CN107275097A - Conductive metal material is used as potassium ion hybrid super capacitor negative pole and potassium ion hybrid super capacitor and preparation method thereof - Google Patents
Conductive metal material is used as potassium ion hybrid super capacitor negative pole and potassium ion hybrid super capacitor and preparation method thereof Download PDFInfo
- Publication number
- CN107275097A CN107275097A CN201710583412.6A CN201710583412A CN107275097A CN 107275097 A CN107275097 A CN 107275097A CN 201710583412 A CN201710583412 A CN 201710583412A CN 107275097 A CN107275097 A CN 107275097A
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- China
- Prior art keywords
- potassium ion
- super capacitor
- hybrid super
- electrolyte
- negative pole
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- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 117
- 239000003990 capacitor Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007769 metal material Substances 0.000 title abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 65
- 239000002131 composite material Substances 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 34
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 238000003795 desorption Methods 0.000 claims abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 26
- 239000001103 potassium chloride Substances 0.000 claims description 25
- 235000011164 potassium chloride Nutrition 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052737 gold Inorganic materials 0.000 claims description 21
- 239000010931 gold Substances 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 21
- 239000011701 zinc Substances 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 18
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 18
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 18
- 229910052793 cadmium Inorganic materials 0.000 claims description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 18
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
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- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical group ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
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- ALTVCFKRYOLNPF-UHFFFAOYSA-N imino(trifluoromethyl)sulfanium Chemical class FC(F)(F)[S+]=N ALTVCFKRYOLNPF-UHFFFAOYSA-N 0.000 description 3
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- 229910001369 Brass Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- WMNPLXMHVCFDKJ-UHFFFAOYSA-N bromoethene;carbonic acid Chemical compound BrC=C.OC(O)=O WMNPLXMHVCFDKJ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BDMUZCMZJISZQO-UHFFFAOYSA-N carbonic acid;3,3-difluoroprop-1-ene Chemical compound OC(O)=O.FC(F)C=C BDMUZCMZJISZQO-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical group CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- IRPDISVJRAYFBI-UHFFFAOYSA-N nitric acid;potassium Chemical compound [K].O[N+]([O-])=O IRPDISVJRAYFBI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- BKIWAQYWKUFSRE-UHFFFAOYSA-N prop-1-ene;sulfuric acid Chemical group CC=C.OS(O)(=O)=O BKIWAQYWKUFSRE-UHFFFAOYSA-N 0.000 description 1
- YCCPTBSIWCOONA-UHFFFAOYSA-N prop-1-ene;sulfurous acid Chemical group CC=C.OS(O)=O YCCPTBSIWCOONA-UHFFFAOYSA-N 0.000 description 1
- BNXAVQNOSHPHJH-UHFFFAOYSA-N prop-2-enyl hydrogen sulfite Chemical compound OS(=O)OCC=C BNXAVQNOSHPHJH-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- WDGRWFSBSJISCI-UHFFFAOYSA-N tripotassium difluoro oxalate borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-].FOC(=O)C(=O)OF WDGRWFSBSJISCI-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to ultracapacitor field, specifically it is used as potassium ion hybrid super capacitor negative pole and potassium ion hybrid super capacitor and preparation method thereof there is provided a kind of conductive metal material.Potassium ion hybrid super capacitor includes negative pole, barrier film, positive pole and electrolyte；Negative pole is can be with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte；Positive pole includes positive electrode and plus plate current-collecting body, the positive electrode active materials in positive electrode for can reversibly in adsorption and desorption electrolyte anion carbon material；Potassium ion is present in the electrolyte of hybrid super capacitor.The potassium ion hybrid super capacitor with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte can be used as negative pole, above-mentioned material plays dual parts of negative active core-shell material and negative current collector, not only simplify the production technology of ultracapacitor, reduce production cost, also improve the energy density and theoretical specific capacity of ultracapacitor.
Description
Technical field
The present invention relates to ultracapacitor field, mixed in particular to a kind of conductive metal material as potassium ion
Super capacitor anode and potassium ion hybrid super capacitor and preparation method thereof.
Background technology
With the development of modern science and technology, people are increasing to the demand of the energy, finding a kind of novel energy turns into current
Exigence.Secondary cell is a kind of widely used electrochemical device, but is due to secondary cell in discharge and recharge
The chemical reaction occurred in journey can cause irreversible wound to it, limit its service life, and easily cause environment
Pollution, serious waste of resources.Ultracapacitor is a kind of new type of energy storage device, adsorbs positive and negative in electrolyte using electrode material
Ion formation double electrical layerses carry out energy storage, and the thermal energy storage process is physical absorption/desorption process, therefore with the longer circulation longevity
Life and higher charge/discharge rates, and it is environment-friendly, stand-by power supply is can be widely applied to, high-frequency discharge and recharge is high-power defeated
The occasion such as go out.Common super capacitor material is main using carbon material as both positive and negative polarity active material, but this super electricity at present
The capacity and energy density of container are relatively low, and negative active core-shell material also needs to mix with binding agent, conductive agent etc., and is coated in metal
On paper tinsel collector, production technology is relatively complicated, and is easily come off between negative active core-shell material and collector, adds production procedure
Complexity and production cost.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is that offer one kind can be with potassium ion alloyed metal (AM), alloy or gold in electrolyte
Belong to application of the composite simultaneously as negative active core-shell material and negative current collector in potassium ion hybrid super capacitor.It is above-mentioned
Metal, alloy or metallic composite can greatly reduce potassium ion as negative active core-shell material and negative current collector simultaneously and mix
The deadweight of ultracapacitor is closed, the energy density and theoretical specific capacity of potassium ion hybrid super capacitor is further improved, simplified
The production technology of capacitor, reduction production cost and more environmentally-friendly.
