CN110571067A - Super capacitor electrode material and preparation method thereof - Google Patents
Super capacitor electrode material and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003990 capacitor Substances 0.000 title abstract description 18
- 239000002071 nanotube Substances 0.000 claims abstract description 92
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 75
- 150000003624 transition metals Chemical class 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000004070 electrodeposition Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 34
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000004323 axial length Effects 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 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 claims description 7
- 238000010586 diagram Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000006172 buffering agent Substances 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910021426 porous silicon Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 229910006072 NiFeO4 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 14
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- 239000011232 storage material Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
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- 238000007600 charging Methods 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 238000010277 constant-current charging Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241001350406 Braya alpina Species 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- 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
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- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a super capacitor electrode material and a preparation method thereof, and belongs to the technical field of energy storage materials and devices. The invention adopts an electrochemical deposition method to respectively prepare transition metal nanotube arrays with different apertures and lengths in a double-pass insulating template, and then prepares a transition metal/metal native oxide nano-ordered array with a double-layer coaxial tubular structure by an integrated method, wherein the transition metal/metal native oxide nano-ordered array material with the double-layer coaxial tubular structure can be applied to high-performance supercapacitor electrode materials.
Description
Technical Field
The invention relates to the technical field of energy storage materials and devices, in particular to a super capacitor electrode material and a preparation method thereof.
Background
conventional energy storage devices mainly include a battery and a capacitor. Generally, a battery has a large energy storage capacity but takes a long time for charging and discharging, and a capacitor has a relatively limited energy storage capacity although the charging and discharging efficiency is high. The super capacitor has the advantages of both the battery and the capacitor, has larger energy storage capacity than the battery, keeps the high-efficiency charging/discharging capacity of the capacitor, and is a novel energy storage device with application potential.
Oxides of transition metals and their alloys are a class of supercapacitor electrode materials with high specific capacitance values. In particular based on Fe2O3、Co3O4、CoO、NiO、MnOx(x＝4/3，3/2,2)、NiFe2O4The electrode material formed by the method generally has higher theoretical and experimental specific capacitance values and has industrial and application potentials.
From the material design, the high-performance supercapacitor electrode material meets the following requirements: (i) the material structure is controllable and has large specific surface area, (ii) an effective ion transport channel can be provided, (iii) a good charge conduction path is provided, (iv) the electrode material has stable structure, and (v) the preparation process is relatively convenient.
In fact, a single material is difficult to combine all the aspects, and most of common composite materials need to be assembled after being synthesized step by step, so that the preparation process of the material is complex, the stability and controllability of the structure are limited, and large-scale preparation and application are difficult to some extent.
Disclosure of Invention
The invention aims to provide a super capacitor electrode material and a preparation method thereof, and aims to solve the problems of low specific capacitance, poor charging and discharging efficiency, low energy storage capacity, poor structural stability and complex preparation of the conventional super capacitor electrode material.
The technical scheme for solving the technical problems is as follows:
An electrode material for a supercapacitor, comprising: the nano double-layer tube array grows vertically and is distributed on the conducting layer in order; the nano double-layer tube array is a nano coaxial tube array prepared by a double-pass insulating template, and the nano double-layer tube comprises a transition metal nano tube layer and a transition metal oxide nano tube layer growing on the inner wall of the transition metal nano tube layer;
The transition metal nanotube layer is transition metal or an alloy thereof, and the transition metal oxide nanotube layer is native oxide of the transition metal or the alloy thereof corresponding to the transition metal nanotube layer.
For convenience of description, the Nano double-layer Tube Array is Nano Bilayer Tube Array, abbreviated as NBTA; the Transition Metal nanotube Layer is a Transition Metal Tube Layer, abbreviated as TMTL; the transition Metal oxide nanotube Layer is a separation-Metal Oxides Tube Layer, abbreviated as TMOTL; the Nano coaxial Tube is Nano Tube, abbreviated as NT.
The invention adopts the ordered porous template, so that a plurality of nano coaxial tubes can form an ordered array vertically growing on the conducting layer; the nano double-layer tube array has a large specific surface area, can provide more reaction points, has high reaction activity and improves the charge-discharge efficiency; the hollow structure of the nano coaxial tube can provide a transmission channel for ion transportation; the transition metal nanotube layer and the transition metal oxide nanotube layer are integrally prepared, connected and compact to provide a good microscopic conductive path; the nano coaxial tube directly grows on the conducting layer, so that the nano double-layer tube array obtains an electrode with good conductivity, and the performance requirement on the electrode material of the super capacitor is met.
