CN108172407A - Composite electrode, preparation method and application thereof - Google Patents
Composite electrode, preparation method and application thereof Download PDFInfo
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- CN108172407A CN108172407A CN201711429800.5A CN201711429800A CN108172407A CN 108172407 A CN108172407 A CN 108172407A CN 201711429800 A CN201711429800 A CN 201711429800A CN 108172407 A CN108172407 A CN 108172407A
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- transition metal
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- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000009713 electroplating Methods 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 79
- 239000011248 coating agent Substances 0.000 claims description 68
- 238000000576 coating method Methods 0.000 claims description 68
- 239000007788 liquid Substances 0.000 claims description 48
- 239000006260 foam Substances 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 33
- 239000000654 additive Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- 239000003575 carbonaceous material Substances 0.000 claims description 21
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 6
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000037303 wrinkles Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 14
- 230000006872 improvement Effects 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000011149 active material Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 8
- 239000011565 manganese chloride Substances 0.000 description 8
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229940101209 mercuric oxide Drugs 0.000 description 7
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- -1 oxo transition metal Chemical class 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910002521 CoMn Inorganic materials 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese 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
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000010792 warming Methods 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/22—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
- H01G11/46—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
- 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
Landscapes
- 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)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a composite electrode, which belongs to the field of electronic materials and devices and comprises a substrate, wherein a carbon layer is electroplated on the surface of the substrate, and a transition metal oxide layer is electroplated on the surface of the carbon layer; the composite electrode is in a three-dimensional porous wrinkle structure, and the mass specific capacitance of the composite electrode can reach 1783F g to the maximum‑1(ii) a The preparation method of the composite electrode comprises 1) preparing a substrate; 2) preparing a solution; 3) electroplating a carbon layer; 4) electroplating a transition metal oxide layer; 5) cleaning and drying; simultaneously, the application of the composite electrode in a super capacitor is provided. The composite electrode has excellent conductivity, high mass-to-capacitance and high cycle stability, and the mass-to-capacitance of the composite electrode can reach 1783F g to the maximum‑1At 6 A.g‑1The current density of the capacitor is circulated for 2000 times, the specific capacitance can be kept to 84.4 percent of the initial value, and the capacitor has wide application prospect.
Description
Technical field
The present invention relates to a kind of combination electrodes and preparation method and application, belong to electronic material and devices field.
Background technology
Ultracapacitor (SC) is a kind of a kind of new type of energy storage device between traditional capacitor and electrochmical power source, tool
Have that the charging time is short, have extended cycle life, broad application temperature range and the advantages such as economic and environment-friendly, closed extensively in various fields
Note.With global warming, environmental pollution and the aggravation of energy shortage problem, it is badly in need of replacing traditional energy using clean energy resource, and
Develop mating energy-storage system.SC is compared with traditional secondary cell and conventional dielectric capacitor, because of its high-energy density, soon
The advantages that fast charge and discharge, can meet the needs of modern electronics industry development.According to charge-storage mechanism and electrode material not
Together, SC common types have：Electrochemical capacitor in double electrode layer (EDLC) and fake capacitance capacitor.EDLC passes through the table in electrode material
Face stored charge carrys out storing up electricity, has high power density, however energy density is relatively low, and specific capacitance is relatively low.Due to additional reversible oxygen
Change reduction process, the specific capacitance of fake capacitance capacitor is one of research hotspot now far above EDLC.Transition metal oxide
It is a kind of common fake capacitance electrode active material, there is low cost and advantages of environment protection, be with a wide range of applications.
Transition metal oxide for the electrode material of fake capacitance capacitor mainly includes RuO2、MnO2、Co3O4、NiO、
CuO etc., in addition, research shows that transition metal oxide/graphene combination electrode has higher specific capacitance and more preferably recycles
Stability.When the transition metal oxide of nanoscale is dispersed on graphene, graphene can effectively prevent oxo transition metal
The reunion of compound, on the other hand, graphene can increase effective contact area between transition metal oxide and electrolyte, improve
Its electro-chemical activity；In addition, graphene has excellent mechanical property and electric conductivity as carrier material so that electrode is whole
With prominent electrochemical stability and electric conductivity.
