CN111261419A - Cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material and preparation method and application thereof - Google Patents
Cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material and preparation method and application thereof Download PDFInfo
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 100
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- 239000004744 fabric Substances 0.000 claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 239000002070 nanowire Substances 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 30
- KVAWXPKAHCGHHN-UHFFFAOYSA-J [Mo](O)(O)(O)O.[Ni] Chemical compound [Mo](O)(O)(O)O.[Ni] KVAWXPKAHCGHHN-UHFFFAOYSA-J 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000004073 vulcanization Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 56
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 40
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 20
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 20
- 229960004011 methenamine Drugs 0.000 claims description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 20
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 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 10
- 235000015393 sodium molybdate Nutrition 0.000 claims description 10
- 239000011684 sodium molybdate Substances 0.000 claims description 10
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 239000000463 material Substances 0.000 description 30
- 239000003990 capacitor Substances 0.000 description 19
- -1 transition metal sulfide Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000007600 charging Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
-
- 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
Abstract
The invention discloses a cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material, which takes carbon cloth or foamed nickel as a substrate, wherein a cobalt hydroxide nanowire array is loaded on the substrate, a nickel-molybdenum hydroxide nanosheet array grows on the surface of a cobalt hydroxide nanowire in situ, and the nickel-molybdenum hydroxide nanosheet array is converted into a nickel-molybdenum sulfide nanosheet array through vulcanization treatment. The invention also discloses a preparation method and application of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material, the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material is synthesized by combining a simple two-step hydrothermal method with vulcanization treatment, the prepared composite material has high specific capacity and good cycling stability, and has good application value in the aspect of energy storage, and the raw materials are easy to obtain, the equipment cost is low, the operation is simple, and the method is suitable for industrial batch production.
Description
Technical Field
The invention relates to preparation of a capacitor electrode material, in particular to a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material and a preparation method and application thereof.
Background
As a novel energy storage device, the super capacitor has the advantages of higher energy density, higher power density, higher cycling stability and the like compared with the conventional energy storage element, and is widely applied to the fields of electric automobiles, portable electronic equipment, high-power supplies and the like. According to the energy storage mechanism, the super capacitor can be classified into an electric double layer capacitor and a faraday capacitor, wherein the faraday capacitor has higher specific capacity and greater development potential than the electric double layer capacitor. The faradaic super capacitor electrode materials are currently researched more as transition metal oxides, transition metal hydroxides, conductive polymer materials and the like. Among them, the transition metal oxide/hydroxide composite material is particularly concerned because of its advantages of low cost, good redox activity, high theoretical specific capacitance, etc., but poor cycle stability is a key problem that needs to be solved urgently at present. Therefore, how to improve the rate capability and the cycling stability of the electrode material while maintaining the high specific capacity of the electrode material is one of the research hotspots of the current electrode material of the super capacitor.
Researches find that the transition metal sulfide not only has better performances in the aspects of electron transport capacity and mechanical thermal stability, but also can provide a more flexible structure due to the fact that the electronegativity of the sulfur ions is lower than that of the oxygen ions, so that the transition metal sulfide has good cycle stability and rate capability, and is very suitable to be used as an electrode material of an energy storage element. Although the hydrothermal method is reported to prepare cobalt hydroxide materials or nickel molybdenum sulfide materials as electrodes of super capacitors, the single cobalt hydroxide material as an electrode has poor cycle stability, and the single nickel molybdenum sulfide material as an electrode has the defects of low specific capacitance value and the like.
CN106340398A discloses a method for preparing a composite material of nickel cobalt hydroxide and molybdenum oxide for an electrode material of a super capacitor, which utilizes a hydrothermal method to synthesize a composite nano material of nickel cobalt hydroxide and molybdenum oxide on a carbon cloth or a foamed nickel substrate in one step, and can be directly used as an electrode material of a super capacitor, and the method has the advantages of simple process flow, low cost, high production efficiency, and suitability for large-scale industrial production. However, the prepared nickel-cobalt hydroxide and molybdenum oxide composite material is of a nanosheet structure directly grown on a substrate, and the specific surface area is limited, so that the comprehensive electrochemical performance of the material is not favorably improved. And the conductivity and electrochemical activity of hydroxide or oxide materials are theoretically poorer than those of sulfide materials, so that the corresponding device has the defect of insufficient long-term stability in the using process, and the application range of the device is limited.
Disclosure of Invention
The invention aims to provide a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material and a preparation method and application thereof.
The cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material takes carbon cloth or foamed nickel as a substrate, a cobalt hydroxide nanowire array is loaded on the substrate, a nickel-molybdenum hydroxide nanosheet array grows on the surface of the cobalt hydroxide nanowire in situ, and the nickel-molybdenum hydroxide nanosheet array is converted into a nickel-molybdenum sulfide nanosheet array through vulcanization treatment.
A preparation method of a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material comprises the following steps:
1) dissolving cobalt nitrate, hexamethylenetetramine and urea in deionized water to obtain a mixed solution A, wherein the concentration of the cobalt nitrate in the mixed solution is 0.05-0.15 mol/L, the concentration of the hexamethylenetetramine in the mixed solution is 6-8 g/L, and the concentration of the urea in the mixed solution is 2-4 g/L, then adding a carbon cloth or a foamed nickel substrate into the mixed solution A to perform a first hydrothermal reaction, cooling to room temperature, washing and drying the obtained reaction product to obtain a carbon cloth or foamed nickel loaded cobalt hydroxide nanowire array;
2) dissolving nickel nitrate and sodium molybdate in deionized water, and then adding hexamethylene tetramine and urea to obtain a mixed solution B, wherein the concentration of nickel nitrate in the mixed solution is 0.05-0.15 mol/L, the concentration of sodium molybdate in the mixed solution is 0.2-0.3 mol/L, the concentration of hexamethylene tetramine in the mixed solution is 6-8 g/L, and the concentration of urea in the mixed solution is 2-4 g/L, then adding the carbon cloth or foamed nickel loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction, growing a nickel molybdenum hydroxide nanosheet array on the surface of the cobalt hydroxide nanowire in situ, cooling to room temperature, washing and drying the obtained reaction product to obtain a carbon cloth or foamed nickel loaded cobalt hydroxide and nickel molybdenum hydroxide composite material;
3) dissolving sodium sulfide in deionized water to form a sodium sulfide solution, immersing the carbon cloth or foamed nickel loaded cobalt hydroxide and nickel molybdenum hydroxide composite material prepared in the step 2) into the sodium sulfide solution, carrying out vulcanization treatment for 10-15 h, converting the nickel molybdenum hydroxide nanosheet array into a nickel molybdenum sulfide nanosheet array through vulcanization treatment, washing and drying the obtained product, and thus obtaining the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material.
Further, the temperature of the first hydrothermal reaction in the step 1) is 120-180 ℃, and the reaction time is 2-6 hours.
Further, the temperature of the second hydrothermal reaction in the step 2) is 120-180 ℃, and the reaction time is 2-8 hours.
Further, the mass fraction of the sodium sulfide in the solution in the step 3) is 30-40%.
Further, in the step 1), the concentration of cobalt nitrate in the mixed solution is 0.1mol/L, the concentration of hexamethylenetetramine in the mixed solution is 7g/L, and the concentration of urea in the mixed solution is 3 g/L;
in the step 2), the concentration of nickel nitrate in the mixed solution is 0.1mol/L, the concentration of sodium molybdate in the mixed solution is 0.27mol/L, the concentration of hexamethylenetetramine in the mixed solution is 7g/L, and the concentration of urea in the mixed solution is 3 g/L.
The application of the cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material or the cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material obtained by any one of the preparation methods in a supercapacitor can be expanded and applied to lithium-sulfur batteries.
Compared with the prior art, the invention has the following beneficial effects.
1. The cobalt hydroxide and nickel molybdenum sulfide composite material provided by the invention directly grows on a carbon cloth or a foamed nickel substrate, avoids the use of a polymer adhesive or a conductive additive, ensures rapid electron transmission capability and good structural integrity and coating property, and is beneficial to obtaining excellent stability of an electrode material. The cobalt hydroxide is in a nanometer linear structure, the nickel molybdenum sulfide is in a nanometer flaky structure, and the nickel molybdenum sulfide nanosheets are connected in a staggered mode to grow the cobalt hydroxide nanowires to form a composite nanometer structure. And the nickel molybdenum sulfide nanosheet has an open structure, so that the specific surface area of the material can be increased, the effective utilization degree of active substances is improved, and the electrode material can obtain higher specific capacity.
2. The cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material is synthesized by combining a simple two-step hydrothermal method with vulcanization treatment, and the prepared composite material has high specific capacity, good circulation stability and good application value in the aspect of energy storage.