The transition metal of the present invention includes but is not limited to Ni, Co, Fe or Mn, and the transition metal alloy of the present invention includes but is not limited to Ni alloy, Co alloy, Fe alloy or Mn alloy. In the preparation of the transition metal nanotube layer of the present invention, a transition metal may be selected, and an alloy of the transition metal may also be selected. The transition metal oxide referred to in the present invention is a native oxide corresponding to the transition metal, that is, an oxide of Ni, Co, Fe or Mn. The transition metal alloy oxide referred to in the present invention is a native oxide of a Ni alloy, a Co alloy, a Fe alloy, or a Mn alloy. When the transition metal oxide nanotube layer of the present invention is prepared, a transition metal native oxide may be selected, or a transition metal alloy native oxide and a mixed oxide layer composed of the transition metal oxide may be selected.
Further, in an embodiment of the present invention, the transition metal nanotube layer is Ni, Co, Fe, Mn, or an alloy thereof, and the transition metal oxide nanotube layer is a native oxide of Ni, Co, Fe, Mn, or an alloy thereof.
Further, in the embodiment of the present invention, the transition metal oxide nanotube layer is NiO, CoO, Co2O3、Co3O4、Mn2O3、MnO2、Mn3O4、CoFeO4And NiFeO4one or more combinations thereof.
further, in the embodiment of the present invention, the template aperture Φ of the double-pass insulating template isT50 nm-2000 nm, axial length d of templateT20 nm-500 mu m; thickness d of the conductive layerCLSmaller than the aperture phi of the templateT。
Template aperture phi of bi-pass insulating templateTCan be 50nm, 100nm or 2000nm, and the axial length d of the templateTIt may be 20nm, 100nm or 500 μm.
Further, in the embodiment of the present invention, the dual-pass insulating template is an aluminum oxide template, a titanium oxide template, a porous silicon template, or an organic porous template; the conducting layer is arranged on one surface of the double-pass insulating template and is an inactive metal film, an organic conducting film, an inorganic non-metal conducting film or an organic-metal composite film.
The inert metal referred to in the present invention includes, but is not limited to, Au or Pt. The inorganic non-metallic conductive film is preferably a graphite sheet.
Further, in the embodiment of the present invention, the inner diameter of the nano double-layer tube is 10nm to phiTWall thickness d 'of the transition metal nanotube layer'TMIs 3nm to dTMWall thickness d of the transition metal oxide nanotube layerTMOxNot less than dTM-d’TMA difference of (d); wherein d isTMThe wall thickness of the transition metal nanotube layer is 0<dTM<ΦT。
The inner diameter of the nano-coaxial tube is preferably 200 nm. Thickness d 'of the transition metal nanotube layer'TMA preferred value is 50 nm.
Further, in the embodiment of the present invention, the axial length L of the nano-double-layer tube array is 50nm to dT. The axial length L of the nano-bilayer tube array is preferably 3 μm.
A preparation method of a supercapacitor electrode material comprises the following steps:
(1) Depositing a conducting layer on one surface of the double-pass insulating template by adopting a physical vapor deposition method, a chemical vapor deposition method or a spin-coating method;
(2) preparing a transition metal nanotube layer in a pore channel of a bi-pass insulating template by adopting electrochemical deposition;
(3) Preparing a transition metal oxide nanotube layer in the transition metal nanotube layer to obtain a double-layer nanotube array generated in the pore channel of the double-pass insulating template;
(4) And (4) washing the nano double-layer tube array prepared in the step (3) with deionized water, then placing the nano double-layer tube array in a reagent which can dissolve the bi-pass insulating template and does not react with the nano double-layer tube array, soaking, removing the bi-pass insulating template, then washing and drying to obtain the electrode material of the supercapacitor.