At this stage, the method for preparing transition metal oxide combination electrode has hydro-thermal method, thermal decomposition method, the precipitation method, electricity to sink
Product, vapor phase method and solid phase method.A kind of existing Chinese patent " Ni-based MnO of foam2/ C combination electrode materials and preparation method thereof "
(102,938 331 A of publication number CN) prepares carbon electrode using simple hydro-thermal method in foam nickel base, recycles electro-deposition
Method prepares composite material.Carbon electrode obtained forms microcosmic spheric granules, and is overlapped mutually between particle, and this self aggregation shows
As electrolyte can be caused to be difficult to penetrate into inside active material, so as to reduce electrode performance, and this hydro-thermal method experimental procedure is answered
It is miscellaneous, experiment condition harshness and long preparation period.Separately there are Chinese patent " electrode of compound transition metal oxide containing manganese and its preparation side
Method and application " (103996547 A of publication number) prepares the electrode of compound transition metal oxide containing manganese, electrode using galvanoplastic
Quality specific capacitance be 313Fg-1, complex process and specific capacitance is relatively low.In addition, Jinbing Cheng et al.
[Materials Letters 165 (2016) 231~234] prepares CoMn by the method for precipitating and annealing2O4Microballoon, and
For electrode of super capacitor, method cost is higher and its quality specific capacitance is relatively low, only 788Fg-1。
Invention content
In view of the above existing problems in the prior art, the present invention provides a kind of compound electrics for possessing better quality specific capacitance
Pole also provides the preparation method and application of the combination electrode simultaneously.
To achieve these goals, the present invention provides a kind of combination electrodes, including substrate, the electroplating surface of the substrate
There is carbon-coating, the electroplating surface of the carbon-coating has transition metal oxide layer；
The active layer of the combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance maximum of combination electrode is reachable
1783F·g-1。
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Substrate is cleaned, removes oxide layer and greasy dirt；
2) preparation of solution：The additive solution containing carbon-based material is prepared, concentration range is 3~7mgmL-1；
The electroplate liquid of transition-containing metal ion is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid；
3) carbon-coating is electroplated：In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2)；
4) transition metal oxide layer is electroplated：In the substrate after carbon-coating is electroplated, continue using the electroplate liquid in step 2)
Transition metal oxide layer is electroplated；
5) it cleans, is dry：It after plating, rinses through deionized water, dry at room temperature repeatedly, combination electrode is made.
As an improvement, in the step 1), the substrate used is nickel foam, conductive carbon paper or carbon fiber.
As an improvement, in the step 1), the substrate that uses is netted or fibrous.
As an improvement, in the step 3), when carbon-coating is electroplated, the temperature that uses is 40~85 DEG C, electroplating time 60
~300s.
As an improvement, in the step 4), when transition metal oxide layer is electroplated, the temperature used for 40~80 DEG C,
Electroplating time is 5~15s.
As an improvement, the carbon-based material in the step 2) is using any in graphene oxide, activated carbon, carbon nanotube
Kind or several mixing.
As an improvement, the electroplate liquid in the step 2), using cabaltous nitrate hexahydrate, four chloride hydrate manganese, six hydrations three
Two or more mixed solutions in iron chloride, Nickel dichloride hexahydrate, Gerhardite.
The present invention also provides application of this kind of combination electrode in ultracapacitor simultaneously.
The principle of the present invention is：Contain carbon material, after sonicated, carbon material in the additive solution that the present invention prepares
In graphene dispersion it is uniform, in electroplating process, by electron exchange, part of hydroxyl and carboxyl functional group on graphene film
It is reduced, so as to which graphene is reduced into redox graphene (rGO), these redox graphene pieces are constantly attached to base
On bottom, planar structure is formed, is increased over time, the graphene film being reduced gradually increases, and part graphene film starts to stand
Vertical to increase as time go on so as to form pleated structure, this pleated structure becomes that higher is thicker, by excellent conduction
Property with pleated structure feature, this carbon-coating is very beneficial for the plating of later stage transition metal oxide layer.