The second object of the present invention is to provide a kind of potassium ion hybrid super capacitor, the potassium ion hybrid capacitor
The negative pole of device for can with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte, above-mentioned metal, alloy or
Metallic composite plays dual parts of negative active core-shell material and negative current collector, can greatly reduce capacitor oneself
Weight, further improve capacitor energy density and theoretical specific capacity, simplify capacitor production technology, reduction production cost and
It is more environmentally-friendly.
The third object of the present invention is to provide a kind of preparation method of potassium ion hybrid super capacitor, above-mentioned preparation side
Method technique is simple, and the potassium ion hybrid super capacitor prepared using this method has energy density high and theoretical specific capacity
High advantage.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, can be with potassium ion alloyed metal (AM), alloy or metallic composite the invention provides one kind
Application as negative active core-shell material and negative current collector in potassium ion hybrid super capacitor simultaneously, potassium ion is present in mixed
In the electrolyte for closing ultracapacitor.
As further preferably technical scheme, the metal is any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Kind；
The alloy is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
The metallic composite is including at least the composite wood of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Material.
Second aspect, the invention provides a kind of potassium ion hybrid super capacitor, including negative pole, barrier film, positive pole and electricity
Solve liquid；
The negative pole is can be with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte；
The positive pole includes positive electrode and plus plate current-collecting body, and the positive electrode active materials in the positive electrode is can
The carbon material of anion in inverse ground adsorption and desorption electrolyte；
Electrolyte is organic solvent and/or ionic liquid containing sylvite.
As further preferably technical scheme, the negative pole is any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Plant simple metal；
Or, the negative pole is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
Or, the negative pole is including at least the composite of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium.
As further preferably technical scheme, the carbon material includes activated carbon, CNT, porous charcoal, graphene
With any one in carbon fiber or at least two combination.
As further preferably technical scheme, the positive electrode also includes conductive agent and binding agent, positive-active material
The content of material is 60-95wt.%, and the content of conductive agent is 2-30wt.%, and the content of binding agent is 3-10wt.%.
It is in the electrolytic solution 0.1- there is provided the concentration range of the sylvite of potassium ion as further preferably technical scheme
10mol/L；
Preferably, sylvite is Potassium Hexafluorophosphate.
As further preferably technical scheme, additive is also included in electrolyte, the additive is selected from esters, sulfone
At least one of class, ethers, nitrile or olefines, the content of the additive is 0.1-20wt.%.
The third aspect, the invention provides a kind of preparation method of potassium ion hybrid super capacitor, by negative pole, electrolysis
Liquid, barrier film and positive pole are assembled, and obtain potassium ion hybrid super capacitor.
As further preferably technical scheme, the preparation method comprises the following steps：
A) negative pole is prepared：Will be standby as negative pole after the metal of required size, alloy or metallic composite surface treated
With；
B) electrolyte is prepared：Sylvite is dissolved in solvent, is sufficiently stirred for obtaining electrolyte；
C) barrier film is prepared：By the porous polymer film of required size, inorganic porous film or organic/inorganic composite film
It is used as barrier film；
D) positive pole is prepared：Anode sizing agent or positive pole flaky material is made in positive electrode active materials, conductive agent and binding agent；Again
Anode sizing agent is coated on plus plate current-collecting body surface or positive pole flaky material is pressed in plus plate current-collecting body surface, needed for being dried to obtain
The positive pole of size；
The barrier film and step d) that electrolyte, the step c) that negative pole, the step b) that step a) is obtained are obtained are obtained are obtained
Positive pole assembled, obtain potassium ion hybrid super capacitor.
Compared with prior art, beneficial effects of the present invention are：
Can be same with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte the invention provides one kind
The application of Shi Zuowei negative active core-shell materials and negative current collector in potassium ion hybrid super capacitor, above-mentioned metal, alloy or
Metallic composite as the negative active core-shell material and negative current collector of potassium ion hybrid super capacitor, will be constituted existing simultaneously
Two key elements (negative active core-shell material and negative current collector) in super capacitor anode save slightly a kind of, so as to reduce one
The volume and weight of part, can significantly reduce capacitor deadweight, volume and materials cost；Negative active core-shell material and negative pole currect collecting
Being designed with beneficial to the transmission range for shortening potassium ion for body integration, is conducive to more effective mass transfer and/or load transfer；Due to increase
The accounting of active material, therefore, it is possible to further improve the energy density of hybrid super capacitor, and using metal and potassium from
Alloying/removal alloying of son realizes the negative reaction of hybrid super capacitor, improves specific capacity；Due to without the use of organic viscous
Knot agent etc. is bonded, therefore enormously simplify the production technology of capacitor, and will not fall off phenomenon, reduce it is artificial with
Equipment cost, and it is more environmentally-friendly.