The conductive layer and the nano double-layer tube array are respectively prepared by adopting a physical vapor deposition method, a chemical vapor deposition method, a spin-coating method and an electrochemical deposition method, the preparation process is simple and controllable, when the nano coaxial tube is prepared by utilizing the electrochemical deposition method, the thickness of the nano coaxial tube can be adjusted by controlling the potential or current, the reaction time and the reaction temperature, and different requirements for the super capacitor can be met.
The bi-pass insulating template of the invention can select the template with the aperture of 50 nm-2000 nm and the axial length of 20 nm-500 μm, and the bi-pass insulating template is preferably an alumina template (AAO), a titanium oxide Template (TAO), a porous silicon template or an organic porous template. The transition metal oxide nanotube layer and the transition metal nanotube layer in the nano coaxial tube prepared by the template have close surface contact, and the hollow tube channel forms an excellent ion migration channel of the super capacitor.
The electrochemical deposition device preferably adopts a three-Electrode aqueous solution system electrochemical deposition device, the general device main body material is made of acid-base resistant and electrochemically stable inert materials, preferably polytetrafluoroethylene or glass, and the three electrodes are respectively a Working Electrode (WE), a Counter Electrode (CE) and a Reference Electrode (RE); the CE is preferably a platinum (Pt) mesh electrode, a graphite electrode and the like, the RE is preferably a calomel electrode or an Ag/AgCl electrode and the like, and an oxygen-free conductive copper sheet is in close contact with a conductive layer of the template to form the WE. Connecting electrodes (CE, WE and RE), injecting electrolyte prepared by salt solution of transition metal or alloy thereof, and standing for a period of time to make the electrolytic deposition solution fully wet with the double-pass insulating template with the conductive layer.
Further, in the embodiment of the present invention, in the step (3), the method for preparing the transition metal oxide nanotube layer on the inner wall of the transition metal nanotube layer includes:
(3-1): adding a buffering agent into the electrolyte system in the step (2) according to the electrolyte system Bbye diagram to adjust the pH value of the electrolyte system, and then carrying out electrochemical deposition in the transition metal nanotube layer to form a transition metal oxide nanotube layer;
Or, (3-2): cleaning the transition metal nanotube layer with the bi-pass insulating template prepared in the step (2), then soaking the transition metal nanotube layer in an oxidant solution, and carrying out oxidation reaction in the transition metal nanotube layer to generate a transition metal oxide nanotube layer;
Or, (3-3): cleaning the transition metal nano tube layer with the bi-pass insulating template prepared in the step (2), and then annealing the transition metal nano tube layer in an oxygen-containing atmosphere at an annealing temperature TaAt 50-900 ℃ for an annealing time taIs 120 s-7200 s.
Further, in an embodiment of the present invention, the step (3-1) further includes: annealing the product after the electrochemical deposition reaction at an annealing temperature TaAt 50-900 ℃ for an annealing time taIs 120s to 7200 s; the product is an oxide or hydroxide of a transition metal or alloy thereof.
the invention has the following beneficial effects:
The invention adopts the ordered porous template, so that a plurality of nano coaxial tubes can form an ordered array vertically growing on the conducting layer; the nano double-layer tube array structure has large specific surface area, can provide more reaction points, has high reaction activity and improves the charge-discharge efficiency; the hollow structure of the nano coaxial tube can provide a transmission channel for ion transportation; the transition metal nanotube layer and the transition metal oxide nanotube layer are integrally prepared, connected and compact to provide a good microscopic conductive path; the nanometer double-layer tube array directly grows on the conducting layer, so that the nanometer double-layer tube array obtains an electrode with good conductivity, and the performance requirement of the electrode material of the super capacitor is met.
according to the electrode material of the super capacitor, the nano double-layer tube array is directly grown on the conducting layer, so that the electrode material has good conducting capacity; the ordered porous template is adopted to ensure that the nano coaxial tubes are orderly arranged to form a nano double-layer tube array, and the hollow ordered tube channel provides an ion migration channel, so that the specific surface area is increased, the energy storage reaction points are increased, and the energy storage density is improved; the nano coaxial tube is composed of a transition metal nano tube layer with a conductive function and a transition metal oxide nano tube layer with an energy storage function, wherein the transition metal or the alloy thereof has the conductive function, the primary oxide of the transition metal or the alloy thereof has the energy storage property, and the integrated nano coaxial tube provides a good charge conduction path; the ordered nano double-layer tube array can be conveniently and integrally prepared at normal temperature and normal pressure, and is convenient for scale production.
