hollow porous structure, and the carbon nano-fiber has the characteristics of flexibility and conductivity at the same time, so that the electronic conductivity of the material is enhanced, and the electrochemical performance is improved.
2. The flexible membrane disclosed by the invention is only composed of hollow porous carbon fibers, does not contain metal oxides, has the advantages of rich raw materials, low cost, simple preparation method, suitability for large-scale industrial production, convenience for storage and strong circulation stability.
3. The flexible membrane prepared into the chargeable and dischargeable room temperature potassium battery has high discharge specific capacity, excellent rate capability and good cycle performance, and has wide practical value and market prospect.
Drawings
FIG. 1 is a digital photograph of a precursor film prepared in example 1 of the present invention;
FIG. 2 is a digital photograph of a flexible film prepared in example 1 of the present invention;
FIG. 3 is a digital photograph of a flexible film prepared in example 1 of the present invention in a folded state;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a flexible membrane prepared in example 1 of the present invention;
FIG. 5 is a Transmission Electron Microscope (TEM) image of a flexible film prepared in example 1 of the present invention;
FIG. 6 is a charge-discharge curve diagram of a potassium battery prepared in example 1 of the present invention;
FIG. 7 is a graph of rate performance of a potassium battery made in example 1 of the present invention;
FIG. 8 is a graph showing the cycle characteristics of a potassium battery obtained in example 1 of the present invention;
FIG. 9 is a charge-discharge curve diagram of a potassium battery prepared in example 2 of the present invention;
FIG. 10 is a graph showing the charge and discharge curves of the potassium battery obtained in example 3 of the present invention;
FIG. 11 is a graph showing the charge and discharge curves of the potassium battery obtained in example 4 of the present invention;
FIG. 12 is a graph showing the charge and discharge curves of the potassium battery obtained in example 5 of the present invention;
FIG. 13 is a graph showing the charge and discharge curves of the potassium battery obtained in example 6 of the present invention;
FIG. 14 is a charge-discharge curve diagram of a potassium battery obtained in example 7 of the present invention;
FIG. 15 is a charge-discharge curve diagram of a potassium battery produced in example 8 of the present invention;
FIG. 16 is a charge-discharge curve diagram of a potassium battery produced in example 9 of the present invention;
FIG. 17 is a charge-discharge curve of a potassium battery produced in comparative example 1 of the present invention;
fig. 18 is a charge and discharge graph of the potassium battery according to comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention will be described clearly and completely with reference to the accompanying drawings and embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
Dispersing 0.01g of polyvinylpyrrolidone in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrial electrostatic spinning device under the spinning conditions: voltage of 30kV and liquid movementThe speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
Fig. 1 is a digital photograph of a film of the precursor prepared in this example.
Fig. 2 is a digital photograph of the flexible film prepared in this example.
Fig. 3 is a digital photograph of a flexible film made according to this example, showing very good flexibility.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the flexible film prepared in this example, with nanofibers 200nm in diameter, exhibiting a hollow structure.
Fig. 5 is a Transmission Electron Microscope (TEM) image of the flexible film prepared in this example, showing a hollow structure.
The flexible membrane material prepared by the embodiment is used as an anode active material, a potassium sheet is used as a cathode (the cathode capacity is far larger than the anode sheet capacity), the anode and the potassium sheet are separated by adopting a glass fiber diaphragm, 3M KFSI is dissolved in EC/DEC to be used as electrolyte, and a stainless steel shell is used as a shell to assemble the CR 2032 type button cell.
The potassium battery assembled by the above process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, and the charge-discharge curve, rate capability and 0.1A/g cycle performance of the potassium battery are shown in FIGS. 6, 7 and 8.
Under the multiplying power of 0.1A/g, the charging specific capacity of the first cycle of the material is 479mAh/g, under the multiplying power of 10A/g, the discharging specific capacity of the material is 120mAh/g, and after the material is circulated for 200 cycles under the multiplying power of 0.1A/g, the discharging specific capacity of 400mAh/g is still maintained.
