CN110010373A - A kind of embedding zinc processing method of electrode and its application in the preparation of cell type supercapacitor - Google Patents
A kind of embedding zinc processing method of electrode and its application in the preparation of cell type supercapacitor Download PDFInfo
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- CN110010373A CN110010373A CN201910239340.2A CN201910239340A CN110010373A CN 110010373 A CN110010373 A CN 110010373A CN 201910239340 A CN201910239340 A CN 201910239340A CN 110010373 A CN110010373 A CN 110010373A
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- zinc
- electrode
- embedding
- cell type
- type supercapacitor
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000011701 zinc Substances 0.000 title claims abstract description 75
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000003672 processing method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 36
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 18
- 238000002848 electrochemical method Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 13
- 229960001763 zinc sulfate Drugs 0.000 claims description 13
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002484 cyclic voltammetry Methods 0.000 claims description 9
- 239000011245 gel electrolyte Substances 0.000 claims description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- NGOCMUBXJDDBLB-UHFFFAOYSA-N trifluoromethanesulfonic acid;zinc Chemical compound [Zn].OS(=O)(=O)C(F)(F)F NGOCMUBXJDDBLB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000230 xanthan gum Substances 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 229940082509 xanthan gum Drugs 0.000 claims description 6
- 235000010493 xanthan gum Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 239000005486 organic electrolyte Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001817 Agar Polymers 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- NFEAMKNIWKYVAL-UHFFFAOYSA-N propane-1-sulfonic acid;zinc Chemical compound [Zn].CCCS(O)(=O)=O NFEAMKNIWKYVAL-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 3
- OMUGFZNEOIWQOD-UHFFFAOYSA-N boric acid;zinc Chemical compound [Zn].OB(O)O OMUGFZNEOIWQOD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021401 carbide-derived carbon Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- ZNVKGUVDRSSWHV-UHFFFAOYSA-L zinc;4-hydroxybenzenesulfonate Chemical compound [Zn+2].OC1=CC=C(S([O-])(=O)=O)C=C1.OC1=CC=C(S([O-])(=O)=O)C=C1 ZNVKGUVDRSSWHV-UHFFFAOYSA-L 0.000 claims description 2
- WYRSGXAIHNMKOL-UHFFFAOYSA-N $l^{1}-sulfanylethane Chemical compound CC[S] WYRSGXAIHNMKOL-UHFFFAOYSA-N 0.000 claims 1
- 239000006183 anode active material Substances 0.000 claims 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000004832 voltammetry Methods 0.000 claims 1
- 210000004027 cell Anatomy 0.000 description 23
- 239000003990 capacitor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 2
- 229910007477 ZnMn2O4 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BFSYMAQRPRBNHX-UHFFFAOYSA-N ethanesulfonic acid;zinc Chemical compound [Zn].CCS(O)(=O)=O BFSYMAQRPRBNHX-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 241000773945 Trimusculidae Species 0.000 description 1
- AHIBWURJLGCHAY-UHFFFAOYSA-N [S].C1=CC=CC=C1 Chemical compound [S].C1=CC=CC=C1 AHIBWURJLGCHAY-UHFFFAOYSA-N 0.000 description 1
- XVSRSRCBUQVNND-UHFFFAOYSA-N acetonitrile;zinc Chemical compound [Zn].CC#N XVSRSRCBUQVNND-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- 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
- H01G11/46—Metal oxides
-
- 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
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of embedding zinc processing method of electrode and its applications in the preparation of Zinc ion battery type supercapacitor.Embedding zinc processing is carried out to electrode with electrochemical method, is to be placed in the solution containing zinc ion to electrode by working electrode and to electrode with conductive electrode specially using electrode to be processed as working electrode, in working electrode and to application voltage or electric current between electrode.A kind of at least one electrode in cell type supercapacitor positive electrode and cathode carries out embedding zinc processing in the method, it can effectively improve the problems such as positive and negative electrode current potential mismatches, operating voltage is low, coulombic efficiency is low and cycle life is poor, obtain the cell type supercapacitor that at low cost, operating voltage is high, capacity is high, can be quickly charged and discharged and has extended cycle life.
Description
Technical field
The invention belongs to electrochemical energy storing device field, it is related to the embedding zinc processing method of a kind of electrode and its super in cell type
Application in capacitor preparation.