The invention can directly obtain the ordered nano double-layer tube array by electrochemical deposition by utilizing the double-pass insulating template, and the obtained nano double-layer tube array has the energy storage property and does not need to additionally prepare and assemble a capacitor conductive structure, such as a conductive net or an electrode.
Drawings
FIG. 1 is a schematic top view of a nanocoaxial tube in an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a self-made electrochemical deposition apparatus with a three-electrode system;
FIG. 3 is a schematic flow chart of a manufacturing process according to an embodiment of the present invention; in the figure: template is a porous bi-pass insulating Template, CL (Conductive Layer, CL) is a conducting Layer of the embodiment of the invention, TMTL (Transition Metal Tube Layer) is a Transition Metal oxide Tube Layer, TMOTL (Transition Metal oxide Tube Layer) is a Transition Metal oxide Tube Layer, and NBTA (Nano double Tube Array) is a Nano double-Layer Tube Array;
FIG. 4 is a scanning electron microscope image of the supercapacitor electrode material according to example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of the supercapacitor electrode material according to example 1 of the present invention;
FIG. 6 is a cyclic voltammogram in a 1M KOH electrolyte in example 1 of the present invention;
FIG. 7 shows the result of constant current charging and discharging test in the three-electrode system in example 1 of the present invention, wherein the electrolyte is 1M KOH;
FIG. 8 is a Pourbaix chart of Co in aqueous solution (Pourbaix Diagram);
FIG. 9 is a schematic representation of the preparation of Co/Co according to FIG. 7 and the protocol provided in this patent3O4Potential, pH and a solution system timing diagram of the electrode material of the nano double-layer tube array supercapacitor.
Detailed Description
the principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Co/Co integrated preparation based on electrochemistry-template method3O4-nanometer double-layer tube array supercapacitor electrode material
The method specifically comprises the following steps:
(1) Template pretreatment:
in this embodiment, an Anodic Aluminum Oxide (AAO) template with short-range ordered arrangement of double-sided through holes is adopted, and the axial length d of the templateAAO150 μm, pore diameter ΦAAO＝250nm。
Depositing a Conductive Layer (CL) on one surface of the double-pass AAO template by adopting a physical vapor deposition method, wherein the thickness d of the Conductive LayerCL75nm, the conductive layer material is Au. The CL/AAO template after deposition is cut into the required size S according to the requirementAAOand (5) standby.
(2) Preparing electrolyte:
Co with a certain mass concentration is prepared2+The ionic water solution is used as electrolytic deposition solution. This example used analytically pure cobalt acetate (Co (Ac)2) Dissolving the mixture in a proper amount of deionized water, and preparing a solution with the concentration of 0.038mol/L and the pH value of 6.9 with acetic acid to serve as an electrolytic deposition solution.
(3) and (3) electrodeposition preparation of a Co nanotube layer based on an AAO template:
The electrochemical deposition device is a three-Electrode system electrochemical deposition device made of polytetrafluoroethylene, wherein three electrodes are respectively a Working Electrode (WE), a Counter Electrode (CE) and a Reference Electrode (RE); in this embodiment, the CE is a platinum (Pt) mesh electrode, the RE is an Ag/AgCl electrode, and the oxygen-free conductive copper sheet is in close contact with the CL to form the WE.
As shown in fig. 2, the three-electrode system electrochemical deposition apparatus was assembled. Connecting the electrochemical station to the electrodes (CE, WE and RE), and injecting a certain amount of CoAc2Standing the electrolytic deposition solution for 5-60 min to enable the electrolytic deposition solution to be fully infiltrated with the CL/AAO template.
this embodiment employs a constant voltage VdepDepositing the Co nanotube layer based on the AAO template at-1V, and keeping the room temperature T at 25 ℃ during the deposition process for the deposition time TdepObtaining a Co nano tube layer with an AAO template, wherein the average wall thickness d of the Co nano coaxial tube is 3600sCoAxial length L is 3 μm at 40 nm.
