CN110993362A - Novel three-dimensional electrode material, preparation method thereof and application thereof in super capacitor - Google Patents
Novel three-dimensional electrode material, preparation method thereof and application thereof in super capacitor Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 78
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 199
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 162
- 239000006260 foam Substances 0.000 claims abstract description 45
- 239000011258 core-shell material Substances 0.000 claims abstract description 41
- 239000002071 nanotube Substances 0.000 claims abstract description 39
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 136
- 239000011787 zinc oxide Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 42
- 239000002073 nanorod Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 40
- 238000004140 cleaning Methods 0.000 claims description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000005530 etching Methods 0.000 claims description 16
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims description 12
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 10
- 238000003487 electrochemical reaction Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000011263 electroactive material Substances 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 44
- 239000002131 composite material Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 22
- 239000004312 hexamethylene tetramine Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000004070 electrodeposition Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 229960004011 methenamine Drugs 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000004246 zinc acetate Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229940075397 calomel Drugs 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0547—Nanofibres or nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Microelectronics & Electronic Packaging (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Metallurgy (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a novel three-dimensional electrode material, a preparation method thereof and application thereof in a super capacitor, and belongs to the technical field of electrochemistry. The electrode material is a nickel @ active component nano-sheet core-shell structure array, and is formed by taking a simple substance hollow nickel nano-tube array which is self-supported by a foam metal substrate as a core and taking active component nano-sheets which grow on the simple substance hollow nickel nano-tube array as shells. The invention provides more space and active sites for electrochemical reaction and adsorption by utilizing the large specific surface area of the orderly three-dimensional nano structure grown on the substrate, and the electroactive material is attached to the surface of the nickel nano tube array for in-situ growth, thereby having more perfect nano structure and better mechanical stability.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a novel three-dimensional electrode material, a preparation method thereof and application thereof in a super capacitor.
Background
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, and has the characteristics of rapid charge and discharge of the capacitor and the energy storage characteristic of the battery. Compared with the performance of the traditional capacitor and the battery, the super capacitor has the following advantages compared with other energy storage devices: (1) high power and energy density; (2) the cycle life is long; (3) the charging and discharging efficiency is high; (4) the charging and discharging time is short; (5) the working temperature range is wide; (6) the placing time is long; (7) environmental protection, green and low maintenance cost. The application is mainly in high-power pulse application and instantaneous power maintenance, and meanwhile, the high-power pulse energy-saving battery can be charged and discharged quickly and can be kept stable.
Nowadays, the use of electric energy is deeply buried in human life, people have more urgent needs for more miniaturized, high-energy and power density power supplies, so that the research on electrode materials of super capacitors is greatly advanced and rapidly developed, and researchers have researched and reported a large number of novel electrode materials. These electrode materials all have the common characteristics of large capacity, good conductivity and excellent rate capability. In order to make the electrode material have these excellent properties, the most effective and most convenient means is to design and prepare the electrode material into a nano structure, such as a manganese oxide nano sheet, an iron oxide quantum dot, an iron oxide nano rod, a tin oxide nano sheet, and the like. The nano material has the characteristics of large specific surface area and small structure size, and when the nano material is used as a capacitor electrode material, a larger capacity and a faster electron transfer channel can be provided, so that the conductivity of the material and the rate capability of the material are effectively improved. The excellent characteristics of the nano materials ensure that the super capacitor formed by the materials has good performance and wide application value.
With the development and technical progress of human society, the exhaustion of fossil energy and the pollution of fossil energy to the environment, the research on new energy and new energy storage equipment is concerned by people. Under such circumstances, supercapacitors have become the mainstream of research with their advantages of environmental protection, high power density, long life, and fast charge and discharge rate, and have been widely used. The electrode material is a major factor affecting supercapacitors. At present, the metal oxide and hydroxide electrode gradually replaces the carbon-based electrode material with the advantages of abundant resources, low price, environmental protection, high specific capacity and the like. Among them, nickel hydroxide is a representative electrode material. However, the conductivity and lower ion transport rate of metal oxide materials are insufficient, and these defects affect their performance as electrodes. In order to solve the existing problems, the mainstream research direction is to prepare nano-scale materials and combine the nano-scale materials with high-conductivity collectors. The material with excellent composite conductivity can improve the conductivity of the oxide electrode, and the specific surface area of the electrode can be improved by preparing the material into a nano scale so as to increase the contact area with the electrolyte and improve the energy of the oxide material.
The present application has been made for the above reasons.
Disclosure of Invention
The invention aims to solve the problems pointed out in the background art and the defects in the prior art, and aims to provide a novel three-dimensional electrode material, a preparation method thereof and application thereof in a super capacitor.
In order to achieve the first object of the present invention, the present invention adopts the following technical solutions:
a novel three-dimensional electrode material is a nickel @ active component nanosheet core-shell structure array, and is formed by taking a simple substance hollow nickel nanotube array self-supported by a foam metal substrate as a core and taking active component nanosheets growing on the simple substance hollow nickel nanotube array as a shell.
Further, according to the technical scheme, the foam metal substrate is any one of foam nickel, foam copper nickel, foam aluminum and the like.