Background technique
In field of batteries, the importance of cost and security performance is increasingly prominent, and then aqueous electrolyte replacement mainstream is organic
Electrolyte becomes the focus of people's research.Currently, the solution containing zinc ion is used for rechargeable battery although having been reported, it is existing
Some Zinc ion battery cycle life is equal less than 500 times.Meanwhile in cyclic process, the shape of zinc metal sheet cathode dendrite easy to form
At negative electrode volume expansion can be caused, while being had and being punctured the risk that diaphragm causes battery short circuit.
Supercapacitor is a kind of new type of energy storage device between battery and conventional electrostatic capacitor.With battery phase
There is bigger specific power (10 times or more) than, supercapacitor, and have that abrupt release ultrahigh current, the charging time is short, fills
The characteristic that discharging efficiency is high, has extended cycle life, but its energy density is far below battery.Patent document CN 103560019B is adopted
With metal composite oxide (two kinds or more the metal-doped energy storage materials being compounded to form, such as ZnCo2O4、ZnMn2O4、
ZnFe2O4) it is positive electrode active materials, zinc and carbon material form negative electrode active material, prepare a kind of zinc ion hybrid capacitor
Device.However, the hybrid super capacitor pressure drop is very big (> 0.4V), and high-temperature calcination is needed to prepare ZnCo2O4、ZnMn2O4、
ZnFe2O4Equal metal composite oxides are as a positive electrode active material, and complex process, at high cost.Simultaneously as metallic zinc exists
Zinc dendrite problem in cathode, high-power charge and discharge process still has.107910195 A of patent document CN uses carbon materials
Material is positive active material, and zinc metal sheet or zinc foil are negative electrode material, prepares a kind of Zinc ion battery type supercapacitor, but zinc metal sheet
Dendrite problems caused by cathode and its security risk still remain.
Summary of the invention
The present invention provides a kind of embedding zinc processing method of electrode, this method comprises: using electrode to be processed as working electrode, with
Conductive electrode is to be placed in the embedding zinc solution containing zinc ion to electrode by working electrode and to electrode, in working electrode and to electricity
Apply voltage or electric current between pole, embedding zinc processing is carried out to electrode with electrochemical method, makes the work electricity of positive and negative electrode before assembling
Position matches.For example, described is at least one of zinc, platinum, graphite, preferably zinc to electrode.
Embedding zinc processing method according to the present invention, the working electrode and the method to application voltage or electric current between electrode
At least one of constant voltage method, galvanostatic method, constant current charge-discharge method, linear scanning method, cyclic voltammetry can be selected from；It is excellent
Selection of land, the voltage or the method for electric current of applying is constant voltage method or galvanostatic charge/discharge.
Further, the current density range of the galvanostatic method be 0.01A/g~50A/g, processing the time be 0.1~
60h。
Further, the voltage range of the constant voltage method is 0~2V, and the processing time is 0.1~48h.For example, the perseverance
The voltage range of voltage method is 0.2~1.8V, 0.5~1.5V；As an example, the voltage can for 0.2V, 0.5V, 0.6V,
1.0V,1.2V,1.4V,1.5V,1.8V,2.0V.For example, the processing time can for 1~for 24 hours, 1.5~8h；As an example,
The processing time is 2h, 4h, 6h.
Further, the current density range of the galvanostatic charge/discharge is 0.01A/g~50A/g, such as 0.1~40A/
G, 1~30A/g, 5~25A/g；Voltage range is 0~2V, such as voltage is 0.2~1.8V, 0.5~1.5V；Processing the time be
0.1~60h, such as 0.5~50h, 1~40h, 2~10h, as an example, the processing time is 2h, 4h, 6h.
Further, the sweep speed range of the linear scanning method is 0.05mV/s~100mV/s, such as 0.1~
80mV/s, 0.5~60mV/s, 1~50mV/s, 5~30mV/s, voltage range are 0~2V, and the processing time is 0.1~60h.Into
One step, the sweep speed range of the cyclic voltammetry are 0.05mV/s~100mV/s, for example, 0.1~80mV/s, 0.5~
60mV/s, 1~50mV/s, 5~30mV/s, voltage range are 0~2V, and cycle-index is 1~20 time.