(4) Preparation of Co/Co with AAO template by secondary deposition3O4nano double-layer tube array:
Adding appropriate amount of buffer such as sodium acetate NaAc into the electrolyte prepared above, adjusting the pH of the electrolyte to 7.5, and applying constant voltage VdepCo is carried out under 0.2-1.2V3O4Depositing the nanotube layer, keeping the room temperature T at 25 ℃ in the deposition process, and depositing for TdepObtaining Co/Co with AAO template in 180-900 s3O4Nano-bilayer tube arrays of Co/Co3O4Thickness d of nano coaxial tubeCo3O44-20 nm, and is adjustable according to potential and deposition time.
The nano double-layer tube array is obtained by directly adding a proper buffer agent into an original electrochemical deposition device to adjust the pH value and changing the potential deposition, so that the original Co nano tube layer does not need to be transferred and can achieve integrated operation.
It should also be noted that those skilled in the art and related arts will appreciate that the foregoing examples have been provided with AAO templates of Co/Co3O4Preparation of nano-double-layer tube array, the buffer used may be, but is not limited to, sodium acetate, and the core idea is to select appropriate potential and pH value according to potential-pH phase diagram (braye diagram) of electrolyte system to obtain nano-double-layer tube array without transferring transition metal nano-tube layer with template.
(5) Removing AAO template to obtain Co/Co3O4-nano double-layer tube array supercapacitor electrode material:
Washing the Co/Co with AAO template with deionized water3O4Nano double-layer tube array with AAO template Co/Co3O4placing the nano double-layer tube array in 1M KOH for dissolving the AAO template, repeatedly washing with deionized water and drying to obtain Co/Co on the oxygen-free conductive copper sheet3O4-nano double-layer tube array supercapacitor electrode material.
The AAO template removing process comprises closing the electrochemical workstation after deposition, disconnecting the electrochemical workstation from each electrode, recovering electrolyte, and washing with deionized water to remove Co/Co with AAO template3O4After the nano double-layer tube array, directly adding 1M KOH into the original electrochemical deposition device, thereby obtaining the Co/Co template with AAO3O4the nano double-layer tube array does not need to be transferred, and the integrated operation is achieved.
Example 2
Electrochemical-template method-assisted integrated preparation of Ni/NiO-nano double-layer tube array supercapacitor electrode material based on oxidant assistance
The method comprises the following steps:
(1) Template pretreatment:
In this embodiment, an Anodic Aluminum Oxide (AAO) template with short-range ordered arrangement of double-sided through holes is adopted, and the axial length d of the templateAAO150 μm, pore diameter ΦAAO＝200nm。
depositing a Conductive Layer (CL) on one surface of the double-pass AAO template by adopting a physical vapor deposition method, wherein the thickness d of the Conductive LayerCL60nm, the conductive layer material is Au. The CL/AAO template after deposition is cut into the required size S according to the requirementAAOAnd (5) standby.
(2) preparing electrolyte:
By analytically pure NiSO4Dissolving in deionized water to prepare 0.038mol/L solution as electrolytic deposition solution.
(3) Electrodeposition preparation of a Ni nanotube layer based on an AAO template:
The electrochemical deposition device is a three-Electrode system electrochemical deposition device made of polytetrafluoroethylene, wherein three electrodes are respectively a Working Electrode (WE), a Counter Electrode (CE) and a Reference Electrode (RE); in this embodiment, the CE is a platinum (Pt) mesh electrode, the RE is an Ag/AgCl electrode, and the oxygen-free conductive copper sheet is in close contact with the CL to form the WE.
Assembling the electrochemical deposition device with the three-electrode system. Connecting the electrochemical workstation to the electrodes (CE, WE and RE), injecting a certain amount of NiSO4Standing the electrolytic deposition solution for 5-60 min to enable the electrolytic deposition solution to be fully infiltrated with the CL/AAO template.
this embodiment employs a constant voltage VdepDepositing the Ni nanotube layer based on the AAO template at-1V, and maintaining the room temperature T at 25 ℃ during the deposition process for the deposition time TdepObtaining a Ni nano tube layer with an AAO template, wherein the average wall thickness d of the Ni nano coaxial tube is 6000sNi50nm, axial length L6 μm.
and (4) closing the electrochemical workstation after the deposition is finished, disconnecting the electrochemical workstation from each electrode, recovering the electrolyte, and washing the Ni nanotube layer with the AAO template by using deionized water.
