CN114400147B - Self-supporting bimetal-based electrode material, and preparation method and application thereof - Google Patents
Self-supporting bimetal-based electrode material, and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000006260 foam Substances 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 55
- 239000011787 zinc oxide Substances 0.000 description 34
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000004146 energy storage Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 229940075397 calomel Drugs 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- LNBBNXBJWLVZLB-UHFFFAOYSA-N cobalt;oxozinc Chemical compound [Zn].[Co]=O LNBBNXBJWLVZLB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a self-supporting bimetallic-based electrode material, a preparation method and application thereof, wherein the material is of a core-shell structure, and a core is ZnCo loaded on a foam nickel matrix 2 O 4 ZnO, shell is deposited on ZnCo 2 O 4 CoS at the surface of ZnO complex. The method comprises the following steps: pre-treating foam nickel; in situ growth of Zn on foam Nickel x Co 1‑x (OH) 2 The precursor is calcined to obtain ZnCo 2 O 4 -ZnO; by electrodeposition in ZnCo 2 O 4 Depositing CoS on the surface of ZnO@C to obtain the composite material. The material forms a stable three-dimensional structure, has a higher specific surface area and a large number of active sites, is fully contacted with electrolyte, has enough free space inside, and can effectively relieve long-term Faraday reaction; exhibit higher energy density, high, longer cycle life; the preparation method has the advantages of simple process, low cost and strong repeatability.
Description
Technical Field
The invention relates to a metal-based electrode material, a preparation method and application thereof, in particular to a self-supporting bimetal-based electrode material, a preparation method and application thereof.
Background
In the context of high-speed economic development, there is an increasing demand for pollution-free, renewable energy sources. The development and utilization scale of green clean energy sources such as solar energy, wind energy, tidal energy, nuclear energy and the like are continuously enlarged, but the energy sources are easily influenced by seasonal and regional changes, and the use continuity and stability are not guaranteed, so that the problems of transportation of the clean energy sources can be effectively solved by developing and using high-performance sustainable energy conversion and energy storage devices in combination with the energy storage devices.
However, the current commercial super capacitor still can only be used in the field of rapid charge and discharge due to low energy densityActing as a medicine. How to increase the energy density of super capacitors has been an important topic in the energy storage field. Electrode materials are one of the key factors affecting supercapacitor performance and production cost, so research and development of high-performance, low-cost electrode materials is an important content of supercapacitor development work. In recent years, binary metal oxides (e.g., niCo 2 O 4 And ZnCo 2 O 4 ) Is receiving more and more attention. They can synergistically enhance electrochemical performance in terms of reversible capacity, structural stability and conductivity. For example, binary zinc cobalt oxide (ZnCo 2 O 4 ) Exhibits a specific ratio to zinc oxide (ZnO) and cobalt oxide (Co) 3 O 4 ) Better conductivity and higher electrochemical activity. However ZnCo 2 O 4 The problems of poor conductivity, low energy density and short cycle life severely limit their development in the field of supercapacitors.
Disclosure of Invention
The invention aims to: the invention aims to provide a self-supporting bimetallic base electrode material with high energy density and long cycle life;
the second object of the invention is to provide a method for preparing the self-supporting bimetallic-based electrode material;
a third object of the present invention is to provide the use of the above-described self-supporting bimetallic-based electrode material.
The technical scheme is as follows: the self-supporting bimetal-based electrode material is of a core-shell structure, and the core of the core-shell structure is ZnCo loaded on a foam nickel matrix 2 O 4 -ZnO, the shell of the core-shell structure being deposited on ZnCo 2 O 4 CoS at the surface of ZnO complex.