3. The preparation method has the advantages of easily available raw materials, low equipment cost and simple operation, is suitable for industrial production, and can be popularized and used for synthesizing other hydroxide and sulfide compounded supercapacitor electrode materials.
Drawings
FIG. 1 is SEM images of different products in the preparation process of the invention, wherein a and b are carbon cloth-supported cobalt hydroxide nanowire arrays, c and d are carbon cloth-supported cobalt hydroxide and nickel molybdenum hydroxide composite materials, and e and f are carbon cloth-supported cobalt hydroxide and nickel molybdenum sulfide composite materials;
FIG. 2 is a TEM image of the carbon cloth-supported cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first example;
FIG. 3 is an SEM image and corresponding EDS image of Co, O, Mo, Ni and S elements in the composite material of cobalt hydroxide and nickel molybdenum sulfide supported on carbon cloth prepared in the first example;
FIG. 4 is a cyclic voltammogram of the carbon cloth supported cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first example at different scanning rates; the scanning speed of g is 10mv/s, the scanning speed of h is 20mv/s, the scanning speed of i is 30mv/s, and the scanning speed of j is 50 mv/s;
FIG. 5 is a constant current charging and discharging curve diagram of the composite material of cobalt hydroxide and nickel molybdenum sulfide prepared in the first embodiment of the present invention under different current densities;
FIG. 6 is a graph showing the relative variation of specific capacitance with the number of charge and discharge times of the cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first embodiment of the present invention during 2000 charge and discharge cycles;
FIG. 7 is a graph showing the relative variation of specific capacitance value of the asymmetric aqueous two-electrode capacitor device composed of the cobalt hydroxide and nickel molybdenum sulfide composite material and activated carbon according to the first embodiment with respect to the number of charging and discharging operations;
FIG. 8 is a constant current charging and discharging curve diagram of the asymmetric aqueous two-electrode capacitor device composed of the cobalt hydroxide and nickel molybdenum sulfide composite material and activated carbon prepared in the first example under different current densities.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
The first embodiment is a preparation method of a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material, which comprises the following steps:
1) the carbon cloth substrate is cut into pieces with the thickness of 0.36mm and the surface area of 3 multiplied by 3cm2Ultrasonic washing with ethanol and deionized water for 15 min, and drying in a drying oven; 3mmol of cobalt nitrate, 0.21g of hexamethylenetetramine and 0.09g of urea are dissolved in 30mL of deionized water, and a uniform clear solution, namely a mixed solution A, is formed under a magnetic stirrer. And transferring the washed carbon cloth substrate and the mixed solution A together to a 50mL polytetrafluoroethylene lining, and loading the lining into a stainless steel autoclave for a first hydrothermal reaction at 120 ℃ for 4 hours. After the reaction is finished and the temperature is cooled to room temperature, the carbon cloth substrate is taken out and sequentially arrangedAnd ultrasonically cleaning the carbon cloth by using ethanol and deionized water, and drying the carbon cloth at the temperature of 60 ℃ for 12 hours to obtain the carbon cloth loaded cobalt hydroxide nanowire array. Performing SEM morphology analysis on the obtained product, and referring to fig. 1a and fig. 1b, SEM images of the material under the conditions of low magnification and high magnification are respectively shown, the obtained cobalt hydroxide material is a nanowire material, the nanowire materials are mutually connected in a staggered manner and uniformly and densely covered on each fiber of the carbon cloth, the length of each nanowire is about 10 micrometers, and the surface of each nanowire is smooth, the diameter of each nanowire is uniform and is between 40 and 100 nm.
2) Dissolving 3mmol of nickel nitrate and 8mmol of sodium molybdate in 30mL of deionized water, adding 0.21g of hexamethylenetetramine and 0.09g of urea, stirring to obtain a uniform mixed solution B, then transferring the mixed solution B into a 50mL polytetrafluoroethylene lining in a high-pressure reaction kettle, adding the carbon cloth loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction at the reaction temperature of 120 ℃ for 4 hours, naturally cooling to room temperature, taking out the carbon cloth substrate, washing with ethanol and deionized water, and drying at the temperature of 60 ℃ for 10 hours to obtain the carbon cloth loaded cobalt hydroxide and nickel molybdenum hydroxide composite material. The obtained product was subjected to SEM morphology analysis, referring to fig. 1c and fig. 1d, which show SEM images of the material under low magnification and high magnification conditions, respectively, and the SEM image at low magnification, i.e. fig. 1c, shows the wire-like material still loaded with carbon cloth at this time, and overall, similar to the morphology shown in fig. 1a, the length of the wire-like material still remained around 10 μm. The SEM image at high power, fig. 1d, further shows that the linear material at this time has a finer structure, which is represented by densely and uniformly growing a layer of nano-sheet material on the original cobalt hydroxide nanowire to form a composite material of cobalt hydroxide nanowire and nickel molybdenum hydroxide nanosheet, so that the diameter of the overall linear material is increased to 200-300 nm, wherein the size of the nanosheet material is about 100nm, the thickness is extremely thin, and is estimated to be about 4-8 nm.