After the completion of carbon-coating plating, it is placed into the electroplate liquid containing transition metal ions, it is molten again by reduction reaction
Transition-metal cation in liquid obtains electronics and forms covalent bond with the carbon atom in rGO, is deposited in the rGO on pieces plated,
Transition metal oxide layer is formed, in deposition process, Spatial Multi-Dimensional lamination is formed between the carbon atom in metallic atom and rGO
Covalent bond, this aspect enhance the binding force between transition metal oxide layer and rGO layers, enhance the mechanically stable of electrode
Property, on the other hand, the resistance between transition metal oxide layer and rGO layers is reduced, enhances the electric conductivity of electrode.With it is existing
Technology is compared, the beneficial effects of the invention are as follows：
1) combination electrode of the invention has obtained monatomic by two-dimentional rGO by plating carbon-coating, transition metal oxide layer
The product with the porous pleated structure of special three dimensions that layer and two-dimentional multi-element transition metal oxides are formed, however, passing
Simple its microstructure of plating GO is two-dimentional paper-like in system technology, in addition, metal oxide electrode prepared by hydro-thermal method is micro-
See the aggregation that structure is spheric granules, the electrode with special three dimensions pleated structure prepared by the present invention, carbon-coating conduct
Skeleton has outstanding electric conductivity, and the multi-element transition metal oxides adhered to thereon have the specific surface area of super large, so as to have
The catalytic activity of super large, overall structure porous, electrically conductive catalysis access.On the one hand this special construction is conducive to electronics in material internal
On the other hand transmission, conducive to the ion transmission inside material void, therefore produces the quality specific capacitance of superelevation.
2) carbon-coating and polynary transiting metal oxidation is successfully electroplated using simple two steps galvanoplastic in the present invention in substrate
Nitride layer, forms combination electrode, and the galvanoplastic experimental procedure of use is simple, it is easy to accomplish, and the addition of carbon-based additive is advantageous
In the plating of transition metal oxide layer, porous pleated structure of the combination electrode obtained for three-dimensional, nanoscale transition metal
Oxide and the compound of graphene can fill the respective material characteristics of part performance：The counterfeit of transition metal oxide can be made full use of
Capacitive property, and the electric double layer capacitance performance of graphene can be made full use of so that combination electrode of the invention has excellent lead
Electrically, higher quality specific capacitance and excellent cyclical stability, quality specific capacitance is up to 1783Fg-1, in 6Ag-1
Current density under after cycle operation 2000 times, specific capacitance still can remain the 84.4% of initial specific capacitance, have wide
Application prospect.
Description of the drawings
Fig. 1 is the structure diagram of the combination electrode of the present invention；In figure：1st, substrate, 2, carbon-coating, 3, transition metal oxide
Layer, as seen from the figure, combination electrode are three-dimensional porous pleated structure.
Fig. 2 is the interior atoms structure chart of the combination electrode of the present invention；Metallic atom in figure in transition metal oxide
Spatial Multi-Dimensional lamination covalent bond is formd with the carbon atom in rGO.It can be seen from the figure that in transition metal atoms and rGO
Carbon atom is combined closely by covalent bond.
Fig. 3 is the scanning electron microscope diagram that first electrode is made in the embodiment of the present invention 1；It can be seen from the figure that by
Fold graphene forms layering porous structure for the self-standing transition metal oxide nano-slice of substrate.
Fig. 4 is the constant current charge-discharge curve that first electrode, second electrode are made in the embodiment of the present invention 1；It can be with from figure
Find out, the constant current charge-discharge curve of two electrodes is triangular in shape symmetrical, shows good electric double layer performance, is in current density
1A·g-1When, first electrode biggest quality specific capacity is up to 1783Fg-1, the quality specific capacitance of second electrode is 863Fg-1。
Fig. 5 is that first electrode, second electrode are made in the embodiment of the present invention 1 in 6Ag-1Current density under carry out constant current
The change curve of quality specific capacitance during cycle charge-discharge 2000 times；As can be seen that first electrode specific capacitance is up to initial specific capacitance
84.4%, second electrode specific capacitance only reach initial specific capacitance 77.7%, i.e. the cyclical stability of first electrode is higher.
Specific embodiment
Understand to make the object, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this
Invention is further elaborated.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention,
The range being not intended to restrict the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with belonging to the technology of the present invention
The normally understood meaning of technical staff in domain is identical, and used term is intended merely to retouch in the description of the invention herein
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
A kind of combination electrode, as shown in Figure 1, including substrate 1, the electroplating surface of the substrate 1 has carbon-coating 2, the carbon-coating 2
Electroplating surface have transition metal oxide layer 3；
The combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance maximum of combination electrode is up to 1783Fg-1。
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Substrate is cleaned, removes oxide layer and greasy dirt；
2) preparation of solution：The additive solution containing carbon-based material is prepared, concentration range is 3~7mgmL-1；
The electroplate liquid containing transition metal oxide is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid；
3) carbon-coating is electroplated：In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2)；
4) transition metal oxide layer is electroplated：In the substrate after carbon-coating is electroplated, continue using the electroplate liquid in step 2)
Transition metal oxide layer is electroplated；
5) it cleans, is dry：After plating, rinsed repeatedly with deionized water, after be dried at room temperature for get compound electric
Pole.
