CN110246705A - A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application - Google Patents
A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application Download PDFInfo
- Publication number
- CN110246705A CN110246705A CN201910628789.8A CN201910628789A CN110246705A CN 110246705 A CN110246705 A CN 110246705A CN 201910628789 A CN201910628789 A CN 201910628789A CN 110246705 A CN110246705 A CN 110246705A
- Authority
- CN
- China
- Prior art keywords
- gel electrolyte
- water
- electrolyte
- super capacitor
- keeping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011245 gel electrolyte Substances 0.000 title claims abstract description 186
- 239000003990 capacitor Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 73
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000010452 phosphate Substances 0.000 claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims abstract description 7
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 7
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims abstract description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims abstract description 5
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims abstract description 5
- 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 abstract description 4
- 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 abstract description 4
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000021317 phosphate Nutrition 0.000 claims abstract description 3
- 239000001103 potassium chloride Substances 0.000 claims abstract description 3
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 3
- 235000007686 potassium Nutrition 0.000 claims abstract 2
- 239000007772 electrode material Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 239000011229 interlayer Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 238000006277 sulfonation reaction Methods 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 abstract description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000499 gel Substances 0.000 description 51
- 238000010586 diagram Methods 0.000 description 16
- 238000005538 encapsulation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000005611 electricity Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000000017 hydrogel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 4
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 4
- 229940105329 carboxymethylcellulose Drugs 0.000 description 4
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 102000004310 Ion Channels Human genes 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention provides a kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application, are related to gel electrolyte and supercapacitor field.Water-keeping gel electrolyte provided by the invention is prepared by electrolyte aqueous solution and oxygen-containing functional group polymer；Electrolyte in the electrolyte aqueous solution is one or more of in lithium perchlorate, double trifluoromethanesulfonimide lithiums, lithium hexafluoro phosphate, lithium nitrate, sodium chloride, sodium perchlorate, double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, sodium nitrate, potassium chloride, potassium hyperchlorate, double trifluoromethanesulfonimide potassium, Potassium Hexafluorophosphate and potassium nitrate；The oxygen-containing functional group polymer is one or more of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and polyacrylamide.Aqueous super capacitor based on water-keeping gel electrolyte of the present invention has overlength cycle life at normal temperature, being capable of normal charge and discharge and stable circulation under 120 DEG C of high temperature.
Description
Technical field
The present invention relates to gel electrolyte and supercapacitor technologies field, in particular to a kind of water-keeping gel electrolyte and
Preparation method and a kind of aqueous super capacitor and its preparation method and application.
Background technique
Supercapacitor is a kind of typical power-type electrochemical energy storing device, can be in automobile starting and braking, army
The fields such as thing satellite, aerospace, smart grid, micro-capacitance sensor and rail traffic are that main power source is provided with effect supplement, in the short time
The interior a large amount of electricity of release.The major advantage of supercapacitor is that fast charging and discharging, high rate performance are excellent, has extended cycle life
It is wide with the temperature range of application.With giving more sustained attention for researcher and industrial circle, the chemical property of supercapacitor
It has been greatly improved.Therefore, the application field of supercapacitor and temperature condition are expected to further extend.
The structure of supercapacitor mainly includes collector, electrode, electrolyte, diaphragm and encapsulating material etc..According to electrolysis
The type of matter, supercapacitor are divided into organic system and water system.The electrolyte of organic system is salt or ion liquid dissolving to having
In solvent, and water-based electrolyte is then aqueous solution.Although organic system supercapacitor has big operating voltage, electric
The inflammable and toxic intrinsic attribute of solution matter brings huge security risk and environmental pollution.Currently, every year can all occur due to
The case that the burning of organic bath at high temperature causes electric car to burn in power supply causes huge economic loss and tight
The personal injury of weight.In contrast, aqueous super capacitor then has better safety and environment friendly.In electrolyte component
Point, water system gel electrolyte be even more because it is safe, at low cost and easily operated the advantages that by extensive concern.
However, the moisture in traditional water system gel electrolyte is easy to volatilize under normal temperature environment, lead to electrode
Between ion channel forfeiture, to cause capacitor devices that cannot continue working.Also, moisture in water system gel electrolyte
Evaporation can also cause pressure in device to increase, there are the risk of explosion, these limit such in addition to causing electrolyte to fail
Electrolyte and capacitor are applied in a high temperauture environment.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of water-keeping gel electrolyte and preparation method thereof and a kind of water system
Supercapacitor and its preparation method and application.Water-keeping gel electrolyte provided by the invention has excellent water holding capacity and low
Vapour pressure, and secure and non-combustible is burnt, high temperature resistant；Aqueous super capacitor based on water-keeping gel electrolyte of the present invention is normal
The lower cycle life with overlength of temperature, under the hot conditions that temperature is up to 120 DEG C can normal charge/discharge operation and stabilization follow
Ring.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of water-keeping gel electrolyte, are prepared by electrolyte aqueous solution and oxygen-containing functional group polymer
It arrives；
Electrolyte in the electrolyte aqueous solution be lithium perchlorate, double trifluoromethanesulfonimide lithiums, lithium hexafluoro phosphate,
Lithium nitrate, sodium chloride, sodium perchlorate, double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, sodium nitrate, potassium chloride, perchloric acid
It is one or more of in potassium, double trifluoromethanesulfonimide potassium, Potassium Hexafluorophosphate and potassium nitrate；
The oxygen-containing functional group polymer be polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and
One or more of polyacrylamide.
Preferably, the molar concentration of electrolyte is 0.5~30mol/kg in the electrolyte aqueous solution.
Preferably, mass percent of the oxygen-containing functional group polymer in water-keeping gel electrolyte is 3~20%.
The present invention provides water-keeping gel electrolyte preparing methods described in above scheme, comprising the following steps:
Under heating conditions, by electrolyte aqueous solution and oxygen-containing functional group mixed with polymers, the guarantor is obtained after cooling
Hydrogel electrolyte；The temperature of the heating is 75~100 DEG C.
The present invention provides a kind of aqueous super capacitor, the aqueous super capacitor has sandwich structure；The folder
The center of cored structure is gel electrolyte, and the two sides ecto-entad of the sandwich structure is followed successively by collector and electrode material；
Or, the center of the interlayer structure is diaphragm, the two sides ecto-entad of the interlayer structure is followed successively by collector, electricity
Pole material and gel electrolyte；
The gel electrolyte is water-keeping gel electrolyte described in above scheme.