The characteristics of potassium ion hybrid super capacitor that the present invention is provided has secondary cell and ultracapacitor concurrently, has simultaneously
There is higher energy density and specific capacity；Its negative pole is metal, alloy or metallic composite that can be with potassium formation alloy, on
State metal, alloy or metallic composite and play dual parts of negative active core-shell material and negative current collector, can greatly drop
The deadweight of low hybrid super capacitor, further improves the energy density and theoretical specific capacity of hybrid super capacitor, simplifies mixed
Close the production technology of ultracapacitor, reduce production cost and more environmentally-friendly；In addition, will be traditional in the electrolyte of the capacitor
Lithium ion is replaced for potassium ion, solves the problem of lithium resource reserves are limited, its application is no longer restricted by lithium resource.
The preparation method technique for the potassium ion hybrid super capacitor that the present invention is provided is simple, is prepared using this method
Potassium ion hybrid super capacitor have the advantages that energy density is high and specific capacity is high.
Brief description of the drawings
Fig. 1 is the structural representation of the potassium ion hybrid super capacitor of one embodiment of the present invention.
Icon：1- negative poles；2- electrolyte；3- barrier films；4- positive electrodes；5- plus plate current-collecting bodies.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.
In a first aspect, can be with potassium ion alloyed metal (AM), alloy or metallic composite the invention provides one kind
Application as negative active core-shell material and negative current collector in potassium ion hybrid super capacitor simultaneously, potassium ion is present in mixed
In the electrolyte for closing ultracapacitor.
In the present invention, " can be with potassium ion alloyed metal (AM), alloy or metallic composite " be refer to potassium from
Son occurs the metal of alloying reaction, the alloy material of alloying reaction can occur with potassium ion or can occur with potassium ion
The metal composite conductive material of alloying reaction.
Alloy refer to as two or more metal and metal or it is nonmetallic through certain method synthesized by there is gold
Belong to the material of characteristic.
Metallic composite refers to that metal is combined formed metal-based compound conductive material with other nonmetallic materials.Allusion quotation
Type but nonrestrictive metallic composite include graphene-metallic composite, carbon fiber reinforced metal matrix composite and ceramics-
Metallic composite etc..
Above-mentioned metal, alloy or metallic composite are simultaneously as the negative active core-shell material of potassium ion hybrid super capacitor
Two key elements (negative active core-shell material and negative current collector) constituted in existing super capacitor anode are saved with negative current collector
It is slightly a kind of, so as to reduce the volume and weight of a part, can significantly reduce hybrid super capacitor deadweight, volume and
Materials cost；Negative active core-shell material and the transmission range being designed with beneficial to shortening potassium ion of negative current collector integration, favorably
In more effective mass transfer and/or load transfer；Due to adding the accounting of active material, therefore, it is possible to further improve the energy of capacitor
Metric density, and the negative reaction of capacitor is realized using alloying/removal alloying of metal and potassium ion, improve specific capacity；By
Bonded in without the use of organic binder bond etc., therefore enormously simplify the production technology of hybrid super capacitor, and will not
Phenomenon is fallen off, artificial and equipment cost is reduced, and it is more environmentally-friendly.
Compared with existing use carbon material is as negative active core-shell material, using above-mentioned metal, alloy or Metals composite
Material not only has higher energy close as the negative active core-shell material and negative current collector of potassium ion hybrid super capacitor simultaneously
Degree, specific capacity, moreover it is possible to significantly simplify production technology, reduce cost and more environmentally-friendly.
It is preferably carried out in one kind in mode, the metal is any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Kind；
The alloy is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
The metallic composite is including at least the composite wood of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Material.
Above-mentioned metal, alloy and metallic composite be respectively provided with rich reserves, it is cheap, be easily obtained and environment friend
Good advantage, the cost of hybrid super capacitor can be significantly reduced as potassium ion hybrid super capacitor negative pole, and it is led
More preferably, easily capturing the potassium ion in more electrolyte, potassium ion is occurred alloying/removal alloying with it anti-for electrical property
Should, thus improve the specific capacity and energy density of hybrid super capacitor.
Above-mentioned metal is preferably metallic tin.Device can be made as the negative pole of potassium ion hybrid super capacitor using metallic tin
The specific capacitance and energy density of part are higher.
In the present invention, alloy is typical but non-limiting to be：Red brass, leypewter, zinc antimony alloy, zinc germanium alloy,
Tin zinc metal etc..Metallic composite is typical but non-limiting to be：Tin/graphene composite foil or polyaniline/tin are compound
Paillon foil etc..