Further, in the above technical scheme, the active component is any one of manganese dioxide, nickel hydroxide, cobalt hydroxide, nickel cobalt double metal hydroxide, and the like.
The second purpose of the present invention is to provide a method for preparing the above-mentioned novel three-dimensional electrode material, which comprises the following steps:
firstly, pretreating a foam metal substrate; then growing a zinc oxide nanorod array on the pretreated foam metal substrate; forming an elemental nickel layer on the zinc oxide nanorod array to obtain a zinc oxide @ nickel core-shell structure array; etching, cleaning and drying the zinc oxide @ nickel core-shell structure array to obtain the foam metal self-supported simple substance hollow nickel nanotube array; and finally, growing an active component nanosheet on the simple substance hollow nickel nanotube array, and drying to obtain the novel three-dimensional electrode material.
Further, according to the technical scheme, the zinc oxide nanorod array can be prepared by a hydrothermal method or an electrodeposition method.
Furthermore, in the technical scheme, the process for growing the zinc oxide nano rod on the surface of the foamed nickel by the hydrothermal method comprises the following steps:
(a) preparing a zinc oxide seed layer: soaking the pretreated foamed nickel in an anhydrous methanol aqueous solution containing 0.005-0.02 mol/L of zinc acetate, ultrasonically stirring for 10-30 min, taking out, then annealing at 150-300 ℃ for 1-3 h, and naturally cooling to obtain a zinc oxide seed layer;
(b) preparing a zinc oxide nanorod: preparing a mixed solution containing hexamethylene tetramine (HMTA) and zinc salt with equal molar concentration, uniformly stirring, transferring the mixed solution into a reaction kettle, vertically and upwards putting the foamed metal substrate containing the seed layer obtained in the step (1) into the reaction kettle, dropwise adding ammonia water, sealing the reaction kettle, heating to 80-100 ℃, reacting for 8-12 hours at a constant temperature, cooling after the reaction is finished, washing, and drying to obtain the zinc oxide nanorod array.
Preferably, in the above technical scheme, the zinc salt in step (b) is any one of zinc acetate, zinc nitrate, zinc chloride, or the like.
Preferably, in the technical scheme, the mass fraction of the ammonia water in the step (b) is 25-28%.
Further, according to the technical scheme, the length of the zinc oxide nano rod is 1-2 mu m, and the diameter of the zinc oxide nano rod is 100-200 nm.
Further, in the above technical scheme, the elemental nickel layer is prepared by an electrodeposition method, for example, the elemental nickel layer can be prepared by a constant potential electrodeposition method or a constant current electrodeposition method. Taking a constant current electrodeposition method for preparing an elemental nickel layer as an example, the method comprises the following steps:
taking a mixed aqueous solution of nickel sulfate and ammonium chloride as an electrolyte, adopting a three-electrode system, taking a foam metal substrate with a zinc oxide nanorod array growing on the surface as a working electrode, taking a platinum electrode or a graphite electrode as a counter electrode, and taking a saturated calomel electrode as a reference electrode, carrying out constant-current electrodeposition at room temperature, and after the electrodeposition is finished, cleaning and drying the working electrode to obtain the zinc oxide @ nickel core-shell structure array.
Preferably, in the above technical scheme, the current density adopted by the constant current method is-1 to-2 mA/cm2。
More preferably, in the above technical solution, the constant current electrodeposition time is not limited, and the electrodeposition time is specifically determined according to the thickness of the elemental nickel layer deposited on the surface of the zinc oxide nanorod, and may be, for example, 10min, 20min, 30min, 40min, and the like.
Further, according to the technical scheme, the etching process specifically comprises the step of removing a zinc oxide core in the zinc oxide @ nickel core shell structure by using concentrated ammonia water to form the simple substance hollow nickel nanotube array.
Preferably, in the technical scheme, the etching process is specifically carried out for 10-12 hours at room temperature in concentrated ammonia water.
Further, according to the technical scheme, the length of the simple substance hollow nickel nanotube is 1-2 μm, the diameter is 100-200 nm, and the thickness is 5-10 nm.
Further, according to the technical scheme, the active component nanosheet is prepared by a hydrothermal method, and specifically, the method comprises the steps of placing a single hollow nickel nanotube array in a reaction precursor containing metal salt and water, reacting at a constant temperature of 120-160 ℃ for 4-10 hours, cleaning and drying.
Preferably, in the above technical scheme, the metal salt is at least one of potassium permanganate, nickel nitrate and cobalt nitrate.
Preferably, in the above technical solution, the reaction precursor further includes hexamethylenetetramine.
Preferably, in the above technical scheme, the molar ratio of the metal salt to the hexamethylenetetramine is (2-6): 10.
the third purpose of the invention is to provide the application of the novel three-dimensional electrode material, which can be applied to a super capacitor.