Preferably, the electrode material include active carbon, graphene, carbon cloth, carbon felt, manganese oxide, ruthenium-oxide, iron oxide,
One of cobalt oxide, nickel oxide and vanadium oxide；The collector includes gold plaque, platinized platinum, silver strip, aluminium flake, copper sheet, titanium sheet, zinc
One of piece and nickel sheet；The diaphragm includes glass fibre, non-woven fabrics, sulfonation non-woven fabrics, polyethylene film, polypropylene screen and filter
One of film.
The present invention provides the preparation methods of aqueous super capacitor described in above scheme, comprising the following steps:
When not including diaphragm in the aqueous super capacitor structure, gel electrolyte is coated in the table of electrode material
Then face is fitted together with collector, obtain the aqueous super capacitor；
When in the aqueous super capacitor structure including diaphragm, gel electrolyte is coated in electrode material and diaphragm
Surface, then fitted together with collector, obtain the aqueous super capacitor；
The gel electrolyte is water-keeping gel electrolyte described in above scheme.
Preferably, the gel electrolyte is in the one side that the coating zone of electrode material surface is electrode material, the electricity
The another side of pole material is collector.
Preferably, when in the aqueous super capacitor structure including diaphragm, the gel electrolyte is in membrane surface
Coating zone be diaphragm two sides.
The water system prepared the present invention provides aqueous super capacitor described in above scheme or above scheme the method is super
Application of the grade capacitor under room temperature and hot environment；When the aqueous super capacitor is under high temperature environment in application, described
It include diaphragm in the structure of aqueous super capacitor；Temperature≤120 DEG C of the hot environment.
The present invention provides a kind of water-keeping gel electrolyte, are prepared by electrolyte aqueous solution and oxygen-containing functional group polymer
It arrives.Water-keeping gel electrolyte provided by the invention has excellent water holding capacity and low-vapor pressure, and secure and non-combustible is burnt, resistance to height
Temperature.The present invention provides the water-keeping gel electrolyte preparing methods, and method provided by the invention is simple, so that water-keeping gel
Electrolyte is easily prepared, is advantageously implemented large-scale production.
The present invention provides a kind of aqueous super capacitor, the aqueous super capacitor has sandwich structure；The folder
The center of cored structure is gel electrolyte, and the two sides ecto-entad of the sandwich structure is followed successively by collector and electrode material；Or,
The center of the interlayer structure is diaphragm, and the two sides ecto-entad of the interlayer structure is followed successively by collector, electrode material and coagulates
Glue electrolyte；The gel electrolyte is water-keeping gel electrolyte described in above scheme.Aqueous super electricity provided by the invention
Container can safely, effectively be applied under room temperature and hot environment, at normal temperature with the cycle life of overlength, in temperature height
It being capable of normal charge/discharge operation and stable circulation under conditions of up to 120 DEG C；Also, biggish work is all had at ambient and elevated temperatures
Make voltage, thus there is bigger energy density, is capable of providing more energy.The present invention provides the aqueous super capacitors
The preparation method of device, method material provided by the invention are easy to get, and assembling mode is simply mature, can need without using encapsulation or only
Want simplified package, it will be apparent that reduce costs, be conducive to quantitatively produce.
Embodiment the result shows that, after water-keeping gel electrolyte provided by the invention places 100 hours under normal temperature conditions,
The 113% of initial weight can still be maintained, not only without dehydration, additionally it is possible to moisture is absorbed from air；In 120 DEG C of items of temperature
After placing 3.2 hours under part, the 98.1% of initial weight can still be maintained, in the dry environment of superhigh temperature, be also
Reduce a small amount of moisture.Aqueous super capacitor provided by the invention based on this water-keeping gel electrolyte is in no any envelope
In the case where dress, after recycling 62 days (1488 hours) in normal temperature environment, capacity retention ratio 98.8%；In 120 DEG C surpass
After being recycled 12.5 hours under hot conditions, capacity retention ratio 79.3%.
Detailed description of the invention
Fig. 1 is that structural form is collector-electrode material-gel electrolyte-electrode material-collector water in the present invention
It is the structural schematic diagram of supercapacitor, 1 expression collector in Fig. 1,2 indicate electrode materials, and 3 indicate water-keeping gel electrolyte；
Fig. 2 is that structural form is collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electricity in the present invention
The structural schematic diagram of the aqueous super capacitor of pole material-current collector, in Fig. 2,1 indicates collector, and 2 indicate electrode materials, 3 tables
Show water-keeping gel electrolyte, 4 indicate diaphragm；
Fig. 3 is the Raman spectrum pair of conventional GPC electrolyte in water-keeping gel electrolyte prepared by embodiment 1 and comparative example
Than figure；
Fig. 4 is the water holding capacity pair of conventional GPC electrolyte in water-keeping gel electrolyte prepared by embodiment 1 and comparative example
Than figure；
Fig. 5 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor chemical property comparison diagram, in Fig. 5, a is cyclic voltammetry curve comparison diagram, and b is that constant current charge-discharge compares
Figure, c are high rate performance comparison diagram, and d is ac impedance spectroscopy；
Fig. 6 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor energy density and power density comparison diagram；
Fig. 7 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor circulation comparison diagram, in Fig. 7, a is the circulation figure of the supercapacitor based on conventional GPC electrolyte, and b is
The circulation figure of supercapacitor based on water-keeping gel electrolyte；
Fig. 8 is quality retention rate figure of the water-keeping gel electrolyte of the preparation of embodiment 5 under different temperature and humidity；
Fig. 9 is electrochemistry of the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 under different high temperature
Performance map, in Fig. 9, a is that sweep speed be 5mV s-1Cyclic voltammetry curve comparison, b is that current density is 4mA cm-2Constant current fill
Electric discharge comparison, c are times of the supercapacitor based on water-keeping gel electrolyte under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions
Rate performance comparison diagram, d are the supercapacitor based on water-keeping gel electrolyte under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions
Ac impedance spectroscopy；
Figure 10 is the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 in 80 DEG C-humidity of temperature 50%
Cycle performance figure under the hot conditions of RH；
Figure 11 is the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 in 100 DEG C-humidity of temperature 10%
Cycle performance figure under the conditions of the high temperature drying of RH；
Figure 12 is superhigh temperature of the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 at 120 DEG C of temperature
Under the conditions of cycle performance figure.
Specific embodiment
The present invention provides a kind of water-keeping gel electrolyte, are prepared by electrolyte aqueous solution and oxygen-containing functional group polymer
It arrives.