3) Dissolving 33g of sodium sulfide in 67g of deionized water to obtain a sodium sulfide solution with the mass fraction of 33%, then immersing the carbon cloth loaded cobalt hydroxide and nickel molybdenum hydroxide composite material prepared in the step 2) into the prepared sodium sulfide solution, carrying out vulcanization treatment for 12 hours, taking out the obtained product, washing the product with ethanol and deionized water, and then drying the product at the temperature of 60 ℃ for 10 hours to obtain the carbon cloth loaded cobalt hydroxide and nickel molybdenum sulfide composite material, namely the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material. The obtained product was subjected to SEM morphology analysis, referring to fig. 1e and fig. 1f, which show SEM images of the material under low magnification and high magnification conditions, respectively, and the SEM image at low magnification, fig. 1e, shows the wire-like material still loaded with carbon cloth as a whole at this time, and the length of the wire-like material was still maintained at about 10 μm, similar to the morphology shown in fig. 1a and fig. 1 c. The SEM image at high magnification, fig. 1f, further shows that the linear material at this time also has a fine structure, and shows a composite material of nanowires and nanosheets similar to fig. 1d, the diameter of the overall linear material is further increased to 300-400 nm, wherein the size of the nanosheet material is slightly increased to about 150nm, and the thickness is estimated to be about 5-10 nm. The composite material of the carbon cloth loaded cobalt hydroxide nanowire and the nickel molybdenum sulfide nanosheet can remarkably increase the specific surface area of the material, can fully contact with electrolyte, and is beneficial to improving the capacitance performance of the material.
The second embodiment is a preparation method of a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material, which comprises the following steps:
1) the foamed nickel substrate was sheared to a thickness of 0.5mm and a surface area of 3X 3cm2Ultrasonic washing with ethanol and deionized water for 15 min, and drying in a drying oven; 1.5mmol of cobalt nitrate, 0.18g of hexamethylenetetramine and 0.06g of urea are dissolved in 30mL of deionized water to form a uniform clear solution, namely a mixed solution A, under a magnetic stirrer. And transferring the washed foam nickel substrate and the mixed solution A together to a 50mL polytetrafluoroethylene lining, and loading the lining into a stainless steel autoclave for a first hydrothermal reaction at 160 ℃ for 6 hours. And after the reaction is finished and the temperature is cooled to room temperature, taking out the foamed nickel substrate, sequentially carrying out ultrasonic cleaning by using ethanol and deionized water, and then drying for 12h at the temperature of 60 ℃ to obtain the foamed nickel loaded cobalt hydroxide nanowire array.
2) Dissolving 1.5mmol of nickel nitrate and 6mmol of sodium molybdate in 30mL of deionized water, adding 0.18g of hexamethylenetetramine and 0.06g of urea, stirring to obtain a uniform mixed solution B, then transferring the mixed solution B into a 50mL polytetrafluoroethylene lining in a high-pressure reaction kettle, adding the foamed nickel-loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction at 160 ℃ for 6 hours, naturally cooling to room temperature, taking out the foamed nickel substrate, washing with ethanol and deionized water, and drying at 60 ℃ for 10 hours to obtain the foamed nickel-loaded cobalt hydroxide and nickel molybdenum hydroxide composite material.
3) Dissolving 30g of sodium sulfide in 70g of deionized water to obtain a sodium sulfide solution with the mass fraction of 30%, then immersing the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum hydroxide composite material prepared in the step 2) into the prepared sodium sulfide solution, carrying out vulcanization treatment for 15h, taking out the foamed nickel substrate, washing the foamed nickel substrate with ethanol and deionized water, and then drying the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum sulfide composite material for 10h at the temperature of 60 ℃ to obtain the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum sulfide composite material, namely the cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material.