The utility model provides a super capacitor, includes anodal, negative pole, sets up diaphragm, electrolyte and the casing between the positive negative pole, wherein: the anode and/or the cathode are/is the novel three-dimensional electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nano array grows on the substrate orderly, and the ordered three-dimensional nano structure has a huge specific surface and can provide more spaces and active sites for electrochemical reaction and adsorption;
(2) compared with powder or block materials, the nano array with the multi-dimensional structure has smaller electronic resistance, so that electrons can be conducted in the material more quickly;
(3) the active component of the invention is attached to the surface of the nickel nanotube array for in-situ growth, and has more perfect nano-structure and better mechanical stability;
(4) the interiors of the nano arrays are not tightly attached to each other, but certain spaces exist, the existence of the spaces improves a rapid diffusion channel for ions in electrolyte, and simultaneously provides spaces for the structural volume change of materials during electrochemical reaction, thereby effectively enhancing the structural stability of electrode materials;
(5) the invention can directly synthesize and obtain the usable electrode material, and does not need to use a binder to prepare the electrode, thereby simplifying the synthesis process and ensuring the perfect performance of the material;
(6) the novel three-dimensional electrode material provided by the invention is green and environment-friendly in preparation method, low in cost and simple in preparation.
Drawings
FIGS. 1(a) and (b) are Scanning Electron Microscope (SEM) images of carbon cloth-based zinc oxide nanorod arrays prepared in example 1 of the present invention;
FIGS. 2(a) and (b) are Scanning Electron Microscope (SEM) images of the ZnO nanorod array based on nickel foam prepared in example 2 of the present invention;
FIGS. 3(a), (b) are Scanning Electron Microscope (SEM) images of the Ni nanotube array prepared in example 2 of the present invention;
FIGS. 4(a), (b) are Scanning Electron Microscope (SEM) images of the Ni @ Mn dioxide core-shell structure array prepared in example 2 of the present invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of an array of nickel @ nickel hydroxide core-shell structures prepared according to example 3 of the present invention;
FIG. 6 is a Scanning Electron Microscope (SEM) image of an array of nickel @ cobalt hydroxide core-shell structures prepared in example 4 of the present invention;
FIG. 7 is a Scanning Electron Microscope (SEM) image of an array of core-shell structures of nickel @ nickel cobalt double metal hydroxide prepared in example 5 of the present invention;
FIG. 8 is a plot of cyclic voltammetry for the nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different scan rates;
FIG. 9 is a plot of cyclic voltammetry for the nickel @ nickel hydroxide composite electrode material of example 3 of the present invention at different scan rates;
FIG. 10 is a plot of cyclic voltammetry for the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different scan rates;
FIG. 11 is a plot of cyclic voltammetry for the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 of the present invention at different scan rates;
FIG. 12 is a constant current charge and discharge graph of the nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different current densities;
FIG. 13 is a constant current charge and discharge graph of the nickel @ nickel hydroxide composite electrode material of example 3 of the present invention at different current densities;
FIG. 14 is a constant current charge-discharge curve diagram of the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different current densities;
FIG. 15 is a constant current charge and discharge graph of the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 of the present invention at different current densities;
FIG. 16 is a graph of mass to specific capacity for nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different current densities;
FIG. 17 is a graph of mass to capacity ratio for different current densities for the nickel @ nickel hydroxide composite electrode material of example 3 in accordance with the present invention;
FIG. 18 is a graph of mass to capacity ratio for the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different current densities;
FIG. 19 is a graph of mass specific capacity versus current density for the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 in accordance with the present invention;
FIG. 20 is a flow chart of the process for preparing the novel three-dimensional electrode material of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The invention relates to a novel three-dimensional electrode material and a preparation method thereof, the invention utilizes the three-dimensional nano structure which grows on a substrate in order and has huge specific surface area, can provide more spaces and active sites for electrochemical reaction and adsorption, the nano array has smaller electronic resistance, electrons can be conducted in the material more quickly, and the electroactive material is attached to the surface of the nickel nano tube array for in-situ growth, so that the three-dimensional electrode material has more perfect nano structure and better mechanical stability, the interiors of the nano array cannot be tightly attached to each other, but certain spaces exist, the existence of the spaces improves a quick diffusion channel for ions in electrolyte, provides a space for the change of the structural volume of the material during the electrochemical reaction, and effectively enhances the structural stability of the electrode material. In addition, the novel three-dimensional electrode material can be directly synthesized to obtain a usable electrode material, and an electrode is prepared without using a binder, so that the synthesis process is simplified, and the performance of the material can be perfectly exerted. Therefore, the preparation process is convenient and simple, green and environment-friendly, has small interface internal resistance, high energy density and high pseudocapacitance, greatly improves the production efficiency, reduces the production cost, and is suitable for industrial large-scale production.
Example 1
The preparation method of the novel three-dimensional electrode material of the embodiment takes the carbon cloth as the substrate, and sequentially comprises the following steps: pretreating a substrate and growing a zinc oxide nanorod array. The method specifically comprises the following steps:
(1) pretreating carbon cloth: obtaining 2X 3cm2The carbon cloth with the specification is sequentially soaked in concentrated nitric acid for 1h, ultrasonically cleaned for 15min, finally cleaned in deionized water for 15min, taken out and dried by cold air for later use.