In the present invention, the electrolyte in the electrolyte aqueous solution be lithium perchlorate, double trifluoromethanesulfonimide lithiums,
Lithium hexafluoro phosphate, lithium nitrate, sodium chloride, sodium perchlorate, double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, sodium nitrate, chlorination
It is one or more of in potassium, potassium hyperchlorate, double trifluoromethanesulfonimide potassium, Potassium Hexafluorophosphate and potassium nitrate.The present invention is to described
The source of electrolyte does not require particularly, using commercial product well known in the art.In the present invention, the electrolyte
The molar concentration of Enthalpy of Electrolytes in Aqueous Solutions is preferably 0.5~30mol/kg, more preferably 5~25mol/kg.In the present invention, institute
It states electrolyte and all has higher solubility in aqueous solution.
In the present invention, the oxygen-containing functional group polymer is polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, carboxylic
One or more of methylcellulose and polyacrylamide.The present invention is to the source of the oxygen-containing functional group polymer without spy
Other requirement, using commercial product well known in the art.In the present invention, the oxygen-containing functional group polymer is solidifying in water conservation
Mass percent in glue electrolyte is preferably 3~20%, and more preferably 5~15%.
Water-keeping gel electrolyte provided by the invention has excellent water holding capacity and low-vapor pressure, and secure and non-combustible
It burns, high temperature resistant.
The present invention provides water-keeping gel electrolyte preparing methods described in above scheme, comprising the following steps:
Under heating conditions, by electrolyte aqueous solution and oxygen-containing functional group mixed with polymers, the guarantor is obtained after cooling
Hydrogel electrolyte.
In the present invention, the temperature of the heating is 75~100 DEG C, preferably 80~95 DEG C；The present invention preferably passes through oil
The mode of bath is heated.In the present invention, the oxygen-containing functional group polymer is preferably added to electrolyte water by the mixing
It is mixed in solution.To guarantee that oxygen-containing functional group polymer preferably dissolves, present invention preferably employs the shape sides being gradually added into
Oxygen-containing functional group is added in formula, specifically: the electrolyte aqueous solution is heated to required temperature in oil bath pan, then to electricity
Oxygen-containing functional group polymer is gradually added into solution matter aqueous solution.In the present invention, the oxygen-containing functional group polymer is preferably 15
~85min is added more preferably in 15~60min and finishes.In the present invention, described to mix preferably under continuous agitation
It carries out, the present invention does not require the time of the stirring particularly, can guarantee that the oxygen-containing functional group polymer is all molten
Solution.The present invention does not require the method for the cooling particularly, using cooling means well known in the art, specifically
Ground such as cooled to room temperature.After cooling, as clear as crystal gel electrolyte is obtained, i.e., the described water-keeping gel electrolyte.This hair
The method of bright offer is simple, so that water-keeping gel electrolyte is easily prepared, is advantageously implemented large-scale production.
The present invention provides a kind of aqueous super capacitor, the aqueous super capacitor has sandwich structure；The folder
The center of cored structure is gel electrolyte, and the two sides ecto-entad of the sandwich structure is followed successively by collector and electrode material；
Or, the center of the interlayer structure is diaphragm, the two sides ecto-entad of the interlayer structure is followed successively by collector, electricity
Pole material and gel electrolyte；
The gel electrolyte is above-described water-keeping gel electrolyte.
In the present invention, the electrode material preferably include active carbon, graphene, carbon cloth, carbon felt, manganese oxide, ruthenium-oxide,
One of iron oxide, cobalt oxide, nickel oxide and vanadium oxide；It is living that electrode material of the present invention all has higher electrochemistry
Property, wherein the active carbon, graphene, carbon cloth, carbon felt specific surface area also with higher.In the present invention, the collector
Preferably include one of gold plaque, platinized platinum, silver strip, aluminium flake, copper sheet, titanium sheet, zinc metal sheet and nickel sheet；Collector tool of the present invention
There are higher electron conduction and chemical stability.In the present invention, the diaphragm preferably includes glass fibre, non-woven fabrics, sulphur
Change one of non-woven fabrics, polyethylene film, polypropylene screen and filter membrane；Diaphragm of the present invention has preferable thermal stability.
The present invention does not require the source of the electrode material, collector and diaphragm particularly, using production that is commercially available or voluntarily preparing
Product.
In the present invention, the aqueous super capacitor has sandwich structure；The center of the sandwich structure is gel electricity
The two sides ecto-entad of Xie Zhi, the sandwich structure are followed successively by collector and electrode material；Or, the center of the interlayer structure is
The two sides ecto-entad of diaphragm, the interlayer structure is followed successively by collector, electrode material and gel electrolyte.It is i.e. of the present invention
Aqueous super capacitor include two kinds of structures: when the center of the sandwich structure be gel electrolyte, the sandwich structure
When two sides ecto-entad is followed successively by collector and electrode material, being formed by aqueous super capacitor is aseptate structure, i.e.,
The structural form of the aqueous super capacitor is collector-electrode material-gel electrolyte-electrode material-collector, is such as schemed
Shown in 1；When the center of the interlayer structure is diaphragm, the two sides ecto-entad of the interlayer structure is followed successively by collector, electrode
When material and gel electrolyte, being formed by aqueous super capacitor is septate structure, i.e., the described aqueous super capacitor
Structural form be collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-collector, such as Fig. 2
It is shown.
The present invention provides the preparation methods of aqueous super capacitor described in above scheme, comprising the following steps:
When not including diaphragm in the aqueous super capacitor structure, gel electrolyte is coated in the table of electrode material
Then face is fitted together with collector, obtain the aqueous super capacitor；
When in the aqueous super capacitor structure including diaphragm, gel electrolyte is coated in electrode material and diaphragm
Surface, then fitted together with collector, obtain the aqueous super capacitor；
The gel electrolyte is water-keeping gel electrolyte described in above scheme.
In the present invention, the gel electrolyte is preferably the one of electrode material in the coating zone of electrode material surface
Face, the another side of the electrode material are preferably collector；It is described when in the aqueous super capacitor structure including diaphragm
Gel electrolyte is on the two sides that the coating zone of membrane surface is preferably diaphragm.The present invention is not special to the thickness of the coating
Requirement, the region is paved with；The present invention does not require the method for the coating particularly, using it is well known that
Coating method.When not including diaphragm in the aqueous super capacitor structure, by collector and it is coated with gel electricity
The electrode material ecto-entad of solution matter is successively arranged to be fitted together as two sides, and interlayer structure, the sandwich are formed after assembling
The center of structure is gel electrolyte, and the two sides ecto-entad of the sandwich structure is followed successively by collector and electrode material；Work as institute
It states in aqueous super capacitor structure when including diaphragm, centered on being coated with the diaphragm of gel electrolyte, collector and coating
There is the electrode material ecto-entad of gel electrolyte successively to arrange to be assembled as two sides, forms interlayer structure after assembling, institute
The center for stating interlayer structure is diaphragm, and the two sides ecto-entad of the interlayer structure is followed successively by collector, electrode material and gel
Electrolyte.Method material provided by the invention is easy to get, and assembling mode is simply mature, can need without using encapsulation or only simple
Encapsulation, it will be apparent that reduce costs, be conducive to quantitatively produce.