The preparation method of the self-supporting bimetallic-based electrode material comprises the following steps:
(1) Pre-treating foam nickel;
(2) In-situ growth of Zn on foam nickel using solvothermal method x Co 1-x (OH) 2 A precursor;
(3) Zn is added x Co 1-x (OH) 2 Calcining the precursor to obtain ZnCo 2 O 4 -ZnO；
(4) By electrodeposition in ZnCo 2 O 4 Depositing CoS on the surface of ZnO@C to obtain ZnCo 2 O 4 -zno@c@cos composite material.
Wherein in the step (3), zn is added x Co 1-x (OH) 2 Before calcining the precursor, zn is added into the precursor x Co 1-x (OH) 2 Mixing the precursor with a carbon source to carry out carbon coating, and calcining to obtain the ZnCo coated with carbon 2 O 4 ZnO, designated ZnCo 2 O 4 -ZnO@C。
Wherein in the step (4), the scanning speed in the electrodeposition is 5-10 mV s -1 The electrodeposition turns are 3-9 turns.
Wherein in step (4), thiourea is added to the cobalt salt aqueous solution to be used as the electrodeposition solution; the mass ratio of the thiourea to the cobalt salt is 10:1-20:1.
Wherein the specific steps of the carbon coating are as follows: zn is added x Co 1-x (OH) 2 Immersing the precursor into glucose aqueous solution for solvothermal reaction; calcining the product obtained after the reaction; the calcination temperature is 350-400 ℃, the time is 2-3 h, and the heating rate is 2-5 ℃/min.
Wherein in the step (2), zn grows in situ on the foam nickel x Co 1-x (OH) 2 The precursor comprises cobalt salt and zinc salt, wherein the mass ratio of the cobalt salt to the zinc salt is 1: 2-2: 1.
wherein in the step (2), the reaction temperature of the solvothermal reaction is 110-130 ℃ and the reaction time is 5-8 h.
Wherein in the step (2), zn grows in situ on the foam nickel x Co 1-x (OH) 2 The raw materials for the precursor also comprise urea; the solvent is water and ethanol. Zn obtained by solvothermal method x Co 1-x (OH) 2 The precursor is spherical.
The self-supporting bimetal-based electrode material is applied to super capacitors.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: 1. ZnCo of the invention 2 O 4 -ZnO@CoS and ZnCo 2 O 4 The ZnO@C@CoS composite material is of a core-shell structure, belongs to a stable three-dimensional structure, has a relatively high specific surface area and a large number of active sites, is fully contacted with electrolyte, has enough free space inside, and can effectively relieve long-term Faraday reaction due to strain and volume expansion caused by rapid expansion; exhibit higher energy density, high, longer cycle life; 2. the preparation method has the advantages of simple process, low cost and strong repeatability; 3. the three-electrode system with the composite material as a working electrode, a platinum sheet electrode as a counter electrode and a calomel electrode as a reference electrode was described in 1.5. 1.5A g -1 At current density, the mass specific capacity is as high as 1944 and 1944F g -1 . 4. The composite material used as the positive electrode material for preparing the asymmetric super capacitor has reasonable structure and stable performance, and is 1A g -1 At current density, the mass specific capacity is up to 160F g -1 。
Drawings
FIG. 1 is ZnCo obtained in example 2 2 O 4 -ZnO、ZnCo 2 O 4 -ZnO@C、ZnCo 2 O 4 -X-ray diffraction pattern of zno@c@cos material;
FIG. 2 is ZnCo obtained in example 2 2 O 4 -a scanning electron microscope image of zno@c@cos material;
FIG. 3 is ZnCo obtained in example 2 2 O 4 Transmission electron microscopy of zno@c@cos material;
FIG. 4 is ZnCo obtained in example 2 2 O 4 -ZnO、ZnCo 2 O 4 -ZnO@C、ZnCo 2 O 4 -voltammetric characteristic curve of zno@c@cos material;
FIG. 5 is ZnCo obtained in example 2 2 O 4 -plot of voltammetric characteristics of zno@c@cos material at different sweep rates;
FIG. 6 is ZnCo obtained in example 2 2 O 4 Constant current charge and discharge of ZnO@C@CoS material under different current densitiesAn electrical curve;
FIG. 7 shows ZnCo obtained in example 2 2 O 4 -a plot of volt-ampere characteristics of zno@c@cos material applied in an asymmetric supercapacitor;
FIG. 8 is ZnCo obtained in example 1 2 O 4 Constant current charge-discharge curves of the ZnO@CoS composite material at different current densities.