(4) Preparing a Ni/NiO-nano double-layer tube array with an AAO template by oxidation assistance:
putting the prepared and cleaned Ni nanotube layer with the AAO template into hydrogen peroxide (H)2O2) Soaking in solution to make oxidation reaction of inner wall of Ni nano tube layer to generate NiO nano tube layer, controlling reaction time tOXthe NiO nano coaxial tube wall thickness d can be obtained within 180-1800 sNiOAnd the Ni/NiO-nano double-layer tube array is provided with an AAO template and is different from the 3nm to 20 nm.
note that this oxidation process can be performed by adding hydrogen peroxide (H) directly to the original electrochemical deposition apparatus after removing CE, RE and cleaning thoroughly2O2) The solution is carried out, so that the Ni nano-tube layer does not need to be transferred, and the integrated operation is achieved.
(5) Removing the AAO template to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material:
And (3) washing the Ni/NiO-nano double-layer tube array with the AAO template by using deionized water, placing the Ni/NiO-nano double-layer tube array with the AAO template in 1M KOH to dissolve the AAO template, repeatedly washing by using deionized water, and drying to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material on the oxygen-free conductive copper sheet.
The AAO template removal process can remove hydrogen peroxide (H)2O2) After the solution is fully cleaned, 1M KOH is directly added into the original electrochemical deposition device, so that the Ni/NiO-nano double-layer tube array with the AAO template does not need to be transferred, and the integrated operation is achieved.
it should be noted that, as will be understood by those skilled in the art and relevant arts, in the step (4) of oxidizing the transition metal nanotube layer with the template in the above embodiment, the oxidant used may be, but is not limited to, hydrogen oxide (H)2O2) The core idea is that proper oxidant is selected according to template material and transition metal material, and transition metal/transition metal native oxide-nano double-layer tube array is obtained without transferring transition metal nano tube layer with template; similarly, it should be understood by those skilled in the art and related arts that in the step (5) of removing the template in the above embodiment, the dissolving agent/reactant can be, but is not limited to, KOH, and the core of the dissolving/reacting is to remove the template according to the template material and the native oxide of the transition metal/transition metal, so as to obtain the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor on the oxygen-free conductive copper sheet.
example 3
Annealing decomposition NiO precursor Ni (OH)2auxiliary electrochemical-template-method-based preparation of Ni/NiO-nano double-layer tube array supercapacitor electrode material
the method comprises the following steps:
(1) Template pretreatment:
In this embodiment, an Anodic Aluminum Oxide (AAO) template with short-range ordered arrangement of double-sided through holes is adopted, and the axial length d of the templateAAO150 μm, pore diameter phiAAO＝200nm。
depositing a Conductive Layer (CL) on one surface of the double-pass AAO template by adopting a physical vapor deposition method, wherein the thickness d of the Conductive LayerCL60nm, the conductive layer material is Au. The CL/AAO template after deposition is cut into the required size S according to the requirementAAOAnd (5) standby.
(2) Preparing electrolyte:
This example uses analytically pure Ni (Ac)2dissolving in deionized water to prepare 0.03mol/L solution as electrolytic deposition solution.
(3) electrodeposition preparation of a Ni nanotube layer based on an AAO template:
The electrochemical deposition device is a three-Electrode system electrochemical deposition device made of polytetrafluoroethylene, wherein three electrodes are respectively a Working Electrode (WE), a Counter Electrode (CE) and a Reference Electrode (RE); in this embodiment, the CE is a platinum (Pt) mesh electrode, the RE is an Ag/AgCl electrode, and the oxygen-free conductive copper sheet is in close contact with the CL to form the WE.
Assembling the electrochemical deposition device with the three-electrode system. Connecting the electrochemical station to the electrodes (CE, WE and RE), injecting a certain amount of Ni (Ac)2Standing the electrolytic deposition solution for 20min after the electrolytic deposition solution is fully infiltrated into the CL/AAO template.
This embodiment employs a constant voltage VdepDepositing the Ni nanotube layer based on the AAO template at-1.1V, and maintaining the room temperature T at 25 deg.C for deposition time TdepObtaining Ni nano tube layer with AAO template, average wall thickness d of Ni nano coaxial tubeNi50nm, axial length L is 3 μm.