The water system prepared the present invention provides aqueous super capacitor described in above scheme or above scheme the method is super
Application of the grade capacitor under room temperature and hot environment.In the present invention, when the aqueous super capacitor is under normal temperature environment
In application, the aqueous super capacitor can be aseptate structure, or septate structure, i.e., the described water system are super
The assembling form of grade capacitor can be collector-electrode material-gel electrolyte-electrode material-collector, as shown in Figure 1；
It may be collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-collector, as shown in Figure 2.
When the aqueous super capacitor be aseptate structure when, because in capacitor from using diaphragm, so as to further drop
Low cost.Because water-keeping gel electrolyte provided by the invention at normal temperature can long time retaining water content, maintain electrode between
Ion transmission, even if therefore the aqueous super capacitor based on this water-keeping gel electrolyte under conditions of no any encapsulation,
Still with the cycle life of overlength, solve the problems, such as that traditional water system capacitor cannot continue working.
In the present invention, when the aqueous super capacitor is under high temperature environment in application, the aqueous super capacitor
Structure in include diaphragm.In the present invention, temperature≤120 DEG C of the hot environment, i.e., aqueous super of the present invention
Capacitor still being capable of normal charge/discharge operation and stable circulation under conditions of temperature is up to 120 DEG C.Because provided by the invention
Water-keeping gel electrolyte can be avoided the evaporation of moisture and be able to maintain ion transmission channel, so that the super capacitor of assembling
Device can also be operated normally even without any encapsulation；Simultaneously because the water-keeping gel only has under 120 DEG C of ultra-high temperature conditions
The characteristics of a small amount of moisture evaporation, low-vapor pressure, which also ensures, will not cause bulge even in the device tightly encapsulated
The case where explosion.Therefore, aqueous super capacitor provided by the invention can be realized safe and effective under the high temperature conditions answer
With solving the problems, such as that traditional aqueous super capacitor high temperature is inoperable；Moreover, 120 DEG C are also water as known in the art
It is the maximum operating temperature that supercapacitor is amenable to live.
Aqueous super capacitor provided by the invention whether under normal temperature environment or under high temperature environment, can pacify
Entirely, it efficiently applies.
Below with reference to embodiment to a kind of water-keeping gel electrolyte provided by the invention and preparation method thereof and a kind of water system
Supercapacitor and its preparation method and application is described in detail, but they cannot be interpreted as protecting model to the present invention
The restriction enclosed.
Embodiment 1
Based on the aqueous super capacitor of water-keeping gel electrolyte, preparation method the following steps are included:
1) nickel sheet that will be cut into the size of 1cm × 1cm and homemade active carbon are respectively as collector and electrode material；
2) the lithium perchlorate aqueous solution of 13mol/kg (i.e. water conservation electrolyte aqueous solution) is heated to 90 DEG C, then constantly stirred
It mixes down, polyacrylamide is added within the 30min time, persistently stir 4h and obtain the gel of clear, polyacrylamide is solidifying
Mass fraction in glue is 8.36%.Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as polyacrylamide-lithium perchlorate
Water-keeping gel electrolyte；
3) polyacrylamide-lithium perchlorate water-keeping gel electrolyte is uniformly coated on homemade activated carbon surface, so
It is assembled into afterwards with collector-electrode material-gel electrolyte-electrode material-collector structure based on water-keeping gel electrolyte
Aqueous super capacitor, as shown in Figure 1.The device is without encapsulation.
Comparative example
The supercapacitor of conventional GPC electrolyte, preparation method the following steps are included:
1) nickel sheet that will be cut into the size of 1cm × 1cm and homemade active carbon are respectively as collector and electrode material；
2) water lithium chloride solution of 1mol/L (i.e. conventional electrolysis matter aqueous solution) is heated to 85 DEG C, be then stirred continuously
Under, polyvinyl alcohol is added within the 30min time, persistently stirs 4h and obtains the gel of clear, polyvinyl alcohol is in gel
Mass fraction is 8.75%；Conventional GPC electrolyte is obtained after being cooled to room temperature；
3) conventional GPC electrolyte is uniformly coated on homemade activated carbon surface, then with collector-electrode material-
Gel electrolyte-electrode material-collector structure is assembled into the aqueous super capacitor based on conventional GPC electrolyte.
Room temperature is carried out to electrolyte aqueous solution, gel electrolyte and the aqueous super capacitor in embodiment 1 and comparative example
Characterization and performance test under environment, specific as follows:
Fig. 3 is the Raman spectrum pair of conventional GPC electrolyte in water-keeping gel electrolyte prepared by embodiment 1 and comparative example
Than figure (in Fig. 3, pure water is as blank control).In wavelength 3000cm-1To 3800cm-1Range in be shown hydrone and
The combination situation of electrolyte ion: from the Raman spectrum of pure water and conventional electrolysis matter aqueous solution it is apparent that water cluster
Characteristic peak, showing hydrone largely is existing for free state；And electrolyte aqueous solution is retained then in wave 3580cm-1Near
There is a spike, what which indicated is the hydration profile peak of ion and hydrone, this show hydrone and electrolyte from
Son has very strong combination, to realize stronger water conservation and water absorbing capacity.After polymer formation gel electrolyte is added,
In addition in wavelength 2950cm-1Nearby occur except the characteristic peak of polymer, other all there is no significantly changing, that is,
Say, the hydrone in conventional GPC electrolyte is still in free state, and the hydrone in water-keeping gel electrolyte still with electrolysis
Matter ion has stronger binding force, illustrates to be formed after gel, and water-keeping gel electrolyte still has stronger water conservation and suction
Outlet capacity.
Fig. 4 is the water holding capacity pair of conventional GPC electrolyte in water-keeping gel electrolyte prepared by embodiment 1 and comparative example
Than figure.Figure 4, it is seen that the quality of conventional GPC electrolyte is to continue to reduce under the conditions of same place, show
Moisture in gel is always in evaporation loss；And not only quality is not reduced water-keeping gel electrolyte, is also being continued to increase,
Show that the moisture in water-keeping gel electrolyte does not lose not only, gel can also absorb moisture from environment.Specific numerical value is,
After placing 100 hours, the quality of conventional GPC electrolyte becomes the 63.2% of initial mass, and water-keeping gel electrolyte
Quality then becomes the 113% of initial mass.These are the result shows that water-keeping gel electrolyte provided by the invention has very strong guarantor
Water and water absorbing capacity.