In a third embodiment, a method for preparing a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material comprises the following steps:
1) the carbon cloth substrate is cut into pieces with a thickness of 0.5mm and a surface area of 3 × 3cm2Ultrasonic washing with ethanol and deionized water for 15 min, and drying in a drying oven; 4.5mmol of cobalt nitrate, 0.18g of hexamethylenetetramine and 0.12g of urea were dissolved in 30mL of deionized water to form a uniform clear solution, i.e., a mixed solution A, under a magnetic stirrer. And transferring the washed carbon cloth substrate and the mixed solution A together to a 50mL polytetrafluoroethylene lining, and loading the lining into a stainless steel autoclave for a first hydrothermal reaction at 120 ℃ for 2 hours. And after the reaction is finished and the temperature is cooled to room temperature, taking out the carbon cloth substrate, sequentially carrying out ultrasonic cleaning by using ethanol and deionized water, and then drying for 12h at the temperature of 60 ℃ to obtain the carbon cloth loaded cobalt hydroxide nanowire array.
2) Dissolving 4.5mmol of nickel nitrate and 9mmol of sodium molybdate in 30mL of deionized water, adding 0.18g of hexamethylenetetramine and 0.12g of urea, stirring to obtain a uniform mixed solution B, then transferring the mixed solution B into a 50mL polytetrafluoroethylene lining in a high-pressure reaction kettle, adding the carbon cloth loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction at the reaction temperature of 120 ℃ for 2h, naturally cooling to room temperature, taking out the carbon cloth substrate, washing with ethanol and deionized water, and drying at the temperature of 60 ℃ for 10h to obtain the carbon cloth loaded cobalt hydroxide and nickel molybdenum hydroxide composite material.
3) Dissolving 40g of sodium sulfide in 60g of deionized water to obtain a sodium sulfide solution with the mass fraction of 40%, then immersing the carbon cloth loaded cobalt hydroxide and nickel molybdenum hydroxide composite material prepared in the step 2) into the prepared sodium sulfide solution, carrying out vulcanization treatment for 10 hours, taking out the carbon cloth substrate, washing the carbon cloth substrate with ethanol and deionized water, and then drying the carbon cloth substrate for 10 hours at the temperature of 60 ℃ to obtain the carbon cloth loaded cobalt hydroxide and nickel molybdenum sulfide composite material, namely the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material.
The embodiment four is a preparation method of a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material, which comprises the following steps:
1) the foamed nickel substrate was sheared to a thickness of 0.3mm and a surface area of 3X 3cm2Ultrasonic washing with ethanol and deionized water for 15 min, and drying in a drying oven; 3mmol of cobalt nitrate, 0.21g of hexamethylenetetramine and 0.09g of urea are dissolved in 30mL of deionized water, and a uniform clear solution, namely a mixed solution A, is formed under a magnetic stirrer. And transferring the washed foam nickel substrate and the mixed solution A together to a 50mL polytetrafluoroethylene lining, and loading the lining into a stainless steel autoclave for a first hydrothermal reaction at 180 ℃ for 4 h. And after the reaction is finished and the temperature is cooled to room temperature, taking out the foamed nickel substrate, sequentially carrying out ultrasonic cleaning by using ethanol and deionized water, and then drying for 12h at the temperature of 60 ℃ to obtain the foamed nickel loaded cobalt hydroxide nanowire array.
2) Dissolving 3mmol of nickel nitrate and 8mmol of sodium molybdate in 30mL of deionized water, adding 0.21g of hexamethylenetetramine and 0.09g of urea, stirring to obtain a uniform mixed solution B, then transferring the mixed solution B into a 50mL polytetrafluoroethylene lining in a high-pressure reaction kettle, adding the foamed nickel-loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction at the reaction temperature of 180 ℃ for 4 hours, naturally cooling to room temperature, taking out the foamed nickel substrate, washing with ethanol and deionized water in sequence, and drying at the temperature of 60 ℃ for 10 hours to obtain the foamed nickel-loaded cobalt hydroxide and nickel molybdenum hydroxide composite material.
3) Dissolving 33g of sodium sulfide in 67g of deionized water to obtain a sodium sulfide solution with the mass fraction of 33%, then immersing the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum hydroxide composite material prepared in the step 2) into the prepared sodium sulfide solution, carrying out vulcanization treatment for 15 hours, taking out the foamed nickel substrate, washing the foamed nickel substrate with ethanol and deionized water, and then drying the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum sulfide composite material for 10 hours at the temperature of 60 ℃ to obtain the foamed nickel-loaded cobalt hydroxide and nickel-molybdenum sulfide composite material, namely the cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material.