As an improvement, in the step 1), the substrate used is nickel foam, conductive carbon paper or carbon fiber.
As an improvement, in the step 1), the substrate that uses is netted or fibrous.
As an improvement, in the step 3), when carbon-coating is electroplated, the temperature that uses is 40~85 DEG C, electroplating time 60
~300s.
As an improvement, in the step 4), when transition metal oxide layer is electroplated, the temperature used for 40~80 DEG C,
Electroplating time is 5~15s.
As an improvement, the carbon-based material in the step 2) is using graphene oxide (GO), activated carbon (AC), carbon nanotube
Or several mixing any one of (CNT).
As an improvement, the transition metal ions in the step 2), using cabaltous nitrate hexahydrate (Co (NO3)2·6H2O)、
Four chloride hydrate manganese (MnCl2·4H2O), Iron(III) chloride hexahydrate (FeCl3·6H2O), Nickel dichloride hexahydrate (NiCl2·
6H2O), Gerhardite (Cu (NO3)2·3H2O the two or more mixing in).
The present invention also provides application of this kind of combination electrode in ultracapacitor simultaneously.
Embodiment 1
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Nickel foam is first taken, is cut into the sample of 1cm × 2cm, successively with hydrochloric acid (6M), acetone, ethyl alcohol
It impregnates and is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, be then placed in drying for standby in nitrogen glove box；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1AC and
Tri- perchloric acid hydrate lithium (LiClO of 0.1M4·3H2O) mixed aqueous solution so that the total concentration of carbon-based material is 4 mg in solution
ml-1, each 1h of ultrasonic mixing, magnetic agitation；
The electroplate liquid of transition-containing metal ion is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O and 1M chlorinations
The mixed aqueous solution of sodium (NaCl) so that in electroplate liquid the total concentration of transition metal ions be 3M, ultrasonic mixing 10min, magnetic force
Stir 1h；
3) carbon-coating is electroplated：In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2)
Carbon-coating is plated, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference
Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating
Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the foam nickel base after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is kept
80 DEG C, time 12s of constant temperature, voltage are -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated
Metal oxide layer, the electrode of gained are known as second electrode.
The scanning electron microscope diagram of first electrode is fig. 3, it is shown that by certainly station of the fold graphene for substrate
Vertical transition metal oxide nano-slice forms layering porous structure.
The performance detection of the obtained combination electrode of the present invention：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, active material in control first electrode and second electrode (on active material basidigitale, obtained by plating all material) matter
Amount is 1 ± 0.2mg, according to multiple loop test as a result, as shown in figure 4, can be calculated, in 1Ag-1When, first electrode
Quality specific capacitance is 1783Fg-1, the quality specific capacitance of second electrode is 863Fg-1.As can be seen that first electrode compared to
Second electrode, quality specific capacitance increase 106%.Fig. 5 is first electrode, second electrode is in 6Ag-1Current density under, into
After row constant current charge-discharge test 2000 times, the change curve of quality specific capacitance as seen from the figure, is surveyed by 2000 cycles
Examination, the quality specific capacitance of first electrode are the 84.4% of its initial specific capacitance, and the quality specific capacitance of second electrode is its initial ratio
The 77.7% of capacitance, it is possible thereby to find, the cyclical stability of first electrode is higher than second electrode.
In addition, with reference to the interior atoms structure chart of combination electrode in Fig. 2, the metallic atom in figure in transition metal oxide
Spatial Multi-Dimensional lamination covalent bond is formd with the carbon atom in rGO.It can be seen from the figure that in transition metal atoms and rGO
Carbon atom is combined closely by covalent bond.
Embodiment 2
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol
And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1AC and
0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 5mgml in solution-1, ultrasonic mixing, magnetic
Power stirs each 1h；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、2M
NiCl2·6H2The mixed aqueous solution of O and 1M NaCl so that in electroplate liquid the total concentration of transition metal ions be 5M, ultrasonic mixing
10min, magnetic agitation 1h；
3) carbon-coating is electroplated：In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2)
Carbon-coating is plated, during plating, electroplate liquid keeps 40 DEG C, time 300s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference
Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating
Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the foam nickel base after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected
40 DEG C, time 15s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated
Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 1481Fg-1, and the quality specific capacitance of second electrode is 981F
g-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 50%.