Example 2
0.005g of polyaniline was dispersed in 4.6g N, N-dimethylformamide, and after dissolving by stirring, 0.439g of zinc acetate was added thereto, followed by stirringAfter dissolving, adding 0.4g of polyacrylonitrile, stirring for 6 hours to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circumference of the potassium battery at the multiplying power of 0.1A/g is shown in figure 9, and the specific charge capacity of the first circumference of the potassium battery at the multiplying power of 0.1A/g is 421 mAh/g.
Example 3
Dispersing 0.01g of reduced graphene oxide in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrial electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 deg.C at a speed of 10 deg.C/minAnd (5) processing for 2h to obtain the flexible membrane material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 10, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 276 mAh/g.
Example 4
Dispersing 0.005g of melamine in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying factor of 0.1A/g is shown in figure 11, and the specific charge capacity of the first circle of the potassium battery at the multiplying factor of 0.1A/g is 243 mAh/g.
Example 5
Dispersing 0.01g of urea in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 12, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 135 mAh/g.
Example 6
Adding 0.439g of zinc acetate into 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6 hours to obtain a uniformly mixed precursor solution, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; then the dried film is heated to 900 ℃ in nitrogen at the speed of 5 ℃/min and calcined2h, after cooling to room temperature in NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 13, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 363 mAh/g.
Example 7
In this embodiment, the flexible film material prepared in example 1 is used as a positive active material, the potassium sheet is used as a negative electrode (the negative electrode capacity is far greater than the positive electrode capacity), the positive electrode and the potassium sheet are separated by a glass fiber diaphragm, 1M KFSI is dissolved in EC/DEC to be used as an electrolyte, and a stainless steel shell is used as a shell to assemble the CR 2032 type button cell.
The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 14, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 314 mAh/g.
Example 8
In this example, the flexible film material prepared in example 1 was used as a positive electrode active material, the potassium sheet was used as a negative electrode (the negative electrode capacity was much greater than that of the positive electrode sheet), the positive electrode and the potassium sheet were separated by a nonwoven fabric, and 0.8M KPF was used6The solution is dissolved in EC/DEC to be electrolyte, and a stainless steel shell is taken as a shell to assemble the CR 2032 type button cell.
The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 15, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 377 mAh/g.
Example 9
This example will be described in more detailThe flexible membrane material prepared in example 1 was used as a positive active material, the potassium sheet was used as a negative electrode (the negative electrode capacity was much greater than the positive electrode capacity), the positive electrode and the potassium sheet were separated by a glass fiber separator, and 1M KClO was used4The solution is dissolved in EC/DEC to be electrolyte, and a stainless steel shell is taken as a shell to assemble the CR 2032 type button cell.
The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 16, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 301 mAh/g.
Comparative example 1
Dispersing 0.01g of polyvinylpyrrolidone in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrial electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the obtained precursor membrane by 12 cm-12 cm (area), placing the precursor membrane into 30ml of methanol solution, standing for 24 hours at 40 ℃, then washing the membrane three times by using methanol, and drying at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the comparative example as an anode active material, taking the potassium sheet as a cathode (the cathode capacity is far larger than the anode sheet capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 17, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 112 mAh/g.
Comparative example 2
To 4.6g of N, N-dimethylformamide, addAdding 0.439g of zinc acetate, stirring and dissolving, then adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the obtained precursor membrane by 12 cm-12 cm (area), placing the precursor membrane into 30ml of methanol solution, standing for 24 hours at 40 ℃, then washing the membrane three times by using methanol, and drying at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
The CR 2032 type button cell is assembled by taking the flexible membrane material prepared by the embodiment as an anode active material, taking a potassium sheet as a cathode (the cathode capacity is far larger than the anode capacity), separating the anode and the potassium sheet by adopting a glass fiber diaphragm, dissolving 3M KFSI in EC/DEC as electrolyte and taking a stainless steel shell as a shell. The potassium battery assembled by the process is subjected to charge-discharge test in a voltage range of 0.01-3.0V at room temperature, the charge-discharge curve of the first circle of the potassium battery at the multiplying power of 0.1A/g is shown in figure 18, and the specific charge capacity of the first circle of the potassium battery at the multiplying power of 0.1A/g is 143 mAh/g.