Fig. 5 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor chemical property comparison diagram.A in Fig. 5 is cyclic voltammetry curve comparison diagram, therefrom this it appears that
Supercapacitor based on water-keeping gel electrolyte has the operating voltage of significantly larger 1.8V, and is electrolysed based on conventional GPC
The operating voltage of the supercapacitor of matter only has 1.0V.B is constant current charge-discharge comparison diagram in Fig. 5, it can be seen that based on protecting
The supercapacitor of hydrogel electrolyte has bigger charging/discharging voltage, this is also consistent with the result of cyclic voltammetry curve.Fig. 5
Middle c is high rate performance comparison diagram, it can be seen that the supercapacitor based on water-keeping gel electrolyte is keeping bigger electricity
On the basis of chemical window, area specific capacity and high rate performance are also and the class of the supercapacitor based on conventional GPC electrolyte
Seemingly.D is ac impedance spectroscopy in Fig. 5, it can be seen that impedance and the base of the supercapacitor based on water-keeping gel electrolyte
In conventional GPC electrolyte supercapacitor impedance contrast away from little, since water-keeping gel electrolyte ion conductivity is lower,
This also causes the Charge-transfer resistance of mid-frequency region bigger.
Fig. 6 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor energy density and power density comparison diagram.Since the supercapacitor based on water-keeping gel electrolyte has
Bigger operating voltage, energy density and power density are all more much bigger than the supercapacitor based on conventional GPC electrolyte.
Specifically, the maximum energy-density of the supercapacitor based on water-keeping gel electrolyte is 243.9 μ Wh cm-2, and based on normal
The maximum energy-density for advising the supercapacitor of gel electrolyte is only 80.8 μ Wh cm-2.This further illustrates that the present invention provides
The supercapacitor based on water-keeping gel electrolyte have bigger application value.
Fig. 7 is that supercapacitor and comparative example of the embodiment 1 based on water-keeping gel electrolyte are based on conventional GPC electrolyte
Supercapacitor circulation comparison diagram, a is the circulation figure of the supercapacitor based on conventional GPC electrolyte in Fig. 7, and b is base
In the circulation figure of the supercapacitor of water-keeping gel electrolyte.As can be seen from Figure 7 the circulation ability of two kinds of supercapacitors
There is huge gap.Specifically, the supercapacitor based on conventional GPC electrolyte is recycling under the conditions of normal temperature environment
Capacity retention rate is just reduced to 0 after 20 hours, and showing that device is no longer valid not can be carried out normal work, this is because
Conventional gel electrolyte has lost the moisture of the overwhelming majority, leads to do not have ion channel between two electrodes, to become
Obtaining shrivelled conventional GPC electrolyte leads to the failure of device.And the supercapacitor based on water-keeping gel electrolyte is in circulation 62
(being up to 1488 hours) after it can still be maintained the 98.8% of initial capacity, this is because water-keeping gel electrolyte is when long
Between cyclic process in can be always maintained at moisture, keep the ion transmission between electrode.Therefore illustrate base provided by the invention
There is apparent long circulation life in the supercapacitor of water-keeping gel electrolyte.
Embodiment 2
Based on the aqueous super capacitor of water-keeping gel electrolyte, preparation method the following steps are included:
1) zinc metal sheet and commercial activated carbons that will be cut into the size of 1cm × 1cm are respectively as collector and electrode material；
2) potassium nitrate solution of 15mol/kg is heated to 95 DEG C, be then stirred continuously down, is added within the 60min time poly-
Ethylene glycol persistently stirs 6h and obtains the gel of clear, and mass fraction of the polyethylene glycol in gel is 10.0%；It is cooled to
Water-keeping gel electrolyte is obtained after room temperature, is denoted as polyethylene glycol-potassium nitrate water-keeping gel electrolyte；
3) polyethylene glycol-potassium nitrate water-keeping gel electrolyte is uniformly coated on commercial activated carbon surface, then with collection
Fluid-electrode material-gel electrolyte-electrode material-collector structure is assembled into the water system based on water-keeping gel electrolyte
Supercapacitor.The device is without further encapsulation.
Embodiment 3
Based on the aqueous super capacitor of water-keeping gel electrolyte, preparation method the following steps are included:
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) titanium sheet and business carbon cloth that will be cut into 1cm × 1cm size are respectively as collector and electrode material；
2) double trifluoromethanesulfonimide lithium highly concentrated solutions of 21mol/kg are heated to 95 DEG C, be then stirred continuously
Under, polyvinyl alcohol is added within the 30min time, persistently stirs 4h and obtains the gel of clear, polyvinyl alcohol is in gel
Mass fraction is 5.38%；Water-keeping gel electrolyte is obtained after being cooled to room temperature, it is sub- to be denoted as the bis- fluoroform sulphonyl of polyvinyl alcohol-
Amine lithium water-keeping gel electrolyte；
3) the bis- trifluoromethanesulfonimide lithium water-keeping gel electrolyte of polyvinyl alcohol-are uniformly coated on business carbon cloth table
Then face is assembled into collector-electrode material-gel electrolyte-electrode material-collector structure based on water-keeping gel electricity
Solve the aqueous super capacitor of matter.The device is without further encapsulation.
Embodiment 4
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) silver strip and carbon felt that will be cut into 1cm × 1cm size are respectively as collector and electrode material；
2) the sodium hexafluoro phosphate highly concentrated solution of 8mol/kg is heated to 85 DEG C, be then stirred continuously down, in 60min
Interior addition carboxymethyl cellulose persistently stirs 5h and obtains the gel of clear, quality of the carboxymethyl cellulose in gel
Score is 12.8%；Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as carboxymethyl cellulose-sodium hexafluoro phosphate water conservation
Gel electrolyte；
3) carboxymethyl cellulose-sodium hexafluoro phosphate water-keeping gel electrolyte is uniformly coated on business Carbon felt surface, so
It is assembled into afterwards with collector-electrode material-gel electrolyte-electrode material-collector structure based on water-keeping gel electrolyte
Aqueous super capacitor.The device is without further encapsulation.