Second aspect, as shown in figure 1, the invention provides a kind of potassium ion hybrid super capacitor, including negative pole 1, every
Film 3, positive pole and electrolyte 2；
The negative pole is can be with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte；
The positive electrode active materials that the positive pole includes in positive electrode 4 and plus plate current-collecting body 5, the positive electrode are can
Reversibly in adsorption and desorption electrolyte anion carbon material；
Electrolyte is organic solvent and/or ionic liquid containing sylvite.
In the present invention, " can be with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte " refers to energy
Potassium ion occurs the metal of alloying reaction, the conjunction of alloying reaction can occur with potassium ion in electrolyte in enough and electrolyte
The metal composite conductive material of alloying reaction can occur with potassium ion in electrolyte for golden material.
Alloy refer to as two or more metal and metal or it is nonmetallic through certain method synthesized by there is gold
Belong to the material of characteristic.
Metallic composite refers to that metal is combined formed metal-based compound conductive material with other nonmetallic materials.Allusion quotation
Type but nonrestrictive metallic composite include graphene-metallic composite, carbon fiber reinforced metal matrix composite and ceramics-
Metallic composite etc..
The characteristics of above-mentioned potassium ion hybrid super capacitor has secondary cell and ultracapacitor concurrently, while having higher
Energy density and specific capacity；Its negative pole for can with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte,
Above-mentioned metal, alloy or metallic composite play dual parts of negative active core-shell material and negative current collector, will constitute existing
Two key elements (negative active core-shell material and negative current collector) in super capacitor anode save slightly a kind of, so as to reduce one
The volume and weight of part, can significantly reduce hybrid super capacitor deadweight, volume and materials cost；Negative active core-shell material and
Being designed with beneficial to the transmission range for shortening potassium ion for negative current collector integration, is conducive to more effective mass transfer and/or load transfer；
Due to adding the accounting of active material, therefore, it is possible to further improve the energy density of device, and metal and potassium ion are utilized
Alloying/removal alloying realize the negative reaction of capacitor, improve specific capacity；Due to being carried out without the use of organic binder bond etc.
Bond, therefore enormously simplify the production technology of hybrid super capacitor, and phenomenon will not be fallen off, reduce artificial and set
Standby cost, and it is more environmentally-friendly.In addition, in the electrolyte of the hybrid super capacitor by traditional lithium ion replace in order to potassium from
Son, alleviates the problem of lithium resource reserves are limited, its application is no longer restricted by lithium resource.
Above-mentioned hybrid super capacitor operation principle is：In charging process, anion transport in electrolyte to positive pole
And be adsorbed in positive electrode, while potassium ion is migrated to negative pole, and obtain electronically forming potassium atom, and with negative pole formation potassium-
Metal alloy, above potassium ion obtains electronics and the process referred to as alloying reaction of potassium-metal alloy is formed with metal；Discharged
Anion is desorbed from positive electrode and returned in electrolyte in journey, potassium ion from negative pole removal alloying returns to electrolyte so that
Realize whole charge and discharge process.
It is preferably carried out in one kind in mode, the negative pole is any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Simple metal；
Or, the negative pole is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
Or, the negative pole is including at least the composite of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium.
Above-mentioned metal, alloy and metallic composite be respectively provided with rich reserves, it is cheap, be easily obtained and environment friend
Good advantage, the cost of capacitor can be significantly reduced as potassium ion hybrid super capacitor negative pole, and its electric conductivity is more
Good, easily capturing the potassium ion in more electrolyte makes potassium ion occur alloying/removal alloying reaction with it, thus carries
The specific capacity and energy density of high capacitance.
Above-mentioned metal is preferably metallic tin.Electricity can be made as the negative pole of potassium ion hybrid super capacitor using metallic tin
The specific capacitance and energy density of container are higher.
In the present invention, alloy is typical but non-limiting to be：Red brass, leypewter, zinc antimony alloy, zinc germanium alloy,
Tin zinc metal etc..Metallic composite is typical but non-limiting to be：Tin/graphene composite foil or polyaniline/tin are compound
Paillon foil etc..
Be preferably carried out in one kind in mode, the carbon material include activated carbon, CNT, porous charcoal, graphene and
In carbon fiber any one or at least two combination.Above-mentioned carbon material is porous form, and specific surface area is big, its to the moon from
The suction-operated of son is stronger.More preferably activated carbon.
In the present invention, carbon material is typical but non-limiting to be：Activated carbon, CNT, porous charcoal, graphene, carbon is fine
Dimension, the combination of activated carbon and CNT, the combination of porous charcoal and graphene, the combination of graphene and carbon fiber, activated carbon, carbon
The combination of nanotube and porous charcoal, combination of porous charcoal, graphene and carbon fiber etc..
It should be noted that the carbon material also include including at least activated carbon, CNT, porous charcoal, graphene or
The composite of any one in carbon fiber, if the composite can reversibly in adsorption and desorption electrolyte it is cloudy from
Son.
It is preferably carried out in one kind in mode, the positive electrode also includes conductive agent and binding agent, positive electrode active materials
Content be 60-95wt.%, the content of conductive agent is 2-30wt.%, and the content of binding agent is 3-10wt.%.