(2) Growing a zinc oxide nanorod array:
(a) a zinc oxide seed layer: dissolving 0.01M zinc acetate in 100ml anhydrous methanol, stirring, adding carbon cloth, ultrasonically stirring for 15min, taking out, and placing in a drying oven for heat preservation at 200 ℃ for 1-2 h;
(b) zinc oxide growth layer: weighing 0.1M of Hexamethylenetetramine (HMTA) and dissolving in 100ml of deionized water, stirring uniformly, weighing 0.1M of zinc nitrate hexahydrate and pouring into the solution, continuously stirring for 30min, pouring 80ml of the solution into a 100ml of polytetrafluoroethylene inner container after the solution is uniform, finally dripping 598 mu l of concentrated ammonia water with the mass fraction of 25-28%, putting into a stainless steel reaction kettle, carrying out hydrothermal reaction at 90 ℃, and keeping the temperature for 10 h.
(3) Cleaning and drying: and (3) repeatedly cleaning the carbon cloth by using deionized water, and finally drying the carbon cloth in a drying oven for 8 hours to obtain the zinc oxide nanorod array.
Fig. 1(a) and (b) are Scanning Electron Microscope (SEM) images of the zinc oxide nanorod array on the carbon cloth substrate prepared in example 1 of the present invention, and it can be seen that the zinc oxide nanorod array uniformly grows on the flexible carbon cloth fiber, the length of the zinc oxide nanorod is 1-2 μm, and the diameter is 100-200 nm.
Example 2
The preparation method of the novel three-dimensional electrode material of the embodiment takes the foamed nickel as a substrate, and sequentially comprises the following steps: the method comprises the following steps of substrate pretreatment, zinc oxide nanorod array growth, zinc oxide @ nickel core-shell structure array growth, zinc oxide etching to obtain a nickel nanotube array, and manganese dioxide nanosheet growth to obtain a nickel @ manganese dioxide core-shell structure array. The method specifically comprises the following steps:
(1) foam nickel pretreatment: obtaining 2X 3cm2Soaking and ultrasonically cleaning the foam nickel with the specification by 3mol/L hydrochloric acid for 15min, then ultrasonically cleaning the foam nickel in absolute ethyl alcohol for three times, finally cleaning the foam nickel in deionized water for 15min, taking out the foam nickel, and drying the foam nickel in a drying oven for 8h at the temperature of 80 ℃ for later use.
(2) Growing a zinc oxide nanorod array:
(a) a zinc oxide seed layer: dissolving 0.01M zinc acetate in 100ml of anhydrous methanol, stirring, adding foamed nickel, performing ultrasonic stirring for 15min respectively, taking out, and putting into a drying oven for heat preservation at 200 ℃ for 1-2 h;
(b) zinc oxide growth layer: weighing 0.1M of Hexamethylenetetramine (HMTA) and dissolving in 100ml of deionized water, stirring uniformly, weighing 0.1M of zinc nitrate hexahydrate and pouring into the solution, continuously stirring for 30min, pouring 80ml of the solution into a 100ml of polytetrafluoroethylene inner container after the solution is uniform, finally dripping 598 mu l of concentrated ammonia water with the mass fraction of 25-28%, putting into a stainless steel reaction kettle for hydrothermal reaction at 90 ℃, preserving heat for 10h to obtain a zinc oxide nanorod array, and cleaning and drying for later use.
(3) Growing a zinc oxide @ nickel core-shell structure array: adopting a three-electrode constant-current electrodeposition process, taking foamed nickel of a growing zinc oxide nanorod array as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a mixed solution of 0.01M nickel sulfate hexahydrate and 0.02M ammonium chloride as an electrolyte, and performing a constant-current electrodeposition process at a current density of-1.5 mA/cm2And reacting for 10min at the temperature of 30 ℃, and obtaining the zinc oxide @ nickel core-shell structure array after the reaction is finished, and cleaning and drying the zinc oxide @ nickel core-shell structure array for later use.
(4) Etching: and etching the obtained array for 10-12 h at room temperature by using concentrated ammonia water to obtain a simple substance nickel nanotube array, and cleaning and drying the simple substance nickel nanotube array for later use.
(5) Growing manganese dioxide nanosheets: preparing 0.03M potassium permanganate solution, pouring the solution into a 100mL polytetrafluoroethylene inner container, vertically immersing the foamed nickel with the nickel nanotube array into the solution, placing the foamed nickel into a stainless steel reaction kettle for hydrothermal reaction at 160 ℃ and keeping the temperature for 4 hours, taking out the foamed nickel, cleaning and drying the foamed nickel to obtain the nickel @ manganese dioxide core-shell structure array.
(6) A three-electrode testing system is used for electrochemical testing of the material, the electrode material is used as a working electrode, a platinum electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, and the tested electrolyte is 6mol/L potassium hydroxide solution.
FIGS. 2(a) and (b) are Scanning Electron Microscope (SEM) images of the zinc oxide nanorod array based on nickel foam prepared in example 2 of the present invention. It can be seen that the zinc oxide nanorod array uniformly grows on the foamed nickel, the length of the zinc oxide nanorod is 1-2 μm, and the diameter of the zinc oxide nanorod is 100-200 nm.