And (4) closing the electrochemical workstation after the deposition is finished, disconnecting the electrochemical workstation from each electrode, recovering the electrolyte, and washing the Ni nanotube layer with the AAO template by using deionized water.
(4) preparing a Ni/NiO-nano double-layer tube array with an AAO template by using high-temperature annealing assistance:
Adding proper amount of buffering agent, such as sodium acetate NaAc, into the electrolyte, adjusting pH to 8, and adopting constant pressure VdepElectrochemical deposition/oxidation to give Ni (OH) as a precursor of NiO2And a Ni nanotube layerNi/Ni (OH)2 nanometer double-layer tube array, keeping the room temperature T at 25 ℃ in the deposition process, and depositing for Tdep＝180～900s。
For the previously prepared and cleaned Ni/Ni (OH) with AAO template2Annealing the nano double-layer tube array at the annealing temperature TaAnnealing and oxidizing at 300 deg.c for taAnd (3) naturally cooling at the heating speed of 10 ℃/min within 2400s to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material with the template.
(5) Removing the AAO template to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material:
And placing the obtained Ni/NiO-nano double-layer tube array with the AAO template in 1M KOH for dissolving the AAO template, repeatedly washing with deionized water, and drying to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material on the oxygen-free conductive copper sheet.
example 4
Preparation of Ni/NiO-nano double-layer tube array supercapacitor electrode material based on electrochemical-template method assisted by annealing oxidation
The method specifically comprises the following steps:
(1) The steps (1) to (3) in the step 2 of preparing the Ni/NiO-nano double-layer tube array supercapacitor electrode material in an integrated manner based on an electrochemical-template method assisted by an oxidant are repeated.
(2) Preparing a Ni/NiO-nano double-layer tube array with an AAO template:
Annealing the prepared and cleaned Ni nanotube array with the AAO template in an oxygen-containing atmosphere at the annealing temperature TaAnnealing and oxidizing at 200 deg.C for taAnd (3) naturally cooling at a heating rate of 5 ℃/min for 3600s to obtain the Ni/NiO-nano double-layer tube array supercapacitor electrode material with the AAO template.
(3) The step (5) in the step 2 of preparing the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor based on the integration of the oxidant and the electrochemical-template method is repeated, and the template is removed to obtain the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor.
Examples 5 to 9
the core idea of the foregoing embodiments 1-4 is that: firstly, preparing a transition metal nanotube layer with a template by adopting an electrochemical-template method; then, in-situ reaction oxidation is adopted or the pH value, the potential and the like of the electrolyte are adjusted according to a Bobye diagram to obtain a transition metal oxide nanotube layer with a coaxial structure with the electrolyte; finally the template is removed using a suitable solvent/reagent.
According to the core idea and the transition metal/transition metal oxide nano double-layer tube array supercapacitor electrode material, examples 5 to 9 provide an integrated preparation method of different transition metal/transition metal native oxide nano double-layer tube arrays at normal temperature (25 ℃), and the specific details are shown in table 1.
TABLE 1
example 10 energy storage application of Ni/NiO-nano double-layer tube array supercapacitor electrode material
Based on the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor prepared in example 1, Cyclic Voltammetry (CV) and constant current charging and discharging (GCD) applications are performed by using a three-electrode system electrochemical cell, wherein the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor is used as a positive electrode, a platinum mesh is used as a negative electrode, and 1M KOH is used as an electrolyte. Performing cyclic voltammetry energy storage characterization under a series of scanning voltage rates, as shown in patent figures 3-5; at current mass density JNiOconstant current charging and discharging are carried out at 3, 5 and 10A/g, and the product is shown in patent figure 6. And calculating the specific capacitance of the electrode material of the Ni/NiO-nano double-layer tube array supercapacitor according to the formula Cs (delta t)/(m delta V). The prepared material has higher specific capacitance value, excellent power characteristic and cycle stability performance, and is an ideal capacitor material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An electrode material for a supercapacitor, comprising: the nano double-layer tube array grows vertically and is distributed on the conducting layer in order; the nano double-layer tube array is a nano coaxial tube array prepared by a double-pass insulating template, and the nano double-layer tube comprises a transition metal nano tube layer and a transition metal oxide nano tube layer growing on the inner wall of the transition metal nano tube layer;
the transition metal nanotube layer is transition metal or an alloy thereof, and the transition metal oxide nanotube layer is native oxide of the transition metal or the alloy thereof corresponding to the transition metal nanotube layer.