Embedding zinc processing method according to the present invention, it is described anode in active material can be Mn oxide.For example, described
Mn oxide can be selected from MnO2、Mn3O4、Mn2O3At least one of with MnO；The crystal form of the Mn oxide does not limit especially
System can be α, β, γ, δ and any one of unformed；Wherein, the Mn oxide source is not particularly limited.Example
Property, the Mn oxide can be selected from α-MnO2、α-Mn2O3、Mn3O4, MnO or unformed MnO2。
Embedding zinc processing method according to the present invention, the active material in the cathode can be carbon material.For example, the carbon
Material can selected from active carbon, activated carbon fibre, carbon aerogels, carbon nanotube, mesoporous carbon, graphene, carbide derived carbon and
At least one of nanometer door charcoal；Preferably at least one of active carbon, carbon aerogels, carbon nanotube and graphene.
Embedding zinc processing method according to the present invention, the zinc ion in the embedding zinc solution come from zinc nitrate, zinc sulfate, chlorination
Zinc, trifluoracetic acid zinc, zine methqne-sulfonate, trifluoromethane sulfonic acid zinc, ethylsulfonic acid zinc, propyl sulfonic acid zinc, tetrafluoro boric acid zinc, benzene sulphur
At least one of sour zinc and the aqueous solution of zinc perchlorate；As an example, the zinc ion can come from zinc nitrate, zinc sulfate,
At least one of zinc chloride, aqueous solution of trifluoromethane sulfonic acid zinc.The concentration of the zinc ion can be 0.1~4mol/L,
Preferably 1~2mol/L, such as 1mol/L, 1.5mol/L, 2mol/L.Further, can also include in the embedding zinc solution
Gel electrolyte, such as the gel electrolyte can be selected from polyvinyl alcohol, polyethylene glycol oxide, agar, gelatin, polyacrylate
At least one of sodium and xanthan gum, preferably xanthan gum, polyvinyl alcohol or polyethylene glycol oxide.Preferably, the embedding zinc solution
Mixture, the zinc sulfate of zinc sulfate solution, trifluoromethane sulfonic acid zinc aqueous solution, zinc sulfate solution and xanthan gum can be selected from
The mixture of the mixture of aqueous solution and polyvinyl alcohol, zinc sulfate solution and polyethylene glycol oxide.
According to an embodiment of the present invention, the operation of the constant voltage method may include: electric using electrode to be processed as work
Pole, zinc metal sheet are used as to electrode, are placed in embedding zinc solution by working electrode and to electrode, and 1~2 is kept at 0~2.0V of constant voltage
Hour.
According to an embodiment of the present invention, the operation of the galvanostatic charge/discharge includes: electric using electrode to be processed as work
Pole, zinc metal sheet are used as to electrode, are placed in embedding zinc solution by working electrode and to electrode, at constant current, keep certain time.
For example, the current density can be 0.05~0.15A/g, such as 0.1A/g.
The present invention also provides the pre- embedding zinc processing method of the electrode answering in the preparation of Zinc ion battery type supercapacitor
With.
The present invention also provides a kind of preparation methods of cell type supercapacitor, and described method includes following steps:
(1) preparation conventional anode and cathode；
(2) conventional cathode is subjected to the embedding zinc of electrochemistry, or conventional anode is subjected to the embedding zinc of electrochemistry, or by conventional cathode and
Conventional anode carries out the embedding zinc of electrochemistry simultaneously；
(3) it is assembled according to the sequence of anode, diaphragm, cathode, and adds electrolyte, be packaged into cell type supercapacitor；
Or assembled according to the sequence of anode, gel electrolyte, cathode, it is packaged into cell type supercapacitor；
Preferably, the embedding zinc of electrochemistry described in step (2) uses the embedding zinc processing method of above-mentioned electrode.
Cell type supercapacitor preparation method according to the present invention, the preparation side of conventional cathode and cathode in step (1)
Method can be using method known to ability.For example, anode is adhered to anode collection by positive active material, conductive agent and binder
It is made on body；Cathode is adhered on negative current collector by negative electrode active material, conductive agent and binder and is made.