Embodiment 3
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol
And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1CNT
With 0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 5mgml in solution-1, ultrasonic mixing,
Each 1h of magnetic agitation；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.5M
FeCl3·6H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.5M in electroplate liquid, and ultrasound is mixed
Close 10min, magnetic agitation 1h；
3) carbon-coating is electroplated：In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2)
Carbon-coating is plated, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference
Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating
Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the foam nickel base after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected
80 DEG C, time 5s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated
Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 960Fg-1, and the quality specific capacitance of second electrode is 501Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 91%.
Embodiment 4
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol
And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1CNT、
2mg·ml-1AC and 0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 7 mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.01M
Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.01M in electroplate liquid, is surpassed
Sound mixing 10min, magnetic agitation 1h；
3) carbon-coating is electroplated：In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2)
Carbon-coating is plated, during plating, electroplate liquid keeps 85 DEG C, time 60s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference
Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating
Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the foam nickel base after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected
50 DEG C, time 10s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated
Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 756Fg-1, and the quality specific capacitance of second electrode is 472Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 60%.
Embodiment 5
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol
And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box；
2) preparation of solution：Prepare the additive solution containing carbon-based material, 3mgml-1GO and 0.1M LiClO4·3H2O
Mixed aqueous solution so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.1M
FeCl3·6H2O、0.1M NiCl2·6H2O、0.1M Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that plating
The total concentration of transition metal ions is 3.3M, ultrasonic mixing 10min, magnetic agitation 1h in liquid；
3) carbon-coating is electroplated：Foam nickel base after cleaning in step 1) is suppressed into 5min under 2000Pa pressure in advance, is adopted
Carbon-coating is electroplated with the additive solution in step 2), during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, voltage for-
1.2V, and using silver-silver chloride electrode as reference electrode, platinized platinum is to electrode, and nickel foam is carried out for the three-electrode method of working electrode
Plating.After plating, rinsed repeatedly with deionized water, be placed in draught cupboard and spontaneously dry, obtain being electroplate with the foam of carbon-coating
Nickel electrode；
4) transition metal oxide layer is electroplated：In the foam nickel base after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected
80 DEG C, time 12s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated
Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 916Fg-1, and the quality specific capacitance of second electrode is 663Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 38%.
Embodiment 6
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Conductive carbon paper is first taken, is cut into the sample of 1cm × 2cm, it is spare；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO and 0.1M LiClO4·
3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.01M
Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.01M in electroplate liquid, is surpassed
Sound mixing 10min, magnetic agitation 1h；
3) carbon-coating is electroplated：In step 1) on conductive carbon paper, carbon-coating, plating are electroplated using the additive solution in step 2)
When, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference electrode, platinized platinum is
To electrode, conductive carbon paper is electroplated for the three-electrode method of working electrode.After plating, rinsed, put repeatedly with deionized water
It is spontaneously dried in draught cupboard, obtains being electroplate with the conductive carbon paper electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the conductive carbon paper substrate after carbon-coating is electroplated, continue using in step 2)
Electroplate liquid plating transition metal oxide layer, first to be coated with the conductive carbon paper electrode of carbon-coating as working electrode, during plating, plating
Liquid keeps 80 DEG C, time 12s of constant temperature, and voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then a piece of conductive carbon paper substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, only plating mixed
Metal oxide layer is crossed, the electrode of gained is known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 303Fg-1, and the quality specific capacitance of second electrode is 158Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 91%.