2. The supercapacitor electrode material according to claim 1, wherein the transition metal nanotube layer is Ni, Co, Fe, Mn or an alloy thereof, and the transition metal oxide nanotube layer is a native oxide of Ni, Co, Fe, Mn or an alloy thereof.
3. The supercapacitor electrode material according to claim 2, wherein the transition metal nanotube layer is Mn1-aFeaOr Ni1-bFebWherein, 0<a<1，b<1; the transition metal oxide nanotube layer is NiO, CoO, Co2O3、Co3O4、Mn2O3、MnO2、Mn3O4、CoFeO4And NiFeO4One or more combinations thereof.
4. The supercapacitor electrode material according to claim 1, wherein the template aperture Φ of the double-pass insulating templateT50 nm-2000 nm, axial length d of templateT20 nm-500 mu m; thickness d of the conductive layerCLNot larger than the aperture phi of the templateT。
5. the supercapacitor electrode material according to claim 1, wherein the double-pass insulating template is an alumina template, a titania template, a porous silicon template or an organic porous template; the conducting layer is arranged on one surface of the double-pass insulating template and is an inactive metal film, an organic conducting film, an inorganic non-metal conducting film or an organic-metal composite film.
6. the supercapacitor electrode material according to any one of claims 1 to 5, wherein the nano-bilayer tube has an inner diameter of 10nm to ΦTWall thickness d 'of the transition metal nanotube layer'TMIs 3nm to dTMWall thickness d of the transition metal oxide nanotube layerTMOxNot less than dTM-d’TMA difference of (d); wherein d isTMThe wall thickness of the transition metal nanotube layer is 0<dTM<ΦT。
7. the electrode material of the supercapacitor according to claim 6, wherein the nano double-layer tube array has an axial length L of 50nm to dT。
8. The method for preparing the electrode material of the supercapacitor according to any one of claims 1 to 7, comprising the steps of:
(1) Depositing a conducting layer on one surface of the double-pass insulating template by adopting a physical vapor deposition method, a chemical vapor deposition method or a spin-coating method;
(2) Preparing a transition metal nanotube layer in a pore channel of a bi-pass insulating template by adopting electrochemical deposition;
(3) preparing a transition metal oxide nanotube layer in the transition metal nanotube layer to obtain a double-layer nanotube array generated in the pore channel of the double-pass insulating template;
(4) And (4) washing the nano double-layer tube array prepared in the step (3) with deionized water, then placing the nano double-layer tube array in a reagent which can dissolve the bi-pass insulating template and does not react with the nano double-layer tube array, soaking, removing the bi-pass insulating template, then washing and drying to obtain the electrode material of the supercapacitor.
9. The preparation method of the electrode material of the supercapacitor, according to claim 8, wherein in the step (3), the method for preparing the transition metal oxide nanotube layer in the transition metal nanotube layer comprises:
(3-1): adding a buffering agent into the electrolyte system in the step (2) according to the electrolyte system Bbye diagram to adjust the pH value of the electrolyte system, and then carrying out electrochemical deposition in the transition metal nanotube layer to form a transition metal oxide nanotube layer;
Or, (3-2): cleaning the transition metal nanotube layer with the bi-pass insulating template prepared in the step (2), then soaking the transition metal nanotube layer in an oxidant solution, and carrying out oxidation reaction in the transition metal nanotube layer to generate a transition metal oxide nanotube layer;
Or, (3-3): cleaning the transition metal nano tube layer with the bi-pass insulating template prepared in the step (2), and then annealing the transition metal nano tube layer in an oxygen-containing atmosphere at an annealing temperature TaAt 50-900 ℃ for an annealing time taIs 120 s-7200 s.
10. The method for preparing the electrode material of the supercapacitor according to claim 9, wherein the step (3-1) further comprises: annealing the product after the electrochemical deposition reaction at an annealing temperature TaAt 50-900 ℃ for an annealing time tais 120s to 7200 s; the product is an oxide or hydroxide of a transition metal or alloy thereof.
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Application publication date: 20191213 |