Detailed Description
The invention is described in further detail below with reference to the drawings.
Example 1
Self-supporting ZnCo 2 O 4 The preparation method of the ZnO@CoS composite material comprises the following steps:
(1) Pretreatment of foam nickel:
in order of 3mol L -1 Ultrasonic cleaning is carried out on the foam nickel by taking dilute hydrochloric acid, deionized water and absolute ethyl alcohol as cleaning agents, and finally vacuum drying is carried out for 12 hours at 60 ℃ to obtain the pretreated foam nickel;
(2) Dissolving 1.5mmol of cobalt nitrate hexahydrate and 1.5mmol of zinc nitrate hexahydrate into 20mL of deionized water and 5mL of absolute ethyl alcohol by a solvothermal method, adding 4mmol of urea, stirring to obtain a pink uniform solution, transferring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the pretreated foam nickel obtained in the step (1), sealing the reaction kettle, placing into a baking oven for reacting at 130 ℃ for 5 hours, naturally cooling to room temperature, washing the foam nickel by sequentially using the deionized water and the absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain Zn-grown surface x Co 1-x (OH) 2 Foam nickel of the precursor;
(3) Growing Zn on the surface x Co 1-x (OH) 2 Placing the foam nickel of the precursor into a tube furnace, and calcining at 400 ℃ for 2 hours to obtain ZnCo 2 O 4 -ZnO；
(4) 20mmol of thiourea were added to a mass concentration of 0.1mol L -1 In a cobalt chloride hexahydrate aqueous solution, uniformly stirring and then using the solution as an electrodeposition solution; electrodepositing CoS nanoplates in a three electrode system using an electrochemical workstation, wherein ZnCo is grown 2 O 4 The foam nickel of ZnO is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, a CV technology is used for electrodepositing CoS nano sheet, and the scanning rate is 5mV s -1 The electro-deposition turns are 6 turns, the voltage range is-1.2-0.2V, the electro-deposition is followed by washing with deionized water and absolute ethyl alcohol, vacuum drying is carried out for 12 hours at 60 ℃ to obtain ZnCo 2 O 4 -zno@cos composite material.
Example 2
On the basis of example 1, the difference from example 1 is that:
in the step (3), zn grows on the surface of the glass bottle with high temperature resistance x Co 1-x (OH) 2 The mass concentration of the foam nickel put-in substance of the precursor is 0.05mol L -1 Placing the mixture in a glucose aqueous solution in a baking oven in a sealing way, reacting for 8 hours at 85 ℃, and cooling to room temperature; placing the wet foam nickel into a tubular furnace, calcining for 2 hours at 400 ℃ to finish the carbonization step to obtain ZnCo 2 O 4 -zno@c composite material;
in step (4), znCo is grown 2 O 4 Foam nickel of-ZnO@C is used as a working electrode to obtain ZnCo 2 O 4 -zno@c@cos-6 composite material.
Example 3
On the basis of example 2, unlike example 2, in step (3), the reaction temperature in the oven was 100℃and the reaction time was 6 hours.
Example 4
On the basis of example 2, in step (4), the electrodeposition number of turns was 3, unlike example 2, to obtain ZnCo 2 O 4 -zno@c@cos-3 composite material.
Example 5
On the basis of example 2, in step (4), the number of electrodeposited turns was 9, unlike example 2, to obtain ZnCo 2 O 4 -zno@c@cos-9 composite material.