Performance of the supercapacitor based on water-keeping gel electrolyte under normal temperature environment prepared by embodiment 2~4 into
Row test, the results showed that the supercapacitor provided by the invention based on water-keeping gel electrolyte not only has bigger work electricity
Pressure and energy density, and cycle life also has big advantage.Specifically, under the conditions of normal temperature environment, based on conventional
The supercapacitor of gel electrolyte is failed due to electrolyte dehydration after recycling 20 hours, and embodiment 2 is super
Grade capacitor retention rate of capacity (up to 1488 hours) after circulation 62 days is that the supercapacitor of 96.5%, embodiment 3 exists
The retention rate of capacity is 99.1% after circulation 62 days, the supercapacitor of embodiment 4 retention rate of capacity after circulation 62 days is
97.3%.
Embodiment 5
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) using the nickel sheet of graphene and the size for being cut into 1cm × 1cm as electrode material and collector；
2) sodium nitrate solution of 6mol/kg is heated to 90 DEG C, be then stirred continuously down, carboxylic is added within the 30min time
Methylcellulose persistently stirs 5h and obtains the gel of clear, and mass fraction of the carboxymethyl cellulose in gel is
10.5%；Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as carboxymethyl cellulose-sodium nitrate water-keeping gel electrolyte；
3) carboxymethyl cellulose-sodium nitrate water-keeping gel electrolyte is uniformly coated on graphene and nonwoven cloth diaphragm table
Face.Then with collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-collector structure type
It is assembled into the aqueous super capacitor based on water-keeping gel electrolyte, as shown in Figure 2.The device is without encapsulation.
To the water-keeping gel electrolyte in embodiment 5 and the aqueous super capacitor based on water-keeping gel electrolyte carries out height
Performance test under warm environment, specific as follows:
Fig. 8 is quality retention rate figure of the water-keeping gel electrolyte of the preparation of embodiment 5 under different temperature and humidity.From Fig. 8
As can be seen that water conservation water system gel electrolyte prepared by the present invention is put under the hot conditions of 80 DEG C-humidity of temperature 50%RH
After setting 12 hours, the 118% of initial weight can still be maintained, under hot conditions, gel electrolyte is not only steamed without moisture
Hair, additionally it is possible to absorb moisture.Under the high temperature wet condition of 100 DEG C-humidity of temperature 50%RH, high temperature resistant prepared by the present invention
After water system gel electrolyte is placed 8 hours, the 118% of initial weight can still be maintained, in the temperature environment of moisture evaporation
In not only without moisture loss, additionally it is possible to absorb moisture.Under the conditions of the high temperature drying of 100 DEG C-humidity of temperature 10%RH, this hair
After bright prepared high temperature resistant water system gel electrolyte is placed 7 hours, the 104% of initial weight can still be maintained, in height
In the dry environment of temperature, gel is able to maintain that own wt, guarantees that moisture will not be lost.In 120 DEG C of ultra-high temperature condition of temperature
Under, after high temperature resistant water system gel electrolyte prepared by the present invention is placed 3.2 hours, initial weight can still be maintained
98.1%, in the dry environment of superhigh temperature, gel is also only the reduction of a small amount of moisture.These are statistics indicate that the present invention provides
Water-keeping gel electrolyte be it is resistant to high temperature, have the ability to work under the conditions of high temperature drying.
Fig. 9 is electrochemistry of the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 under different high temperature
Performance map (electrochemical property test is to be tested in a climatic chamber by the fixed temperature and humidity of control).
A is 5mV s to sweep speed in Fig. 9-1Cyclic voltammetry curve comparison, it can be seen that the super electricity based on water-keeping gel electrolyte
Container has the operating voltage of 1.8 V, this voltage value than the supercapacitor based on conventional GPC electrolyte 1.0 V (see
Comparative example) operating voltage will be high, under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions, device can be carried out normally
Operation.It is 4mA cm that b, which is current density, in Fig. 9-2Constant current charge-discharge comparison, it can be seen that be based on moisturizing gel electrolyte
Supercapacitor be able to carry out normal charge and discharge under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions, this also with circulation lie prostrate
The result for pacifying curve is consistent, and at 80 DEG C, 100 DEG C and 120 DEG C, the capacity of device is respectively 956.2mF cm-2、534.6mF
cm-2With 528.9mF cm-2；It can also be seen that the operating voltage of device also has decline as the temperature rises from figure b, this is
The common phenomenon of high temperature ultracapacitor.In Fig. 9 c be the supercapacitor based on water-keeping gel electrolyte at 80 DEG C, 100 DEG C and
High rate performance comparison diagram under 120 DEG C of hot conditions, it can be seen that the supercapacitor based on water-keeping gel electrolyte
It can be operated normally under different current densities under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions.D is based on guarantor in Fig. 9
Ac impedance spectroscopy of the supercapacitor of hydrogel electrolyte under 80 DEG C, 100 DEG C and 120 DEG C of hot conditions, Cong Zhongke
Impedance to find out the device in 80 DEG C of high temperature is very low, but as temperature increases, and the Charge-transfer resistance of device is also therewith
Increase, this is because electrolyte ion motion frequency increases after temperature increases, the directed movement of electrolyte ion is caused to be obstructed.
Figure 10 is the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 in 80 DEG C-humidity of temperature 50%
Cycle performance figure under the hot conditions of RH.It can be seen from fig. 10 that it is prepared by the present invention without any encapsulation based on guarantor
The supercapacitor of hydrogel electrolyte is after circulation 100 hours, capacity retention ratio 80.8%.
Figure 11 is the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 in 100 DEG C-humidity of temperature 10%
Cycle performance figure under the conditions of the high temperature drying of RH.It can be seen from fig. 11 that the base prepared by the present invention without any encapsulation
In water-keeping gel electrolyte supercapacitor circulation 44.1 hours after, capacity retention ratio 80.1%.
Figure 12 is superhigh temperature of the supercapacitor based on water-keeping gel electrolyte of the preparation of embodiment 5 at 120 DEG C of temperature
Under the conditions of cycle performance figure.In figure 12 it can be seen that prepared by the present invention without the electric based on water-keeping gel of any encapsulation
The supercapacitor of matter is solved after circulation 12.5 hours, capacity retention ratio 79.3%.
Embodiment 6
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) using the titanium sheet of carbon cloth and the size for being cut into 1cm × 1cm as electrode material and collector；
2) double trifluoromethanesulfonimide lithium solution of 21mol/kg are heated to 95 DEG C, be then stirred continuously down,
Polyvinyl alcohol is added in the 30min time, persistently stirs 4h and obtains the gel of clear, quality of the polyvinyl alcohol in gel
Score is 5.38%；Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as the bis- trifluoromethanesulfonimide lithiums of polyvinyl alcohol-
Water-keeping gel electrolyte；
3) the bis- trifluoromethanesulfonimide lithium water-keeping gel electrolyte of polyvinyl alcohol-are uniformly coated on carbon cloth and sulfonation
Non-woven fabrics membrane surface, then with collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-afflux
The structure type of body is assembled into the aqueous super capacitor based on water-keeping gel electrolyte.The device is without encapsulation.