Example five, the product obtained in example one was analyzed for performance testing.
The carbon cloth-supported cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first embodiment is analyzed by using a transmission electron microscope, and as a result, referring to fig. 2, a low-power TEM image shows that a small segment of linear material is formed by uniformly coating nickel molybdenum sulfide nanosheets, the overall diameter is about 400nm, the nanosheets are arranged in a staggered manner, and a plurality of small gaps are formed between the nanosheets, so that the material is in full contact with an electrolyte. The high-power TEM image proves that the thickness of the nano sheets is between 5 and 10nm, and the nano sheets have a polycrystalline structure consisting of a large number of particles.
The carbon cloth-supported cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first example was analyzed by an energy spectrometer attached to a scanning electron microscope, and the result is shown in fig. 3, which shows that the prepared composite material mainly consists of Co, O, Ni, Mo, and S elements, and is uniformly dispersed in the structure, indicating that the finally synthesized material is a cobalt hydroxide and nickel molybdenum sulfide composite material.
The cyclic voltammetry curves of the carbon cloth loaded cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first embodiment at different scanning rates are tested by adopting an electrochemical workstation, a three-electrode system is adopted for testing, the working electrode is a cut product prepared in the first embodiment with the thickness of 10mm multiplied by 10mm, the counter electrode is a platinum sheet, the reference electrode is a silver/silver chloride electrode, and the electrolyte is 2mol/L KOH, so that the result is shown in figure 4, obvious oxidation peaks and reduction peaks can be seen from the cyclic voltammetry curves, and the peak values of the corresponding oxidation peaks and reduction peaks are increased along with the increase of the scanning rate, which shows that a good reversible oxidation-reduction reaction occurs on the electrode, and the prepared carbon cloth loaded cobalt hydroxide and nickel molybdenum sulfide composite material has a Faraday quasi-capacitance characteristic.
Referring to fig. 5, the charging and discharging behavior of the constant current charging and discharging curve of the cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first embodiment under different current densities also shows obvious pseudocapacitance characteristics, and the calculation shows that the specific capacitance at 1A/g is the maximum and reaches 2229F/g; when the discharge current density is respectively 2A/g, 3A/g, 5A/g and 10A/g, the corresponding specific capacitance values are respectively 2094F/g, 1989F/g, 1797F/g and 1436F/g. When the current density is increased from 1A/g to 10A/g, the specific capacity is attenuated along with the increase of the current density, and the specific capacity retention rate is 64 percent, which indicates that the prepared composite material of nickel-cobalt hydroxide and molybdenum oxide has better high-current rate capacity performance under high-current density.
By analyzing the relative change graph of the specific capacitance value of the cobalt hydroxide and nickel molybdenum sulfide composite material prepared in the first embodiment in 2000 times of charging and discharging, the result is shown in fig. 6, which shows that the specific capacitance value is slightly reduced along with the increase of the charging and discharging times, and the cobalt hydroxide and nickel molybdenum sulfide composite material can still keep more than 84% of the initial specific capacitance value after 2000 times of charging and discharging, and shows that the prepared cobalt hydroxide and nickel molybdenum sulfide composite material has better cycle stability.
In a sixth embodiment, in the application of the cobalt hydroxide/nickel-molybdenum sulfide composite supercapacitor electrode material obtained in the first embodiment in a supercapacitor, an asymmetric aqueous two-electrode capacitor device is composed of the cobalt hydroxide, nickel-molybdenum sulfide composite material prepared in the first embodiment and activated carbon, and charge and discharge analysis is performed on the obtained two-electrode capacitor device, the current density is 4A/g, and the cycle number is 5000 times, as shown in fig. 7, the specific capacitance value of the two-electrode capacitor device is slightly attenuated at the beginning and then slightly increased, and after 5000 cycles of testing, the stability of the two-electrode capacitor device is still maintained at about 100%, and excellent long-term stability is shown.