Cell type supercapacitor preparation method according to the present invention, it is described anode in active material have such as institute above
The meaning stated.Active material in the cathode has meaning as described above.For example, negative electrode active material and positive-active
The mass ratio of substance can be (2~10): 1, such as (4.5~6): 1, as an example, mass ratio can for 2:1,3:1,4:1,
5:1、6:1、7:1、8:1、9:1、10:1。
Preparation method according to the present invention, the electrolyte can for containing zinc ion aqueous solution, organic electrolyte and from
At least one of sub- liquid.For example, the zinc ion can be by including but is not limited to that following substance provides: zinc nitrate, sulfuric acid
Zinc, zinc chloride, trifluoracetic acid zinc, zine methqne-sulfonate, trifluoromethane sulfonic acid zinc, ethylsulfonic acid zinc, propyl sulfonic acid zinc, tetrafluoro boric acid
At least one of zinc, ZINC P-PHENOLSULFONATE, zinc perchlorate；Preferably zinc sulfate, trifluoromethane sulfonic acid zinc.In the electrolyte solution
The concentration of zinc ion can be 0.1~4mol/L, it is therefore preferable to 1~2mol/L；As an example, concentration is 1mol/L, 1.5mol/
L, 2mol/L.Preferably, can also contain manganese sulfate in the electrolyte solution, for example, the concentration of manganese sulfate be 0.01~
2mol/L, preferably 0.1~1mol/L.Wherein, the organic solvent can selected from esters, sulfone class, ethers, nitrile, alkane and
At least one of olefines organic solvent；It such as can be ethers, esters；Illustratively, the organic flux can be two
Methyl ether, propene carbonate, ethylene carbonate.Wherein, the ionic liquid can be selected from imidazoles, piperidines, pyroles, quaternary ammonium
At least one of class and amides ionic liquid.Illustratively, the electrolyte solution can be selected from: zinc sulfate solution,
Zinc sulfate solution+manganese sulfate solution, trifluoromethayl sulfonic acid zinc aqueous solution, trifluoromethayl sulfonic acid zinc acetonitrile solution.
Preparation method according to the present invention, gel polymer in the gel electrolyte can selected from polyvinyl alcohol,
At least one of polyethylene glycol oxide, agar, gelatin, one of sodium polyacrylate and xanthan gum；Preferably xanthan gum.
Preparation method according to the present invention, the cell type supercapacitor can be all-solid-state battery type supercapacitor
And/or semisolid cell type supercapacitor.
Preparation method according to the present invention, specific capacity >=30mAh/g of the cell type supercapacitor, illustratively,
The specific capacity of the capacitor be 30mAh/g, 36mAh/g, 40mAh/g, 41mAh/g, 45mAh/g, 48mAh/g, 50mAh/g,
53mAh/g,56mAh/g,60mAh/g.Preparation method according to the present invention, the cycle charge-discharge of the cell type supercapacitor
Number >=100 time, such as >=1000 times, >=2000 times, >=2500 times.
The present invention also provides the cell type supercapacitors obtained by above-mentioned preparation method.
Beneficial effects of the present invention:
In embedding zinc processing method of the invention, as a positive electrode active material using manganese compound, carbon material is living as cathode
Property substance, aqueous solution, organic electrolyte or ionic liquid containing zinc ion be electrolyte or the gel electrolyte containing zinc ion, just
Pole or/and cathode are handled through embedding zinc, can efficiently solve before assembling that positive electrode and negative electrode current potential mismatches, internal resistance is big, coulomb effect
The problems such as rate is low and cycle life is poor, makes the maximum capacity of cell type supercapacitor.The supercapacitor being prepared is negative
Pole material is not present the safety problem of zinc dendrite, and cell type supercapacitor also has low pressure drop, higher specific capacity and excellent
Different cycle performance.
Detailed description of the invention
Fig. 1 is the cell type supercapacitor charging and discharging curve figure of the embodiment of the present invention 1.
Fig. 2 is the cyclic voltammetry curve figure of the cell type supercapacitor of the embodiment of the present invention 1.
Fig. 3 is the cycle performance test curve figure of the cell type supercapacitor of the embodiment of the present invention 1.
Fig. 4 is the cyclic voltammetry curve figure of the cell type supercapacitor of comparative example 1 of the present invention.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
The constant current charge-discharge of product prepared by embodiment and comparative example, cyclic voltammetry use the blue electricity in Wuhan at room temperature
The Land equipment of company is tested.