Conductive agent is to ensure that electrode has good charge-discharge performance, be usually added into when pole piece makes a certain amount of
Conductive materials, play a part of collecting micro-current, to reduce electrode between active material, between active material and collector
Contact resistance accelerates the rate travel of electronics, while migration rate of the potassium ion in electrode material can be also effectively improved, from
And improve the efficiency for charge-discharge of electrode.The main function of binding agent is to bond and keep active material, strengthens positive electrode active materials
The electronics of (carbon material) between conductive agent and positive electrode active materials and collector is contacted, preferably the structure of stabilized electrodes,
And certain cushioning effect is played in hybrid super capacitor charge and discharge process.The main positive-active by above-mentioned weight content
The positive electrode that material, conductive agent and binding agent are prepared from not only form stable, difficult for drop-off, and electric conductivity is more preferable.
It should be noted that the content of above-mentioned positive electrode active materials, conductive agent and binding agent is referred both in positive electrode
Content.The present invention positive electrode in, the typical but non-limiting percentage by weight of positive electrode active materials be 60%, 70%,
75%th, 80%, 85%, 90% or 95%；The typical but non-limiting percentage by weight of conductive agent be 2%, 5%, 10%,
15%th, 20%, 25% or 30%；The typical but non-limiting percentage by weight of binding agent be 3%, 4%, 5%, 6%, 7%,
8%th, 9% or 10%.
In the present invention, conductive agent and binding agent in positive electrode are not particularly limited, from conduction commonly used in the art
Agent and binding agent.Alternatively, conductive agent be conductive black, conductive carbon ball, electrically conductive graphite, CNT, conductive carbon fibre,
One or more in graphene, redox graphene.Binding agent is Kynoar, polytetrafluoroethylene (PTFE), polyvinyl alcohol, carboxylic
One or more in methylcellulose, SBR rubber, TPO.
In the present invention, plus plate current-collecting body is not particularly limited, from plus plate current-collecting body commonly used in the art.It is optional
Ground, the plus plate current-collecting body includes metal, alloy or metal composite conductive material；Further, plus plate current-collecting body includes
Any one in aluminium, copper, iron, tin, zinc, nickel, titanium or manganese, or including at least any in aluminium, copper, iron, tin, zinc, nickel, titanium or manganese
A kind of alloy, or including at least the composite of any one in aluminium, copper, iron, tin, zinc, nickel, titanium or manganese.
It is preferably carried out in one kind in mode, is in the electrolytic solution 0.1- there is provided the concentration range of the sylvite of potassium ion
10mol/L.Sylvite concentration is too low in the ion transmission performance of ion concentration influence electrolyte, electrolyte, and ion transmission performance is poor,
Conductance is low；Sylvite excessive concentration in electrolyte, ion is excessive, and the viscosity of electrolyte and the degree of ion association also can be with sylvite
Concentration increases and increased, and this can reduce electrical conductivity again.Originally it is preferably carried out the conduction of the sylvite for the certain concentration that mode is provided
Property is optimal.
In the present invention, the typical but non-limiting concentration of sylvite is：0.1mol/L、0.2mol/L、0.3mol/L、
0.4mol/L、0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1.0mol/L、2mol/L、3mol/L、
4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L.
It is highly preferred that being in the electrolytic solution 0.1-1mol/L there is provided the concentration range of the sylvite of potassium ion.
In the present invention, if as electrolyte sylvite it is not also specifically limited, can be dissociated into cation and it is cloudy from
Son.Alternatively, the sylvite includes Potassium Hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, nitric acid
Potassium, difluoro oxalate potassium borate, potassium pyrophosphate, Potassium dodecylbenzenesulfonate, dodecyl sulphate potassium, citric acid tri potassium, metaboric acid
Potassium, potassium borate, potassium molybdate, potassium tungstate, KBr, potassium nitrite, Potassiumiodate, KI, potassium silicate, lignin sulfonic acid potassium, grass
Sour potassium, potassium aluminate, pyrovinic acid potassium, potassium acetate, potassium bichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium hyperchlorate, fluoroform
Any one in alkane sulfimide potassium and trifluoromethayl sulfonic acid potassium or at least two.
Sylvite in the present invention is preferably Potassium Hexafluorophosphate.When from Potassium Hexafluorophosphate, the ratio of hybrid super capacitor
Electric capacity and energy density highest.
In the present invention, the solvent in electrolyte is not particularly limited, if solvent can make electrolyte be dissociated into sun from
Son and anion, and cation and anion can be with free migrations.Alternatively, the solvent of electrolyte include esters, sulfone class,
One or more in ethers, nitrile or ionic liquid.