Embodiment 7
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) using the copper sheet of manganese oxide and the size for being cut into 1cm × 1cm as electrode material and collector；
2) the potassium hyperchlorate solution of 12mol/kg is heated to 80 DEG C, be then stirred continuously down, is added within the 50min time
Polyvinylpyrrolidone persistently stirs 8h and obtains the gel of clear, mass fraction of the polyvinylpyrrolidone in gel
It is 8.65%；Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as polyvinylpyrrolidone-potassium hyperchlorate water-keeping gel electricity
Xie Zhi；
3) polyvinylpyrrolidone-potassium hyperchlorate water-keeping gel electrolyte is uniformly coated on manganese oxide and glass fibre
Membrane surface, then with collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-collector knot
Configuration formula is assembled into the aqueous super capacitor based on water-keeping gel electrolyte.The device is without encapsulation.
Embodiment 8
The preparation method of the supercapacitor of long circulation life based on water-keeping gel electrolyte, comprising the following steps:
1) using the zinc of nickel oxide and the size for being cut into 1cm × 1cm as electrode material and collector；
2) sodium perchlorate solution of 25mol/kg is heated to 95 DEG C, be then stirred continuously down, is added within the 60min time
Polyacrylamide persistently stirs 6h and obtains the gel of clear, and mass fraction of the polyacrylamide in gel is 15.5%；
Water-keeping gel electrolyte is obtained after being cooled to room temperature, is denoted as polyacrylamide-sodium perchlorate water-keeping gel electrolyte；
3) polyacrylamide-sodium perchlorate water-keeping gel electrolyte is uniformly coated on nickel oxide and polyethylene diagrams table
Face, then with collector-electrode material-gel electrolyte-diaphragm-gel electrolyte-electrode material-collector structure type
It is assembled into the aqueous super capacitor based on water-keeping gel electrolyte.The device is without encapsulation.
The water-keeping gel electrolyte prepare to embodiment 6~8 and the supercapacitor based on water-keeping gel electrolyte carry out
Performance test under hot environment, the results showed that water-keeping gel electrolyte prepared by the present invention can be at 80 DEG C, 100 DEG C and 120
DEG C hot conditions and various wet and dry relative humidities under keep gel quality that significant change does not occur.The present invention
The supercapacitor based on water-keeping gel electrolyte of preparation still being capable of normal charge and discharge under conditions of temperature is up to 120 DEG C
It works and stablizes circulation, and there is biggish operating voltage.
As can be seen from the above embodiments, water-keeping gel electrolyte provided by the invention has excellent water holding capacity and resistance to
High temperature, the supercapacitor provided by the invention based on water-keeping gel electrolyte have the cycle life of overlength at normal temperature,
Temperature normal charge/discharge operation and can stablize circulation under conditions of being up to 120 DEG C, also, all have at ambient and elevated temperatures compared with
Big operating voltage, thus there is bigger energy density, it is capable of providing more energy.Therefore, provided by the invention to be based on
The aqueous super capacitor of water-keeping gel electrolyte can be safe and efficient under room temperature and hot environment apply.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of water-keeping gel electrolyte, which is characterized in that be prepared by electrolyte aqueous solution and oxygen-containing functional group polymer；
Electrolyte in the electrolyte aqueous solution is lithium perchlorate, double trifluoromethanesulfonimide lithiums, lithium hexafluoro phosphate, nitric acid
It is lithium, sodium chloride, sodium perchlorate, double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, sodium nitrate, potassium chloride, potassium hyperchlorate, double
It is one or more of in trifluoromethanesulfonimide potassium, Potassium Hexafluorophosphate and potassium nitrate；
The oxygen-containing functional group polymer is polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and poly- third
One or more of acrylamide.
2. water-keeping gel electrolyte according to claim 1, which is characterized in that electrolyte in the electrolyte aqueous solution
Molar concentration is 0.5~30mol/kg.
3. water-keeping gel electrolyte according to claim 1, which is characterized in that the oxygen-containing functional group polymer is being retained
Mass percent in gel electrolyte is 3~20%.
4. water-keeping gel electrolyte preparation method described in claims 1 to 3 any one, which is characterized in that including following step
It is rapid:
Under heating conditions, by electrolyte aqueous solution and oxygen-containing functional group mixed with polymers, it is solidifying that the water conservation is obtained after cooling
Glue electrolyte；The temperature of the heating is 75~100 DEG C.
5. a kind of aqueous super capacitor, which is characterized in that the aqueous super capacitor has sandwich structure；The sandwich knot
The center of structure is gel electrolyte, and the two sides ecto-entad of the sandwich structure is followed successively by collector and electrode material；
Or, the center of the interlayer structure is diaphragm, the two sides ecto-entad of the interlayer structure is followed successively by collector, electrode material
Material and gel electrolyte；
The gel electrolyte is water-keeping gel electrolyte described in claims 1 to 3 any one.
6. aqueous super capacitor according to claim 5, which is characterized in that the electrode material includes active carbon, stone
One of black alkene, carbon cloth, carbon felt, manganese oxide, ruthenium-oxide, iron oxide, cobalt oxide, nickel oxide and vanadium oxide；The collector
Including one of gold plaque, platinized platinum, silver strip, aluminium flake, copper sheet, titanium sheet, zinc metal sheet and nickel sheet；The diaphragm includes glass fibre, nothing
One of woven fabric, sulfonation non-woven fabrics, polyethylene film, polypropylene screen and filter membrane.
7. the preparation method of the aqueous super capacitor of claim 5 or 6, which comprises the following steps:
When not including diaphragm in the aqueous super capacitor structure, gel electrolyte is coated in the surface of electrode material,
Then it is fitted together with collector, obtains the aqueous super capacitor；
When in the aqueous super capacitor structure including diaphragm, gel electrolyte is coated in the table of electrode material and diaphragm
Then face is fitted together with collector, obtain the aqueous super capacitor；
The gel electrolyte is water-keeping gel electrolyte described in claims 1 to 3 any one.
8. preparation method according to claim 7, which is characterized in that painting of the gel electrolyte in electrode material surface
The one side that region is electrode material is covered, the another side of the electrode material is collector.
9. preparation method according to claim 7, which is characterized in that when include in the aqueous super capacitor structure every
When film, the gel electrolyte is on the two sides that the coating zone of membrane surface is diaphragm.