Embodiment 1
The preparation of conventional cathode and cathode: by α-manganese dioxide, acetylene black, butadiene-styrene rubber (SBR) according to mass ratio 80:
Electrode slurry is made in 10:10, is coated on titanium foil, is used as anode after dry；Active carbon, second are weighed according to mass ratio 80:10:10
Electrode slurry is made in acetylene black, SBR, is coated on titanium foil, is used as cathode after dry.
The embedding zinc of positive electrode and negative electrode is handled: using α-manganese dioxide positive pole as working electrode, zinc is to electrode, by working electrode
It is placed in 2mol/L solution of zinc sulfate with to electrode, in working electrode and to 1V constant voltage is applied between electrode, holding 2 is small
When, embedding zinc processing is carried out to anode；Using activated carbon negative electrode as working electrode, zinc be to electrode, working electrode with to electrode it
Between the time in 1V constant potential, potentiostatic method is kept for 2 hours, carries out embedding zinc to cathode.
The assembling of supercapacitor: treated that cathode is successively stacked to shell for embedding zinc treated anode, diaphragm, embedding zinc
In, it adds electrolyte (aqueous solution of 2mol/L zinc sulfate and 0.1mol/L manganese sulfate), is assembled into cell type supercapacitor.
Embodiment 2~15
Positive embedding zinc voltage or the embedding zinc voltage of current density, cathode or current density unlike the first embodiment, when embedding zinc
Between, embedding zinc solution, the power-up mode of embedding zinc, the mass ratio (abbreviation cathode/anode) of cathode and positive active material, specific such as table
Shown in 1.
Table 1.
Comparative example 1
The preparation of conventional cathode and cathode: electricity is made according to mass ratio 80:10:10 in α-manganese dioxide, acetylene black, SBR
Pole slurry is coated on titanium foil, is used as anode after dry；Active carbon, acetylene black, SBR are made according to mass ratio 80:10:10
Electrode slurry is coated on titanium foil, is used as cathode after dry, and the mass ratio of cathode activated charcoal and positive α-manganese dioxide is 1:1.
The assembling of cell type supercapacitor: positive plate, diaphragm, negative electrode tab are sequentially overlapped, and are put into button shell, are added
Conventional batteries type supercapacitor is made in the aqueous solution for entering 2mol/L zinc sulfate and 0.1mol/L manganese sulfate.
Embodiment 16
The capacitor provided at room temperature embodiment 1~15 and comparative example 1 is tested, in constant current charge-discharge method and
Cyclic voltammetry test, voltage range are 0~1.6V.Specific test method: in 0.5A/g current density, 0~1.6V voltage model
It encloses interior progress constant current charge-discharge curve test: carrying out cyclic voltammetry curve in 2mV/s sweep speed, 0~1.6V voltage range
Test；Cycle performance test is carried out in 0.5A/g current density, 0~1.6V voltage range.The capacitor of embodiment 1~15 with
The performance test results of the conventional capacitor of comparative example 1 are shown in Table 2.
Table 2.
From Fig. 1~3 as can be seen that 1 cell type supercapacitor of embodiment has high specific discharge capacity (42mAh/g), surely
Fixed charge and discharge curve and superior cyclical stability (up to 2500 times, capacity hardly loses circulation), illustrate prepared by embodiment 1
Cell type supercapacitor has excellent chemical property.
It is the cyclic voltammetry curve figure of conventional batteries type supercapacitor prepared by comparative example 1 from Fig. 4, it can be seen that should
The specific discharge capacity of cell type supercapacitor is much smaller than embodiment 1, illustrates to pre-process without electrode, device performance is by very big
Influence.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of embedding zinc processing method of electrode, this method comprises: being carried out with electrochemical method to electrode in solution containing zinc ion
Embedding zinc processing；
It preferably, is to be placed in electrode by working electrode and to electrode with conductive electrode using electrode to be processed as working electrode
In embedding zinc solution containing zinc ion, in working electrode and to voltage or electric current is applied between electrode, make positive and negative electrode before assembling
Operating potential matches.