FIGS. 3(a), (b) are Scanning Electron Microscope (SEM) images of the Ni nanotube array prepared in example 2 of the present invention; it can be seen that the length of the nickel nanotube is 1-2 μm, the diameter is 100-200 nm, and the thickness is 5-10 nm. The nano nickel tube array with the structure can provide a nano-scale growth environment and sites for active components.
FIGS. 4(a), (b) are Scanning Electron Microscope (SEM) images of the Ni @ Mn dioxide core-shell structure array prepared in example 2 of the present invention; the manganese dioxide nanosheets uniformly grow on the foamed nickel, the thickness of the manganese dioxide nanosheets is small, the three-dimensional structure formed by the nanosheets is favorable for the diffusion of the electrolyte, the diffusion of hydroxide ions in the water-based electrolyte to the surface of the electrode can be accelerated, and the electron transmission and the rapid electrochemical reaction are facilitated.
FIG. 8 is a plot of cyclic voltammetry for the nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different scan rates; obvious redox peaks can be observed from curves, the upper part and the lower part are approximately symmetrical, the nickel @ manganese dioxide nanosheet composite electrode material is proved to have good capacitance reversibility, and when the scanning rate is increased from 10mV/s to 100mV/s, the change of the profile of the cyclic voltammetry curve is not obvious, which shows that the structure has good capacitance performance.
FIG. 12 is a constant current charge and discharge graph of the nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different current densities; FIG. 16 is a graph of mass to specific capacity for nickel @ manganese dioxide composite electrode material of example 2 of the present invention at different current densities; the current density is 0.5A/g, 1A/g, 3A/g, 5A/g and 7A/g in sequence, and the specific capacitance is 305-479F/g as can be seen from FIG. 16.
Example 3
The preparation method of the novel three-dimensional electrode material of the embodiment takes the foamed nickel as a substrate, and sequentially comprises the following steps: the method comprises the following steps of substrate pretreatment, zinc oxide nanorod array growth, zinc oxide @ nickel core-shell structure array growth, zinc oxide etching to obtain a nickel nanotube array, and nickel hydroxide nanosheet growth to obtain a nickel @ nickel hydroxide core-shell structure array. The method specifically comprises the following steps:
(1) foam nickel pretreatment: obtaining 2X 3cm2Soaking and ultrasonically cleaning the foam nickel with the specification by 3mol/L hydrochloric acid for 15min, then ultrasonically cleaning the foam nickel in absolute ethyl alcohol for three times, finally cleaning the foam nickel in deionized water for 15min, taking out the foam nickel, and drying the foam nickel in a drying oven for 8h at the temperature of 80 ℃ for later use.
(2) Growing a zinc oxide nanorod array:
(a) a zinc oxide seed layer: dissolving 0.01M zinc acetate in 100ml of anhydrous methanol, stirring, adding foamed nickel, performing ultrasonic stirring for 15min respectively, taking out, and putting into a drying oven for heat preservation at 200 ℃ for 1-2 h;
(b) zinc oxide growth layer: weighing 0.1M of Hexamethylenetetramine (HMTA) and dissolving in 100ml of deionized water, stirring uniformly, weighing 0.1M of zinc nitrate hexahydrate and pouring into the solution, continuously stirring for 30min, pouring 80ml of the solution into a 100ml of polytetrafluoroethylene inner container after the solution is uniform, finally dripping 598 mu l of concentrated ammonia water with the mass fraction of 25-28%, putting into a stainless steel reaction kettle for hydrothermal reaction at 90 ℃, preserving heat for 10h to obtain a zinc oxide nanorod array, and cleaning and drying for later use.
(3) Growing zinc oxide @ nickel core-shell structure array: adopting a three-electrode constant-current electrodeposition process, taking foamed nickel of a growing zinc oxide nanorod array as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a mixed solution of 0.01M nickel sulfate hexahydrate and 0.02M ammonium chloride as an electrolyte, and performing a constant-current electrodeposition process at a current density of-1.5 mA/cm2And reacting for 10min at the temperature of 30 ℃, and obtaining the zinc oxide @ nickel core-shell structure array after the reaction is finished, and cleaning and drying the zinc oxide @ nickel core-shell structure array for later use.
(4) Etching: and etching the obtained array for 10-12 h at room temperature by using concentrated ammonia water to obtain a simple substance nickel nanotube array, and cleaning and drying the simple substance nickel nanotube array for later use.
(5) Growing a nickel hydroxide nanosheet: preparing 4mmol of nickel nitrate hexahydrate and 10mmol of Hexamethylenetetramine (HMTA) to be dissolved in 60mL of deionized water, pouring into a 100mL polytetrafluoroethylene inner container, vertically immersing the foamed nickel with the nickel nanotube array into the solution, placing into a stainless steel reaction kettle for hydrothermal reaction at 120 ℃ for heat preservation for 10h, taking out, cleaning and drying to obtain the nickel @ nickel hydroxide core-shell structure array.
(6) A three-electrode testing system is used for electrochemical testing of the material, the electrode material is used as a working electrode, a platinum electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, and the tested electrolyte is 6mol/L potassium hydroxide solution.
FIG. 5 is a Scanning Electron Microscope (SEM) image of an array of nickel @ nickel hydroxide core-shell structures prepared according to example 3 of the present invention; it can be seen that a large amount of nickel hydroxide nanosheets are uniformly wrapped on the surface of the nickel nanotube array.