10. the aqueous super capacitor of claim 5 or 6 or the water system of claim 7~9 any one the method preparation
Application of the supercapacitor under room temperature and hot environment；When the aqueous super capacitor is under high temperature environment in application, institute
Stating includes diaphragm in the structure of aqueous super capacitor；Temperature≤120 DEG C of the hot environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910628789.8A CN110246705A (en) | 2019-07-12 | 2019-07-12 | A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910628789.8A CN110246705A (en) | 2019-07-12 | 2019-07-12 | A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110246705A true CN110246705A (en) | 2019-09-17 |
Family
ID=67891949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910628789.8A Pending CN110246705A (en) | 2019-07-12 | 2019-07-12 | A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110246705A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724288A (en) * | 2019-11-15 | 2020-01-24 | 东南大学 | Preparation method of flexible electrode membrane based on polyacrylamide hydrogel |
| CN110752098A (en) * | 2019-10-15 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Flexible supercapacitor based on temperature-sensitive gel electrolyte and preparation method thereof |
| CN111647111A (en) * | 2020-06-18 | 2020-09-11 | 南京邮电大学 | Hydrogel electrolyte film with double-network structure and preparation method and application thereof |
| CN112103094A (en) * | 2020-09-15 | 2020-12-18 | 电子科技大学 | All-solid-state flexible supercapacitor and preparation method thereof |
| CN113936927A (en) * | 2020-07-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | High-voltage aqueous electrolyte and application thereof |
| CN114644765A (en) * | 2022-03-09 | 2022-06-21 | 中国科学院上海硅酸盐研究所 | Composite ionic hydrogel composition and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916455A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Colloidal electrolyte super capacitor adopting reticular diaphragm |
| CN105161315A (en) * | 2015-09-16 | 2015-12-16 | 中国科学院电工研究所 | Hydrogel electrolyte thin film, and preparation method and application therefor |
| CN108807007A (en) * | 2018-08-08 | 2018-11-13 | 武汉理工大学 | The manufacture craft of three-dimensional manometer threadiness hole carbon material and high voltage micro super capacitor |
-
2019
- 2019-07-12 CN CN201910628789.8A patent/CN110246705A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916455A (en) * | 2014-03-12 | 2015-09-16 | 中国科学院大连化学物理研究所 | Colloidal electrolyte super capacitor adopting reticular diaphragm |
| CN105161315A (en) * | 2015-09-16 | 2015-12-16 | 中国科学院电工研究所 | Hydrogel electrolyte thin film, and preparation method and application therefor |
| CN108807007A (en) * | 2018-08-08 | 2018-11-13 | 武汉理工大学 | The manufacture craft of three-dimensional manometer threadiness hole carbon material and high voltage micro super capacitor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110752098A (en) * | 2019-10-15 | 2020-02-04 | 肇庆市华师大光电产业研究院 | Flexible supercapacitor based on temperature-sensitive gel electrolyte and preparation method thereof |
| CN110724288A (en) * | 2019-11-15 | 2020-01-24 | 东南大学 | Preparation method of flexible electrode membrane based on polyacrylamide hydrogel |
| CN111647111A (en) * | 2020-06-18 | 2020-09-11 | 南京邮电大学 | Hydrogel electrolyte film with double-network structure and preparation method and application thereof |
| CN113936927A (en) * | 2020-07-13 | 2022-01-14 | 中国科学院大连化学物理研究所 | High-voltage aqueous electrolyte and application thereof |
| CN112103094A (en) * | 2020-09-15 | 2020-12-18 | 电子科技大学 | All-solid-state flexible supercapacitor and preparation method thereof |
| CN114644765A (en) * | 2022-03-09 | 2022-06-21 | 中国科学院上海硅酸盐研究所 | Composite ionic hydrogel composition and preparation method and application thereof |
| CN114644765B (en) * | 2022-03-09 | 2023-12-08 | 中国科学院上海硅酸盐研究所 | Composite ion hydrogel composition and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110246705A (en) | A kind of water-keeping gel electrolyte and preparation method thereof and a kind of aqueous super capacitor and its preparation method and application | |
| Li et al. | Cobalt-embedded carbon nanofiber as electrocatalyst for polysulfide redox reaction in lithium sulfur batteries | |
| CN101800131B (en) | Active carbon-based material and preparation method thereof | |
| CN109818051A (en) | Lithium lanthanum zirconium oxygen solid electrolyte and preparation method thereof, lithium ion battery | |
| CN105218992B (en) | sulfonated graphene metal salt solid polymer electrolyte and its preparation method and application | |
| Guo et al. | Tailoring kirkendall effect of the KCu7S4 microwires towards CuO@ MnO2 core-shell nanostructures for supercapacitors | |
| CN106057477B (en) | A kind of water system Na ion chargeable capacitor batteries and preparation method thereof | |
| CN107221665A (en) | A kind of preparation method of Zinc ion battery barium oxide combination electrode material | |
| CN109081342A (en) | A kind of biomass porous active carbon of nipa palm leaf and its preparation method and application | |
| CN108281299A (en) | A kind of preparation method of bimetallic MOFs derivative electrode materials | |
| CN106981374B (en) | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application | |
| CN106816603B (en) | A kind of three-dimensional grapheme aeroge carries sulphur composite material and preparation method and application | |
| CN103579638A (en) | Air electrode catalyst of lithium air battery and preparation method of air electrode catalyst | |
| CN103811190A (en) | Antimony-doped tin dioxide coated porous manganese dioxide composite electrode material and preparation | |
| CN107134372A (en) | Ultracapacitor based on transient metal sulfide/nitrogen-doped graphene Yu di-iron trioxide/graphene | |
| CN103618056A (en) | Preparation method of nano-fiber membrane with three-dimensional porous structure for lithium ion battery diaphragm | |
| CN104681864A (en) | Gel type polymer electrolyte with high energy density and high ionic conductivity | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN110079895A (en) | A kind of titanate and titanium dioxide compound nano wire and preparation method thereof | |
| CN106384674A (en) | Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material | |
| CN109671946A (en) | Zinc ion battery positive electrode active materials, positive electrode, Zinc ion battery anode, Zinc ion battery and its preparation method and application | |
| CN106450444A (en) | Electrolyte for lithium-sulfur battery and preparation method for electrolyte | |
| Devi et al. | Fabrication of energy storage EDLC device based on self-synthesized TiO2 nanowire dispersed polymer nanocomposite films | |
| CN105271438A (en) | Preparation method of magnesium cobaltate porous structure electrode material with double-sea urchin shape | |
| CN110491684A (en) | Needle-shaped colored cobalt nickel bimetal hydroxide composite material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190917 |
|
| RJ01 | Rejection of invention patent application after publication |