2. the embedding zinc processing method of electrode according to claim 1, which is characterized in that described is zinc to electrode, in platinum, graphite
At least one, preferably zinc.
3. the embedding zinc processing method of electrode according to claim 1 or 2, which is characterized in that the working electrode with to electrode
Between apply the method for voltage or electric current and be selected from constant voltage method, galvanostatic method, constant current charge-discharge method, linear scanning method, circulation
At least one of voltammetry；
Preferably, the electrochemical method is constant voltage method or galvanostatic charge/discharge.
4. the embedding zinc processing method of electrode according to claim 3, which is characterized in that the voltage range of the constant voltage method is
0~2 V, processing time are 0.1~48h；
Preferably, the current density of the galvanostatic method is the A/g of 0.01 A/g~50, and the processing time is 0.1~60h；
Preferably, the current density range of the galvanostatic charge/discharge is the A/g of 0.01 A/g~50, and voltage range is 0~2 V,
The processing time is 0.1~60h；
Preferably, the sweep speed range of the linear scanning method is 0.05mV/s~100mV/s, and voltage range is 0~2 V,
The processing time is 0.1~60h；
Preferably, the sweep speed range of the cyclic voltammetry is 0.05mV/s~100mV/s, and potential range is 0~2 V,
Cycle-index is 1~20 time.
5. the embedding zinc processing method of electrode according to any one of claims 1 to 4, which is characterized in that in the embedding zinc solution
Zinc ion come from zinc nitrate, zinc sulfate, zinc chloride, trifluoracetic acid zinc, zine methqne-sulfonate, trifluoromethane sulfonic acid zinc, ethyl sulphur
At least one of sour zinc, propyl sulfonic acid zinc, tetrafluoro boric acid zinc, ZINC P-PHENOLSULFONATE, zinc perchlorate；
Preferably, the molar concentration of zinc ion is 0.1mol/L~4mol/L in the embedding zinc solution；
It preferably, further include gel electrolyte in the embedding zinc solution；Preferably, the gel electrolyte be selected from polyvinyl alcohol,
At least one of polyethylene glycol oxide, agar, penetrating judgment, one of sodium polyacrylate and xanthan gum.
6. the embedding zinc processing method of described in any item electrodes according to claim 1~5, which is characterized in that the activity of the anode
Substance is Mn oxide, and the Mn oxide is selected from MnO2、Mn3O4、Mn2O3At least one of with MnO；
The active material of the cathode is carbon material, and the carbon material is selected from active carbon, activated carbon fibre, carbon aerogels, carbon and receives
At least one of mitron, mesoporous carbon, graphene, carbide derived carbon and nanometer door charcoal.
7. application of any one of the claim 1~6 embedding zinc processing method of electrode in the preparation of cell type supercapacitor, excellent
The application being selected in the preparation of Zinc ion battery type supercapacitor.
8. a kind of preparation method of cell type supercapacitor, which is characterized in that it the described method comprises the following steps,
(1) anode and cathode are prepared respectively；
(2) anode is subjected to embedding zinc processing, or cathode is subjected to embedding zinc processing, or anode and cathode are carried out at embedding zinc simultaneously
Reason；
(3) it is assembled according to the sequence of anode, diaphragm, cathode, and adds electrolyte, be packaged into cell type supercapacitor；Or it presses
It assembles according to the sequence of anode, gel electrolyte, cathode and is packaged into cell type supercapacitor；
Electrode uses the described in any item embedding zinc processing methods of claim 1~6 in step (2).
9. a kind of preparation method of cell type supercapacitor according to claim 8, which is characterized in that in the anode
Active material in active material and cathode has meaning as claimed in claim 6；
Preferably, the mass ratio of the negative electrode active material and positive active material is (2~10): 1；Preferred mass ratio is (4.5
~6): 1；
The electrolyte is at least one of aqueous solution, organic electrolyte and ionic liquid containing zinc ion；
The gel electrolyte has meaning as claimed in claim 5.
10. preparation method according to claim 8 or claim 9, which is characterized in that the cell type supercapacitor is all solid state
Cell type supercapacitor and/or semisolid cell type supercapacitor；
Preferably, specific capacity >=30nAh/g of the cell type supercapacitor；
Preferably, cycle charge-discharge number >=100 time of the cell type supercapacitor.
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