Alternatively, solvent is selected from propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid diformazan
Ester (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), DMAC N,N' dimethyl acetamide (DMA), fluoro
Ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), gamma-butyrolacton (GBL), tetrahydrochysene furan
Mutter (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-dioxy pentamethylene
(4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), TRIGLYME (DG), dimethyl sulfone
(MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene fat (PS), the formicester of sulfurous acid two (DMS), sulfurous acid
Diethyl fat (DES), crown ether (12-crown-4), 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoro
Borate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl group -3- methylimidazoles-hexafluorophosphate, 1-
Propyl group -3- methylimidazoles-tetrafluoroborate, 1- propyl group -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- first
Base imidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulphur
The double trifluoros of imide salts, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin-
Sulfonyloxy methyl inferior amine salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, propylpiperdine-bis- trifluoros
One or more in sulfonyloxy methyl inferior amine salt, N- first, butyl piperidine-bis trifluoromethyl sulfimide salt.
In order to prevent destruction of the negative pole in discharge and recharge caused by Volume Changes, make negative pole structure stable, improve negative pole
Service life and performance, and then improve in the cycle performance of the hybrid super capacitor, electrolyte of the present invention preferred increase and add
Plus agent, additive is selected from least one of esters, sulfone class, ethers, nitrile or olefines, the addition of additive in the electrolytic solution
Measure as 0.1-20wt.%.Increased additive can form stable solid electrolyte film in negative terminal surface so that negative pole conduct
Active material is not destroyed when reacting, to improve the cycle life of hybrid super capacitor.
In the present invention, the content of additive in the electrolytic solution is typical but non-limiting to be：0.1wt.%, 0.5wt.%,
1wt.%, 2wt.%, 4wt.%, 6wt.%, 8wt.%, 10wt.%, 12wt.%, 14wt.%, 16wt.%, 18wt.% or
20wt.%.
Further, additive is selected from fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3-
Propane sultone, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid propylene, ethyl sulfate, ethylene sulfite, sulfurous
Acid propylene ester, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide (DMSO),
Methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain
Ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, three
Fluoro ethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, monoethanolamine, carbonization dimethylamine,
Cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate,
One or more in carbon dioxide, sulfur dioxide, lithium carbonate.
In the present invention, barrier film is it is not also specifically limited, using the existing common diaphragm in this area.The barrier film typical case
But the organic/inorganic THIN COMPOSITE of nonrestrictive porous polymer film, the inorganic porous film of insulation or insulation for insulation
Film.Preferably porous polypropylene film, porous polyethylene film, porous polymer laminated film, fibreglass diaphragm or porous
One or more in ceramic diaphragm.
The third aspect, the invention provides a kind of preparation method of potassium ion hybrid super capacitor, by negative pole, electrolysis
Liquid, barrier film and positive pole are assembled, and obtain potassium ion hybrid super capacitor.Above-mentioned preparation method technique is simple, using this
The potassium ion hybrid super capacitor that method is prepared has the advantages that energy density is high and theoretical specific capacity is high.
It is preferably carried out in one kind in mode, the preparation method comprises the following steps：
A) negative pole is prepared：Will be standby as negative pole after the metal of required size, alloy or metallic composite surface treated
With；
B) electrolyte is prepared：Sylvite is dissolved in solvent and additive, is sufficiently stirred for obtaining electrolyte；
C) barrier film is prepared：By the porous polymer film of required size, inorganic porous film or organic/inorganic composite film
It is used as barrier film；
D) positive pole is prepared：Anode sizing agent or positive pole flaky material is made in positive electrode active materials, conductive agent and binding agent；Again
Anode sizing agent is coated on plus plate current-collecting body surface or positive pole flaky material is pressed in plus plate current-collecting body surface, needed for being dried to obtain
The positive pole of size；
The barrier film and step d) that electrolyte, the step c) that negative pole, the step b) that step a) is obtained are obtained are obtained are obtained
Positive pole assembled, obtain potassium ion hybrid super capacitor.
Preferably, specifically included during assembling：Under inert gas or anhydrous and oxygen-free environment, by the negative pole prepared, barrier film,
Positive pole Close stack successively, electrolyte, which is added dropwise, makes barrier film complete wetting, is then encapsulated into housing, completes potassium ion hybrid super electricity
Container is assembled.
The potassium ion hybrid super capacitor form of the present invention is not limited to button capacitor, can also be set according to nucleus
Count into the forms such as plate, cylindrical type.
With reference to embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of potassium ion hybrid super capacitor, including positive pole, negative pole, electrolyte, barrier film and housing.