FIG. 9 is a plot of cyclic voltammetry for the nickel @ nickel hydroxide composite electrode material of example 3 of the present invention at different scan rates; obvious redox peaks can be observed by curves, the upper part and the lower part are approximately symmetrical, the nickel @ nickel hydroxide nanosheet composite electrode material is proved to have good capacitance reversibility, and when the scanning rate is increased from 10mV/s to 100mV/s, the change of the profile of the cyclic voltammetry curve is not obvious, which shows that the structure has good capacitance performance.
FIG. 13 is a constant current charge and discharge graph of the nickel @ nickel hydroxide composite electrode material of example 3 of the present invention at different current densities; FIG. 17 is a graph of mass to capacity ratio for different current densities for the nickel @ nickel hydroxide composite electrode material of example 3 in accordance with the present invention; when the current density is respectively 0.5A/g, 1A/g, 2A/g, 4A/g and 8A/g, the corresponding specific mass capacities are 890F/g, 790F/g, 656F/g, 552F/g and 448F/g.
Example 4
The preparation method of the novel three-dimensional electrode material of the embodiment takes the foamed nickel as a substrate, and sequentially comprises the following steps: the method comprises the following steps of substrate pretreatment, zinc oxide nanorod array growth, zinc oxide @ nickel core-shell structure array growth, zinc oxide etching to obtain a nickel nanotube array, and cobalt hydroxide nanosheet growth to obtain a nickel @ cobalt hydroxide core-shell structure array. The method specifically comprises the following steps:
(1) foam nickel pretreatment: obtaining 2X 3cm2Soaking and ultrasonically cleaning the foam nickel with the specification by 3mol/L hydrochloric acid for 15min, then ultrasonically cleaning the foam nickel in absolute ethyl alcohol for three times, finally cleaning the foam nickel in deionized water for 15min, taking out the foam nickel, and drying the foam nickel in a drying oven for 8h at the temperature of 80 ℃ for later use.
(2) Growing a zinc oxide nanorod array:
(a) a zinc oxide seed layer: dissolving 0.01M zinc acetate in 100ml of anhydrous methanol, stirring, adding foamed nickel, performing ultrasonic stirring for 15min respectively, taking out, and putting into a drying oven for heat preservation at 200 ℃ for 1-2 h;
(b) zinc oxide growth layer: weighing 0.1M of Hexamethylenetetramine (HMTA) and dissolving in 100ml of deionized water, stirring uniformly, weighing 0.1M of zinc nitrate hexahydrate and pouring into the solution, continuously stirring for 30min, pouring 80ml of the solution into a 100ml of polytetrafluoroethylene inner container after the solution is uniform, finally dripping 598 mu l of concentrated ammonia water with the mass fraction of 25-28%, putting into a stainless steel reaction kettle for hydrothermal reaction at 90 ℃, preserving heat for 10h to obtain a zinc oxide nanorod array, and cleaning and drying for later use.
(3) Growing a zinc oxide @ nickel core-shell structure array: adopting a three-electrode constant-current electrodeposition process, taking foamed nickel of a growing zinc oxide nanorod array as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a mixed solution of 0.01M nickel sulfate hexahydrate and 0.02M ammonium chloride as an electrolyte, and performing a constant-current electrodeposition process at a current density of-1.5 mA/cm2At a temperature ofAnd (3) reacting for 10min at the temperature of 30 ℃, and obtaining the zinc oxide @ nickel core-shell structure array after the reaction is finished, and cleaning and drying the zinc oxide @ nickel core-shell structure array for later use.
(4) Etching: and etching the obtained array for 10-12 h at room temperature by using concentrated ammonia water to obtain a simple substance nickel nanotube array, and cleaning and drying the simple substance nickel nanotube array for later use.
(5) Growing cobalt hydroxide nanosheets: dissolving 4mmol of cobalt nitrate hexahydrate and 10mmol of Hexamethylenetetramine (HMTA) in 60mL of deionized water, pouring into a 100mL polytetrafluoroethylene inner container, vertically immersing the foamed nickel with the nickel nanotube array into the solution, placing into a stainless steel reaction kettle for hydrothermal reaction at 120 ℃ for heat preservation for 10h, taking out, cleaning and drying to obtain the nickel @ cobalt hydroxide core-shell structure array.
(6) A three-electrode testing system is used for electrochemical testing of the material, the electrode material is used as a working electrode, a platinum electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, and the tested electrolyte is 6mol/L potassium hydroxide solution.
FIG. 6 is a Scanning Electron Microscope (SEM) image of an array of nickel @ cobalt hydroxide core-shell structures prepared in example 4 of the present invention; a large amount of cobalt hydroxide nanosheets are uniformly wrapped on the surface of the nickel nanotube array.
FIG. 10 is a plot of cyclic voltammetry for the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different scan rates; the scanning rates were 10mV/s, 20mV/s, 40mV/s, 60mV/s, 80mV/s, and 100mV/s, respectively. When the sweep rate was increased from 10mV/s to 100mV/s, the change in the profile of the cyclic voltammetry curve was insignificant, indicating that the structure had better capacitive performance.