Example 6
On the basis of example 2, unlike example 2, in step (4), the amount of the substance of the aqueous cobalt chloride hexahydrate solution was concentratedDegree of refraction of 0.05mol L -1 The scanning rate is 10mV s -1 。
Example 7
On the basis of example 2, the difference from example 2 is that: in step (2), cobalt nitrate hexahydrate was 1mmol, and zinc nitrate hexahydrate was 2mmol.
Example 8
On the basis of example 2, the difference from example 2 is that: in step (2), cobalt nitrate hexahydrate was 2mmol, and zinc nitrate hexahydrate was 1mmol.
As shown in FIG. 1, wherein line a in FIG. 1 is ZnCo prepared in step (3) of example 1 2 O 4 X-ray diffraction spectrum of ZnO, line b in FIG. 1 is ZnCo prepared in step (3) of example 2 2 O 4 X-ray diffraction pattern of-ZnO@C, line c in FIG. 1 is ZnCo obtained in step (4) of example 2 2 O 4 X-ray diffraction pattern of ZnO@C@CoS. As can be seen from FIG. 1, no diffraction peak of carbon appears in line b, no diffraction peak of CoS appears in line c, but ZnCo compared with line a 2 O 4 And the diffraction peak of ZnO was shifted to the left, indicating that both the newly formed carbon and CoS were amorphous structures.
As shown in FIGS. 2 and 3, znCo obtained in example 2 2 O 4 Scanning electron microscope image and transmission electron microscope image of-ZnO@C@CoS composite material, as can be seen from FIG. 2, znCo 2 O 4 The ZnO@C@CoS composite material is in a spherical shape, the diameter of the composite material is about 15 mu m, and the surfaces of the microspheres are mutually connected CoS nano sheets; as can be seen from fig. 3, nanowires and nanoplatelets are present in the composite material, wherein the CoS nanoplatelets are amorphous in structure and porous in structure.
As shown in FIG. 4, lines 1, 2 and 3 in FIG. 4 are ZnCo obtained in example 2 2 O 4 -ZnO、ZnCo 2 O 4 -ZnO@C、ZnCo 2 O 4 ZnO@C@CoS serving as working electrode and sweeping speed of 10mV s in a three-electrode system -1 Cyclic voltammetry characteristic under conditions; as can be seen, znCo 2 O 4 The cyclic voltammetric characteristic of ZnO@C@CoS has a pair of distinct redox peaks and a maximum closureAnd (5) the total area.
FIG. 5 is ZnCo obtained in example 2 at different sweep rates 2 O 4 Voltammogram of the ZnO@C@CoS composite, line 1 in FIG. 5, scans at a speed of 5mV s -1 The scan speed of line 2 was 10mV s -1 The scan speed of line 3 was 20mV s -1 The scan speed of line 4 was 30mV s -1 The scanning speed of line 5 was 50mV s -1 The method comprises the steps of carrying out a first treatment on the surface of the It can be seen that ZnCo as the scanning rate increases 2 O 4 The voltammetric characteristic curve of the ZnO@C@CoS composite material still keeps a good shape, and has good rate capability.
FIG. 6 is ZnCo obtained in example 2 at different current densities 2 O 4 Constant current charge-discharge curves for the ZnO@C@CoS composite material, lines 1, 2, 3, 4, 5, 6 and 7 in FIG. 6 are current densities of 1.5, 2, 3, 5, 8, 10 and 20A g, respectively -1 Constant current charge-discharge curve; it can be seen that the constant current charge-discharge curve of the composite material has no obvious platform and good symmetry, and is 1.5. 1.5A g -1 At a specific mass capacity of 1944 and 1944F g -1 。
FIG. 7 shows ZnCo obtained in example 2 2 O 4 Voltage current characteristic curve graph of ZnO@C@CoS material applied to asymmetric supercapacitor, and scanning speed of line 1 in FIG. 7 is 5mV s -1 The scan speed of line 2 was 10mV s -1 The scan speed of line 3 was 20mV s -1 The scan speed of line 4 was 30mV s -1 The scanning speed of line 5 was 50mV s -1 The method comprises the steps of carrying out a first treatment on the surface of the It can be seen that there is no significant redox peak in the volt-ampere characteristic of the asymmetric supercapacitor, but the curve shape remains good with increasing scan rate, without significant polarization.