Comparative example 3
Dispersing 0.01g of polyvinylpyrrolidone in 4.6g of N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; dissolving 0.5g of dimethyl imidazole in 30ml of methanol solution, taking out the obtained precursor membrane and putting the precursor membrane into the methanol solution by 12cm x 12cm (area), standing the precursor membrane for 24 hours at 40 ℃, then washing the membrane for three times by using methanol, and drying the membrane at 60 ℃; and then heating the dried membrane to 900 ℃ at the speed of 5 ℃/min in nitrogen and calcining for 2h to obtain the flexible membrane material.
Comparative example 4
Dispersing 0.005g of polyaniline in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.5g of cobalt acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the precursor film with the area of 12cm x 12cm, placing the precursor film into 30ml of methanol solution, standing for 24h at 40 ℃, washing the film three times by using methanol, drying at 60 ℃, heating the dried film to 900 ℃ by using the temperature rise speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at a heating rate of 10 ℃/min for treatment for 2h, then treating the obtained flexible membrane material in a mixed acid solution with a hydrochloric acid/nitric acid volume ratio of 3:1 at a constant temperature of 80 ℃ for 24h, washing with water for three times, washing with ethanol once, and drying at 60 ℃ to obtain the flexible membrane material.
Comparative example 5
Dispersing 0.05g of polyvinylpyrrolidone in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrial electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the obtained precursor membrane by 12 cm-12 cm (area), placing the precursor membrane into 30ml of methanol solution, standing for 24 hours at 40 ℃, then washing the membrane three times by using methanol, and drying at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for treatment for 2h to obtain the flexible film material
Comparative example 6
Dispersing 0.05g of melamine in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, dissolving the precursor solutionSpinning the liquid in an industrialized electrostatic spinning device under the following spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the obtained precursor membrane by 12 cm-12 cm (area), placing the precursor membrane into 30ml of methanol solution, standing for 24 hours at 40 ℃, then washing the membrane three times by using methanol, and drying at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
Comparative example 7
Dispersing 0.01g of polyaniline in 4.6g N, N-dimethylformamide, stirring for dissolving, adding 0.439g of zinc acetate, stirring for dissolving, adding 0.4g of polyacrylonitrile, stirring for 6h to obtain a precursor solution which is uniformly mixed, and spinning the precursor solution in an industrialized electrostatic spinning device under the spinning conditions: the voltage is 30kV, the liquid moving speed is 100cm/s, the aperture is 0.6mm, the environmental humidity is 30 percent, and the spinning temperature is 30 ℃; taking out the obtained precursor membrane by 12 cm-12 cm (area), placing the precursor membrane into 30ml of methanol solution, standing for 24 hours at 40 ℃, then washing the membrane three times by using methanol, and drying at 60 ℃; then heating the dried film to 900 ℃ at the speed of 5 ℃/min in nitrogen, calcining for 2h, cooling to room temperature, and then adding NH3Heating to 600 ℃ at the speed of 10 ℃/min for processing for 2h to obtain the flexible film material.
In summary, the flexible membrane disclosed by the invention has a three-dimensional cross-linked structure and does not contain metal oxide, and the carbon nanofibers in the flexible membrane have a hollow porous structure, so that on one hand, the membrane material has a large specific surface due to the hollow porous structure, and is favorable for improving the potassium storage capacity, on the other hand, the electrolyte and electrons are favorably transmitted inside the electrode material due to the hollow porous structure, and the carbon nanofibers have the characteristics of flexibility and conductivity at the same time, so that the electronic conductivity of the material is enhanced, and the electrochemical performance is improved.
The flexible membrane disclosed by the invention is only composed of hollow porous carbon fibers, does not contain metal oxides, has the advantages of rich raw materials, low cost, simple preparation method, suitability for large-scale industrial production, convenience for storage and strong circulation stability.
The flexible membrane prepared into the chargeable and dischargeable room temperature potassium battery has high discharge specific capacity, excellent rate capability and good cycle performance, and has wide practical value and market prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A flexible film, characterized by: the flexible membrane is a flexible membrane material formed by hollow porous carbon fibers, has a three-dimensional cross-linked structure, and is uniform in carbon fiber particle size.