Prepare hybrid super capacitor negative pole：The tinfoil paper for taking thickness to be 0.2mm, cuts into diameter 12mm disk, uses second
Alcohol cleaning tinfoil paper surface, dries standby as negative pole；
Prepare barrier film：Polypropylene diaphragm is cut into standby as barrier film after diameter 16mm disk；
Prepare electrolyte：Weigh 0.736g Potassium Hexafluorophosphates and be added to 5ml ethylene carbonates, dimethyl carbonate and carbonic acid first
(three's volume ratio is 4 to the mixed solvent of ethyl ester:3:2) and in 1wt% vinylene carbonate, stir complete to Potassium Hexafluorophosphate
Dissolving, the fluorinated ethylene carbonate that then addition mass fraction is 10% is used as electrolysis as additive after stirring
Liquid is standby；
Prepare hybrid super capacitor positive pole：By 0.8g asphalt based active carbons (specific surface area 2000m2/ g), 0.1g carbon blacks,
0.1g polytetrafluoroethylene (PTFE) is added in 2ml water, is fully ground acquisition uniform sizing material；Then slurry is evenly applied to aluminium foil surface
(i.e. plus plate current-collecting body) is simultaneously dried in vacuo；Dry the electrode obtained piece is cut into diameter 10mm disk, mixing is used as after compacting
Supercapacitor positive electrode is standby；
Hybrid super capacitor is assembled：In the glove box of inert gas shielding, by the above-mentioned negative pole prepared, barrier film,
Positive pole Close stack successively, electrolyte, which is added dropwise, makes barrier film complete wetting, and above-mentioned stacking portion then is encapsulated into button capacitor
Housing, completes hybrid super capacitor assembling.
Embodiment 2-10
Embodiment 2-10 prepares what is used during negative pole with being removed in the potassium ion hybrid super capacitor preparation process of embodiment 1
Beyond tinsel is different, other all steps and the material used are all identical, to embodiment 1-10 potassium ion hybrid super
The energy stores performance of capacitor is tested, and negative material used in embodiment 1-10 and its energy stores performance are specifically joined
It is shown in Table 1.
Table 1：The performance parameter table of embodiment 1-10 potassium ion hybrid super capacitor
Embodiment 11-16
Embodiment 11-16 in the potassium ion hybrid super capacitor preparation process of embodiment 1 with removing positive electrode active materials not
With beyond, other all steps and the material used are all identical, to embodiment 1 and 11-16 potassium ion hybrid super capacitor
Energy stores performance tested, positive electrode active materials and its energy stores performance are specific used in embodiment 1 and 11-16
Referring to table 2.
Table 2：The performance parameter table of embodiment 1 and 11-16 potassium ion hybrid super capacitor
Embodiment 17-22
Embodiment 17-22 is with removing conductive agent and binding agent in the potassium ion hybrid super capacitor preparation process of embodiment 1
And its beyond content is different, other all steps and the material used are all identical, embodiment 1 and 17-22 potassium ion are mixed
The energy stores performance of ultracapacitor is tested, conductive agent and binding agent and its energy used in embodiment 1 and 17-22
Storage performance is referring specifically to table 3.
Table 3：The performance parameter table of embodiment 1 and 17-22 potassium ion hybrid super capacitor
Embodiment 23-25
Embodiment 23-25 is different from the concentration in the potassium ion hybrid super capacitor preparation process of embodiment 1 except sylvite
In addition, other all steps and the material used are all identical, to embodiment 1 and 23-25 potassium ion hybrid super capacitor
Energy stores performance is tested, the concentration and its energy stores performance of sylvite used in embodiment 1 and 23-25 referring specifically to
Table 4.
Table 4：The performance parameter table of embodiment 1 and 23-25 potassium ion hybrid super capacitor
Embodiment 26-29
Embodiment 26-29 is different from the selection in the potassium ion hybrid super capacitor preparation process of embodiment 1 except sylvite
In addition, other all steps and the material used are all identical, to embodiment 1 and 26-29 potassium ion hybrid super capacitor
Energy stores performance is tested, and sylvite and its energy stores performance are referring specifically to table 5 used in embodiment 1 and 26-29.
Table 5：The performance parameter table of embodiment 1 and 26-29 potassium ion hybrid super capacitor
Embodiment 30-33
Embodiment 30-33 is with removing used in electrolyte add in the potassium ion hybrid super capacitor preparation process of embodiment 1
Plus beyond agent and its content difference, other all steps and the material used are all identical, to embodiment 1 and 30-33 potassium ion
The energy stores performance of hybrid super capacitor is tested, additive and content and its energy used in embodiment 1 and 30-33
Storage performance is measured referring specifically to table 6.
Table 6：The performance parameter table of embodiment 1 and 30-33 potassium ion hybrid super capacitor
Embodiment 34-37
Embodiment 34-37 is with removing the material used in barrier film in the potassium ion hybrid super capacitor preparation process of embodiment 1
Beyond difference, other all steps and the material used are all identical, to embodiment 1 and 34-37 potassium ion hybrid capacitor
The energy stores performance of device is tested, and diaphragm material and its energy stores performance are specifically joined used in embodiment 1 and 34-37
It is shown in Table 7.
Table 7：The performance parameter table of embodiment 1 and 34-37 potassium ion hybrid super capacitor
Comparative example 1
As different from Example 1, the positive and negative electrode material of comparative example 1 is activated carbon, conductive black, polytetrafluoroethylene (PTFE),
Wherein activated carbon, conductive black, the mass ratio of polytetrafluoroethylene (PTFE) are 8:1:1.