FIG. 14 is a constant current charge-discharge curve diagram of the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different current densities; FIG. 18 is a graph of mass to capacity ratio for the nickel @ cobalt hydroxide composite electrode material of example 4 of the present invention at different current densities; the current density is 0.5A/g, 1A/g, 2A/g, 4A/g and 8A/g in sequence, and the specific capacitance is 576-1467F/g.
Example 5
The preparation method of the novel three-dimensional electrode material of the embodiment takes the foamed nickel as a substrate, and sequentially comprises the following steps: the method comprises the following steps of substrate pretreatment, zinc oxide nanorod array growth, zinc oxide @ nickel core-shell structure array growth, zinc oxide etching to obtain a nickel nanotube array, and nickel cobalt double metal hydroxide growth to obtain a nickel @ nickel cobalt double metal hydroxide core-shell structure array. The method specifically comprises the following steps:
(1) foam nickel pretreatment: obtaining 2X 3cm2Soaking and ultrasonically cleaning the foam nickel with the specification by 3mol/L hydrochloric acid for 15min, then ultrasonically cleaning the foam nickel in absolute ethyl alcohol for three times, finally cleaning the foam nickel in deionized water for 15min, taking out the foam nickel, and drying the foam nickel in a drying oven for 8h at the temperature of 80 ℃ for later use.
(2) Growing a zinc oxide nanorod array:
(a) a zinc oxide seed layer: dissolving 0.01M zinc acetate in 100ml of anhydrous methanol, stirring, adding foamed nickel, performing ultrasonic stirring for 15min respectively, taking out, and putting into a drying oven for heat preservation at 200 ℃ for 1-2 h;
(b) zinc oxide growth layer: weighing 0.1M of Hexamethylenetetramine (HMTA) and dissolving in 100ml of deionized water, stirring uniformly, weighing 0.1M of zinc nitrate hexahydrate and pouring into the solution, continuously stirring for 30min, pouring 80ml of the solution into a 100ml of polytetrafluoroethylene inner container after the solution is uniform, finally dripping 598 mu l of concentrated ammonia water with the mass fraction of 25-28%, putting into a stainless steel reaction kettle for hydrothermal reaction at 90 ℃, preserving heat for 10h to obtain a zinc oxide nanorod array, and cleaning and drying for later use.
(3) Growing a zinc oxide @ nickel core-shell structure array: adopting a three-electrode constant-current electrodeposition process, taking foamed nickel of a growing zinc oxide nanorod array as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as a counter electrode, taking a mixed solution of 0.01M nickel sulfate hexahydrate and 0.02M ammonium chloride as an electrolyte, and performing a constant-current electrodeposition process at a current density of-1.5 mA/cm2And reacting for 10min at the temperature of 30 ℃, and obtaining the zinc oxide @ nickel core-shell structure array after the reaction is finished, and cleaning and drying the zinc oxide @ nickel core-shell structure array for later use.
(4) Etching: and etching the obtained array for 10-12 h at room temperature by using concentrated ammonia water to obtain a simple substance nickel nanotube array, and cleaning and drying the simple substance nickel nanotube array for later use.
(5) Growing a nickel-cobalt double-metal hydroxide nanosheet: preparing 2mmol of nickel nitrate hexahydrate, 2mmol of cobalt nitrate hexahydrate and 10mmol of Hexamethylenetetramine (HMTA) and dissolving the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the Hexamethylenetetramine (HMTA) in 60mL of deionized water, pouring the mixture into a 100mL polytetrafluoroethylene inner container, vertically immersing the foamed nickel with the nickel nanotube array into the solution, placing the foamed nickel into a stainless steel reaction kettle for hydrothermal reaction at 120 ℃ and keeping the temperature for 10 hours, taking out the foamed nickel, cleaning and drying the foamed nickel to obtain the nickel @ nickel cobalt double-metal hydroxide core-shell structure.
(6) A three-electrode testing system is used for electrochemical testing of the material, the electrode material is used as a working electrode, a platinum electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, and the tested electrolyte is 6mol/L potassium hydroxide solution.
FIG. 7 is a Scanning Electron Microscope (SEM) image of an array of nickel @ nickel cobalt double metal hydroxide core-shell structures prepared in example 5 of the invention; it can be seen that the nickel cobalt bimetallic hydroxide nanosheets grew uniformly on the nickel foam.
FIG. 11 is a plot of cyclic voltammetry for the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 of the present invention at different scan rates; the scanning rates were 10mV/s, 20mV/s, 40mV/s, 60mV/s, 80mV/s, and 100mV/s, respectively. When the sweep rate was increased from 10mV/s to 100mV/s, the change in the profile of the cyclic voltammetry curve was insignificant, indicating that the structure had better capacitive performance.
FIG. 15 is a constant current charge and discharge graph of the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 of the present invention at different current densities; fig. 19 is a graph of mass specific capacity versus current density for the nickel @ nickel cobalt double metal hydroxide composite electrode material of example 5 in accordance with the present invention. The current density is 0.5A/g, 1A/g, 2A/g, 3A/g and 5A/g in sequence, and the specific capacitance is 256-418F/g.