FIG. 8 is ZnCo obtained in example 1 at different current densities 2 O 4 Constant current charge-discharge curves for the ZnO@CoS composite material, lines 1, 2, 3, 4, 5 and 6 in FIG. 8 are current densities of 1, 2, 3, 5, 10 and 20A g, respectively -1 Constant current charge-discharge curve; as can be seen, znCo 2 O 4 The constant current charge-discharge curve of the ZnO@CoS composite material has good symmetry and is 1A g -1 At the time of mass specific capacity of 1696F g -1 。
Claims (9)
1. The preparation method of the self-supporting bimetal-based electrode material is characterized by comprising the following steps of:
(1) Pre-treating foam nickel;
(2) In-situ growth of Zn on foam nickel using solvothermal method x Co 1-x (OH) 2 A precursor;
(3) Zn is added x Co 1-x (OH) 2 Calcining the precursor to obtain ZnCo 2 O 4 -ZnO; zn is added x Co 1-x (OH) 2 Before calcining the precursor, zn is added into the precursor x Co 1-x (OH) 2 Mixing the precursor with a carbon source to carry out carbon coating, and calcining to obtain the ZnCo coated with carbon 2 O 4 ZnO, designated ZnCo 2 O 4 -ZnO@C；
(4) By electrodeposition in ZnCo 2 O 4 Depositing CoS on the surface of ZnO@C to obtain ZnCo 2 O 4 -zno@c@cos composite material.
2. The method for preparing a self-supporting bimetallic-based electrode material according to claim 1, wherein in step (4), the scanning rate in electrodeposition is 5-10 mV s -1 The electrodeposition turns are 3-9 turns.
3. The method of preparing a self-supporting bimetallic-based electrode material of claim 1, wherein in step (4), thiourea is added to an aqueous cobalt salt solution for use as an electrodeposition solution; the mass ratio of the thiourea to the cobalt salt is 10:1-20:1.
4. The method for preparing a self-supporting bimetallic-based electrode material according to claim 1, wherein the specific steps of carbon coating are as follows: zn is added x Co 1-x (OH) 2 Immersing the precursor into glucose aqueous solution for solvothermal reaction; the product obtained after the reaction is put intoCalcining; the calcination temperature is 350-400 ℃, the time is 2-3 h, and the heating rate is 2-5 ℃/min.
5. The method of preparing a self-supporting bimetallic-based electrode material of claim 1, wherein in step (2), zn is grown in situ on nickel foam x Co 1-x (OH) 2 The precursor comprises cobalt salt and zinc salt, wherein the mass ratio of the cobalt salt to the zinc salt is 1: 2-2: 1.
6. the method for preparing a self-supporting bimetallic electrode material according to claim 1, wherein in the step (2), the solvothermal reaction temperature is 110-130 ℃ and the reaction time is 5-8 h.
7. The method of preparing a self-supporting bimetallic-based electrode material of claim 1, wherein in step (2), zn is grown in situ on nickel foam x Co 1-x (OH) 2 The raw materials for the precursor also comprise urea; the solvent is water and ethanol.
8. The self-supporting bimetallic electrode material prepared by the method of claim 1, wherein the self-supporting bimetallic electrode material is of a core-shell structure, and the core of the core-shell structure is ZnCo loaded on a foam nickel matrix 2 O 4 -ZnO, the shell of the core-shell structure being deposited on ZnCo 2 O 4 CoS at the surface of ZnO complex.
9. Use of a self-supporting bimetallic-based electrode material prepared by the method of claim 1 in a supercapacitor.
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