Embodiment 7
A kind of preparation method of combination electrode, specifically includes following steps：
1) preparation of substrate：Carbon fiber is first taken, carbon fiber is cut into the sample of long 2cm, with ultrasound after acetone soak 2h
5min is cleaned, dries, takes out spare under the conditions of 60 DEG C；
2) preparation of solution：The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、0.1M LiClO4·
3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation；
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O and 1M
The mixed aqueous solution of NaCl so that in electroplate liquid the total concentration of transition metal ions be 3M, ultrasonic mixing 10min, magnetic agitation
1h；
3) carbon-coating is electroplated：On carbon fiber in step 1) after cleaning, using the additive solution carbon electroplating in step 2)
Layer, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and electric by reference of silver-silver chloride electrode
Pole, platinized platinum are to electrode, and carbon fiber is electroplated for the three-electrode method of working electrode.After plating, with deionized water repeatedly
Rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the carbon fiber electrode of carbon-coating；
4) transition metal oxide layer is electroplated：In the carbon fiber substrates after carbon-coating is electroplated, continue using in step 2)
Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the carbon fiber electrically of carbon-coating extremely working electrode, during plating, electroplate liquid is protected
80 DEG C, time 12s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated；
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first
Electrode, then a carbon fiber substrates are separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition gold is only electroplated
Belong to oxide skin(coating), the electrode of gained is known as second electrode.
The performance detection of combination electrode is made in the present embodiment：
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's
Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated
When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating
It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 498Fg-1, and the quality specific capacitance of second electrode is 332Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 50%.
The specific performance testing result of the various embodiments described above is as shown in table 1 below.
The performance test results of electrode in 1 each embodiment of table
Carbon-coating, transition metal oxide layer is electroplated it is found that the combination electrode of the present invention passes through with reference to the testing result of table 1,
It has obtained being made of two-dimentional rGO monoatomic layers and two-dimentional multi-element transition metal oxides layer porous with special three dimensions
The product of pleated structure, however, the GO formed using conventional plating techniques, paper-like of the microstructure for two dimension, hydro-thermal legal system
Its microstructure of standby metal oxide electrode is the aggregation of spheric granules, and prepared by the present invention has special three dimensions fold
The electrode of structure, carbon-coating have outstanding electric conductivity as skeleton, and the multi-element transition metal oxides adhered to thereon have super
Big specific surface area, so as to the catalytic activity with super large, on the one hand overall structure porous, electrically conductive catalysis access exists conducive to electronics
Material internal transmits, and on the other hand, is transmitted, therefore produce higher quality specific capacitance conducive to the ion of material pore interior.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of combination electrode, which is characterized in that including substrate (1), the electroplating surface of the substrate (1) has carbon-coating (2), described
The electroplating surface of carbon-coating (2) has transition metal oxide layer (3)；
The combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance of combination electrode reaches as high as 1783Fg-1。
2. the preparation method of combination electrode described in a kind of claim 1, which is characterized in that specifically include following steps：
1) preparation of substrate：Substrate is cleaned, removes oxide layer and greasy dirt；
2) preparation of solution：The additive solution containing carbon-based material is prepared, concentration range is 3~7mgml-1；
The electroplate liquid of transition-containing metal ion is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid；
3) carbon-coating is electroplated：In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2)；
4) transition metal oxide layer is electroplated：In the substrate after carbon-coating is electroplated, continue using the electroplate liquid plating in step 2)
Transition metal oxide layer；
5) it cleans, is dry：It after plating, rinses through deionized water, dry at room temperature repeatedly, combination electrode is made.
3. the preparation method of a kind of combination electrode according to claim 2, which is characterized in that in the step 1), use
Substrate be nickel foam, conductive carbon paper or carbon fiber.
4. the preparation method of a kind of combination electrode according to Claims 2 or 3, which is characterized in that in the step 1), adopt
Substrate is netted or fibrous.
5. a kind of preparation method of combination electrode according to claim 2, which is characterized in that in the step 3), electricity
When plating carbon-coating, for the temperature used for 40~85 DEG C, electroplating time is 60~300s.
6. a kind of preparation method of combination electrode according to claim 2, which is characterized in that in the step 4), electricity
When plating transition metal oxide layer, for the temperature used for 40~80 DEG C, electroplating time is 5~15s.
7. the preparation method of a kind of combination electrode according to claim 2, which is characterized in that carbon-based in the step 2)
Material is using any one of graphene oxide, activated carbon, carbon nanotube or several mixing.
8. the preparation method of a kind of combination electrode according to claim 2 or 7, which is characterized in that in the step 2)
Electroplate liquid, using cabaltous nitrate hexahydrate, four chloride hydrate manganese, Iron(III) chloride hexahydrate, Nickel dichloride hexahydrate, Gerhardite
In two or more mixed solutions.
9. described in a kind of claim 1 or any one of claim 2-8 combination electrode made from the preparation method is in super electricity
Application in container.
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