Claims (10)
1. A novel three-dimensional electrode material is characterized in that: the electrode material is a nickel @ active component nano sheet core-shell structure array, and is formed by taking a simple substance hollow nickel nano tube array which is self-supported by a foam metal substrate as a core and taking an active component nano sheet which grows on the simple substance hollow nickel nano tube array as a shell.
2. The novel three-dimensional electrode material according to claim 1, characterized in that: the foam metal substrate is any one of foam nickel, foam copper nickel and foam aluminum.
3. The novel three-dimensional electrode material according to claim 1, characterized in that: the active component is any one of manganese dioxide, nickel hydroxide, cobalt hydroxide and nickel-cobalt double metal hydroxide.
4. The method for preparing a novel three-dimensional electrode material according to claim 1, wherein: the method comprises the following steps:
firstly, pretreating a foam metal substrate; then growing a zinc oxide nanorod array on the pretreated foam metal substrate; forming an elemental nickel layer on the zinc oxide nanorod array to obtain a zinc oxide @ nickel core-shell structure array; etching, cleaning and drying the zinc oxide @ nickel core-shell structure array to obtain the foam metal self-supported simple substance hollow nickel nanotube array; and finally, growing an active component nanosheet on the simple substance hollow nickel nanotube array, and drying to obtain the novel three-dimensional electrode material.
5. The method for preparing the novel three-dimensional electrode material according to claim 4, wherein: the zinc oxide nano rod has the length of 1-2 mu m and the diameter of 100-200 nm.
6. The method for preparing the novel three-dimensional electrode material according to claim 4, wherein: the length of the simple substance hollow nickel nano tube is 1-2 mu m, the diameter is 100-200 nm, and the thickness is 5-10 nm.
7. The method for preparing the novel three-dimensional electrode material according to claim 4, wherein: the active component nanosheet is prepared by a hydrothermal method, and specifically, the active component nanosheet is prepared by placing a single hollow nickel nanotube array in a reaction precursor containing metal salt and water, then reacting for 4-10 hours at a constant temperature of 120-160 ℃, cleaning and drying.
8. The method for preparing the novel three-dimensional electrode material according to claim 7, wherein: the metal salt is at least one of potassium permanganate, nickel nitrate and cobalt nitrate.
9. Use of the novel three-dimensional electrode material according to any one of claims 1 to 3 or the novel three-dimensional electrode material prepared by the method according to any one of claims 4 to 8, wherein: can be applied to super capacitors.
10. The utility model provides a super capacitor, includes anodal, negative pole, sets up diaphragm, electrolyte and the casing between the positive negative pole, its characterized in that: the positive electrode and/or the negative electrode is the novel three-dimensional electrode material as defined in any one of claims 1 to 3 or the novel three-dimensional electrode material prepared by the method as defined in any one of claims 4 to 8.
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| CN112090436A (en) * | 2020-09-14 | 2020-12-18 | 江浩 | Nickel-based catalyst, preparation method and application |
| CN112779586A (en) * | 2020-12-23 | 2021-05-11 | 华南理工大学 | Nickel phosphide with nanotube array structure and preparation method and application thereof |
| CN114429865A (en) * | 2022-01-10 | 2022-05-03 | 重庆文理学院 | Preparation method of nickel wire/ferric oxide/manganese dioxide composite fiber |
| WO2022143568A1 (en) * | 2020-12-30 | 2022-07-07 | Tcl科技集团股份有限公司 | Composite electron transport material and preparation method therefor, and light-emitting diode |
| CN115477338A (en) * | 2022-09-23 | 2022-12-16 | 淮阴师范学院 | Method for preparing hollow nano nickel oxide by using nickel powder as raw material |
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| CN112090436A (en) * | 2020-09-14 | 2020-12-18 | 江浩 | Nickel-based catalyst, preparation method and application |
| CN112779586A (en) * | 2020-12-23 | 2021-05-11 | 华南理工大学 | Nickel phosphide with nanotube array structure and preparation method and application thereof |
| CN112779586B (en) * | 2020-12-23 | 2022-05-24 | 华南理工大学 | Nickel phosphide with nanotube array structure and preparation method and application thereof |
| WO2022143568A1 (en) * | 2020-12-30 | 2022-07-07 | Tcl科技集团股份有限公司 | Composite electron transport material and preparation method therefor, and light-emitting diode |
| CN114429865A (en) * | 2022-01-10 | 2022-05-03 | 重庆文理学院 | Preparation method of nickel wire/ferric oxide/manganese dioxide composite fiber |
| CN114429865B (en) * | 2022-01-10 | 2023-10-13 | 重庆文理学院 | Preparation method of nickel wire/ferric oxide/manganese dioxide composite fiber |
| CN115477338A (en) * | 2022-09-23 | 2022-12-16 | 淮阴师范学院 | Method for preparing hollow nano nickel oxide by using nickel powder as raw material |
| CN115477338B (en) * | 2022-09-23 | 2023-09-26 | 淮阴师范学院 | Method for preparing hollow nano nickel oxide by taking nickel powder as raw material |
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