Prepare symmetrical potassium ion ultracapacitor positive/negative：By 0.8g asphalt based active carbons (specific surface area 2000m2/g)、
0.1g carbon blacks, 0.1g Kynoar are added in 2ml water, are fully ground acquisition uniform sizing material；Then slurry is uniformly coated
In aluminium foil surface (i.e. plus plate current-collecting body) and it is dried in vacuo；Dry the electrode obtained piece is cut into diameter 10mm disk, compacting
It is standby as hybrid super capacitor positive pole afterwards；
Remaining material and preparation process are same as Example 1.
Comparative example 2
As different from Example 1, electrolyte is lithium hexafluoro phosphate, its concentration and embodiment 1 in the electrolyte of comparative example 2
In Potassium Hexafluorophosphate concentration it is identical.
Remaining material and preparation process are same as Example 1.
The energy stores performance to comparative example 1-2 capacitor is tested respectively, and with the performance of the embodiment of the present invention 1
It is compared, energy stores performance is referring specifically to table 8.
Table 8：The performance parameter table of comparative example 1-2 capacitor
| Numbering | Specific capacitance (F/g) | Energy density (Wh/kg) |
| Comparative example 1 | 60 | 12 |
| Comparative example 2 | 73 | 48 |
| Embodiment 1 | 80 | 55 |
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. one kind as negative active core-shell material and can be born simultaneously with potassium ion alloyed metal (AM), alloy or metallic composite
Application of the pole collector in potassium ion hybrid super capacitor, potassium ion is present in the electrolyte of hybrid super capacitor.
2. application according to claim 1, it is characterised in that the metal is in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium
Any one；
The alloy is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
The metallic composite is including at least the composite of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium.
3. a kind of potassium ion hybrid super capacitor, it is characterised in that including negative pole, barrier film, positive pole and electrolyte；
The negative pole is can be with potassium ion alloyed metal (AM), alloy or metallic composite in electrolyte；
The positive electrode active materials that the positive pole includes in positive electrode and plus plate current-collecting body, the positive electrode are can be reversibly
The carbon material of anion in adsorption and desorption electrolyte；
Electrolyte is organic solvent and/or ionic liquid containing sylvite.
4. potassium ion hybrid super capacitor according to claim 3, it is characterised in that the negative pole be tin, zinc, lead,
Any one simple metal in antimony, cadmium, gold, bismuth or germanium；
Or, the negative pole is including at least the alloy of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium；
Or, the negative pole is including at least the composite of any one in tin, zinc, lead, antimony, cadmium, gold, bismuth or germanium.
5. potassium ion hybrid super capacitor according to claim 3, it is characterised in that the carbon material includes activity
In charcoal, CNT, porous charcoal, graphene and carbon fiber any one or at least two combination.
6. potassium ion hybrid super capacitor according to claim 3, it is characterised in that the positive electrode also includes leading
Electric agent and binding agent, the content of positive electrode active materials is 60-95wt.%, and the content of conductive agent is 2-30wt.%, binding agent
Content is 3-10wt.%.
7. potassium ion hybrid super capacitor according to claim 3, it is characterised in that in the electrolytic solution there is provided potassium from
The concentration range of the sylvite of son is 0.1-10mol/L；
Preferably, sylvite is Potassium Hexafluorophosphate.
8. the potassium ion hybrid super capacitor according to claim any one of 3-7, it is characterised in that also wrapped in electrolyte
Include additive, the additive is selected from least one of esters, sulfone class, ethers, nitrile or olefines, the additive contains
Measure as 0.1-20wt.%.
9. the preparation method of the potassium ion hybrid super capacitor described in claim any one of 3-8, it is characterised in that will be negative
Pole, electrolyte, barrier film and positive pole are assembled, and obtain potassium ion hybrid super capacitor.
10. the preparation method of potassium ion hybrid super capacitor according to claim 9, it is characterised in that including following
Step：
A) negative pole is prepared：Will be standby as negative pole after the metal of required size, alloy or metallic composite surface treated；
B) electrolyte is prepared：Sylvite is dissolved in solvent, is sufficiently stirred for obtaining electrolyte；
C) barrier film is prepared：Using the porous polymer film of required size, inorganic porous film or organic/inorganic composite film as
Barrier film；
D) positive pole is prepared：Anode sizing agent or positive pole flaky material is made in positive electrode active materials, conductive agent and binding agent；Again will just
Pole slurry is coated on plus plate current-collecting body surface or positive pole flaky material is pressed in into plus plate current-collecting body surface, is dried to obtain required size
Positive pole；
The barrier film and step d) that electrolyte, the step c) that negative pole, the step b) that step a) is obtained are obtained are obtained are obtained just
Pole is assembled, and obtains potassium ion hybrid super capacitor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110310840A (en) * | 2019-03-22 | 2019-10-08 | 厦门稀土材料研究所 | Potassium ion hybrid super capacitor positive electrode active materials and potassium ion hybrid super capacitor |
| CN111584248A (en) * | 2020-05-29 | 2020-08-25 | 湖南大学 | Potassium ion hybrid capacitor and preparation method thereof |
| CN112599361A (en) * | 2020-12-14 | 2021-04-02 | 湖南大学 | Wide-temperature-range high-performance electrochemical energy storage device based on bismuth-based electrode |
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