Referring to fig. 8, a constant current charging and discharging curve diagram of the two-electrode capacitor device under different current densities is shown. The calculation shows that the specific capacitance is maximum at 1A/g and reaches 107.4F/g; when the discharge current density is respectively 2A/g, 3A/g and 4A/g, the corresponding specific capacitance values are respectively 84.5F/g, 67.7F/g and 51.3F/g. Further calculations showed that the highest energy density of the device was 59.47 Wh/kg when the power density was 1000W/kg. Under the high power density of 4000W/kg, the fine energy density of 28.37 Wh/kg can be still obtained, and the result shows that the prepared cobalt hydroxide and nickel molybdenum sulfide composite material has higher practical application value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material is characterized in that: the method comprises the steps of taking carbon cloth or foamed nickel as a substrate, loading a cobalt hydroxide nanowire array on the substrate, wherein a nickel-molybdenum sulfide nanosheet array is arranged on the surface of the cobalt hydroxide nanowire, and the nickel-molybdenum sulfide nanosheet array is converted into a nickel-molybdenum sulfide nanosheet array through in-situ growth of the nickel-molybdenum hydroxide nanosheet array on the surface of the cobalt hydroxide nanowire and vulcanization treatment.
2. A preparation method of a cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material is characterized by comprising the following steps:
1) dissolving cobalt nitrate, hexamethylenetetramine and urea in deionized water to obtain a mixed solution A, wherein the concentration of the cobalt nitrate in the mixed solution is 0.05-0.15 mol/L, the concentration of the hexamethylenetetramine in the mixed solution is 6-8 g/L, and the concentration of the urea in the mixed solution is 2-4 g/L, then adding a carbon cloth or a foamed nickel substrate into the mixed solution A to perform a first hydrothermal reaction, cooling to room temperature, washing and drying the obtained reaction product to obtain a carbon cloth or foamed nickel loaded cobalt hydroxide nanowire array;
2) dissolving nickel nitrate and sodium molybdate in deionized water, and then adding hexamethylene tetramine and urea to obtain a mixed solution B, wherein the concentration of nickel nitrate in the mixed solution is 0.05-0.15 mol/L, the concentration of sodium molybdate in the mixed solution is 0.2-0.3 mol/L, the concentration of hexamethylene tetramine in the mixed solution is 6-8 g/L, and the concentration of urea in the mixed solution is 2-4 g/L, then adding the carbon cloth or foamed nickel loaded cobalt hydroxide nanowire array prepared in the step 1) into the mixed solution B, carrying out a second hydrothermal reaction, growing a nickel molybdenum hydroxide nanosheet array on the surface of the cobalt hydroxide nanowire in situ, cooling to room temperature, washing and drying the obtained reaction product to obtain a carbon cloth or foamed nickel loaded cobalt hydroxide and nickel molybdenum hydroxide composite material;
3) dissolving sodium sulfide in deionized water to form a sodium sulfide solution, immersing the carbon cloth or foamed nickel loaded cobalt hydroxide and nickel molybdenum hydroxide composite material prepared in the step 2) into the sodium sulfide solution, carrying out vulcanization treatment for 10-15 h, converting the nickel molybdenum hydroxide nanosheet array into a nickel molybdenum sulfide nanosheet array through vulcanization treatment, washing and drying the obtained product, and thus obtaining the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material.
3. The preparation method of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material according to claim 2, characterized by comprising the following steps: the temperature of the first hydrothermal reaction in the step 1) is 120-180 ℃, and the reaction time is 2-6 h.
4. The preparation method of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material according to claim 2 or 3, characterized by comprising the following steps: the temperature of the second hydrothermal reaction in the step 2) is 120-180 ℃, and the reaction time is 2-8 h.
5. The preparation method of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material according to claim 2 or 3, characterized by comprising the following steps: the mass fraction of the sodium sulfide in the solution in the step 3) is 30-40%.
6. The preparation method of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material according to claim 2 or 3, characterized by comprising the following steps: in the step 1), the concentration of cobalt nitrate in the mixed solution is 0.1mol/L, the concentration of hexamethylenetetramine in the mixed solution is 7g/L, and the concentration of urea in the mixed solution is 3 g/L;
in the step 2), the concentration of nickel nitrate in the mixed solution is 0.1mol/L, the concentration of sodium molybdate in the mixed solution is 0.27mol/L, the concentration of hexamethylenetetramine in the mixed solution is 7g/L, and the concentration of urea in the mixed solution is 3 g/L.
7. An application of the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material according to claim 1 or the cobalt hydroxide/nickel molybdenum sulfide composite supercapacitor electrode material obtained according to any one of claims 2 to 6 in a supercapacitor.
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