2. A method of making the flexible film of claim 1, comprising the steps of:
(1) dispersing the additive into the N, N-dimethylformamide solution according to the mass ratio of 0-0.05:4.6 to form a mixed solution I;
(2) dissolving acetate in the mixed solution I obtained in the step (1), and stirring to form a mixed solution II, wherein the addition amount of the acetate is 0.01-1g based on the addition amount of N, N-dimethylformamide;
(3) dispersing polyacrylonitrile in the mixed solution II obtained in the step (2), and stirring for 2-24h at 20-60 ℃ to obtain a uniformly dispersed mixed solution III, wherein the adding amount of the polyacrylonitrile is 0.3-1g based on the adding amount of the N, N-dimethylformamide;
(4) spinning the mixed solution tee obtained in the step (3) into a precursor film I through industrialized electrostatic spinning equipment;
(5) dissolving a proper amount of dimethyl imidazole in methanol to obtain a mixed solution IV, placing the precursor membrane I obtained in the step (4) with the size of 12cm x 12cm in the solution IV, washing for three times by using methanol at the temperature of 20-80 ℃ for 20-24h, and drying at the temperature of 60 ℃ to obtain a membrane II, wherein the addition amount of the dimethyl imidazole is 0.2-5g by taking the addition amount of the N, N-dimethylformamide as a reference;
(6) calcining the second membrane material obtained in the step (5) in an inert atmosphere to obtain a third membrane, wherein the calcining temperature is 500-950 ℃, the heating speed is 3-15 ℃/min, and the calcining time is 0.5-24 h;
(7) and (4) calcining the membrane III obtained in the step (6) in an ammonia atmosphere to obtain a membrane IV material, wherein the calcining temperature is 400-900 ℃, the calcining time is 0.5-24h, and the heating speed is 3-15 ℃/min.
(8) And (3) placing the membrane IV obtained in the step (7) in a mixed acid solution, treating for 1-3h at 20-120 ℃, washing and drying to obtain the final flexible membrane material, wherein the volume of the mixed acid solution is 0-100 ml.
3. The method for producing a flexible film according to claim 2, characterized in that: the additive in the step (1) comprises one or more of polyvinylpyrrolidone, reduced graphene oxide, polyaniline, melamine and urea.
4. The method for producing a flexible film according to claim 2, characterized in that: the acetate in the step (2) comprises one of zinc acetate, iron, cobalt and nickel.
5. The method for producing a flexible film according to claim 2, characterized in that: the spinning conditions in the step (4) are as follows: the voltage is 14-40kV, the moving speed of the solution is 20-500cm/s, and the aperture is 0.6-0.9 mm; the environmental humidity is 20-45%, and the spinning temperature is 20-50 ℃.
6. The method for producing a flexible film according to claim 2, characterized in that: the inert atmosphere in the step (6) comprises nitrogen or argon.
7. The method for producing a flexible film according to claim 2, characterized in that: the mixed acid in the step (8) comprises hydrochloric acid/nitric acid or hydrochloric acid/sulfuric acid, and the volume ratio of the mixed acid to the mixed acid is 0-100% to 0-100%.
8. A potassium battery, characterized in that: the lithium battery comprises a positive plate, a negative plate, electrolyte, a diaphragm and a shell; the positive plate adopts the flexible membrane of claim 1;
the negative plate is metal potassium;
the diaphragm comprises a composite diaphragm made of one or more of polyethylene, polypropylene microporous membranes, glass fiber diaphragms and non-woven fabrics diaphragms.
9. The potassium battery of claim 8, wherein: the electrolyte is obtained by dissolving sylvite in an organic solvent; the potassium salt comprises one or more of potassium bis (fluorosulfonyl) imide, potassium perchlorate, potassium hexafluorophosphate, potassium trifluoromethanesulfonate and potassium bis (trifluoromethanesulfonyl) imide; the organic solvent comprises one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, tetraethylene glycol dimethyl ether, fluoroethylene carbonate, diglyme, 1, 3-cyclopentanediol, ethylene glycol dimethyl ether and triglyme.
10. The potassium battery according to claim 8, wherein: the shell of the battery is made of one or more of aluminum shell, aluminum plastic film and stainless steel; the shape of the battery comprises a button type, a column type or a square type.
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Application publication date: 20220610 |