CN109346330B - Flexible cotton cloth loaded with metal selenide NixCo9-x-Se electrode material and preparation method and application thereof - Google Patents
Flexible cotton cloth loaded with metal selenide NixCo9-x-Se electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 239000004744 fabric Substances 0.000 title claims abstract description 44
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 42
- 229920000742 Cotton Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000758 substrate Substances 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 37
- 238000007747 plating Methods 0.000 claims abstract description 36
- 239000003990 capacitor Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 11
- 230000008313 sensitization Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 70
- 239000000463 material Substances 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 53
- 229910021641 deionized water Inorganic materials 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000011669 selenium Substances 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 29
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 17
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 17
- 230000003213 activating effect Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 230000001235 sensitizing effect Effects 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 13
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 13
- 229940038773 trisodium citrate Drugs 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 12
- 239000012279 sodium borohydride Substances 0.000 claims description 12
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 239000001119 stannous chloride Substances 0.000 claims description 10
- 235000011150 stannous chloride Nutrition 0.000 claims description 10
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229940053662 nickel sulfate Drugs 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 238000005238 degreasing Methods 0.000 claims description 6
- 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 claims description 6
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 239000002131 composite material Substances 0.000 description 7
- 229910017709 Ni Co Inorganic materials 0.000 description 5
- 229910003267 Ni-Co Inorganic materials 0.000 description 5
- 229910003262 Ni‐Co Inorganic materials 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 239000002114 nanocomposite Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemically Coating (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to a flexible cotton cloth loaded with metal selenide NixCo9‑x-Se supercapacitor electrode material and electrode thereofA preparation method and application. The flexible cotton cloth of the invention loads metal selenide NixCo9‑x-Se supercapacitor electrode material, said NixCo9‑xIn the-Se, x is more than or equal to 0 and less than or equal to 9, x is preferably 4.5 or 9, the electrode material is prepared by taking pure cotton cloth as a substrate and sequentially performing oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on the substrate. Ni prepared by the inventionxCo9‑xThe Se electrode material is applied to a super capacitor, and test results show that the electrode material provided by the invention has high-efficiency pseudocapacitance performance and specific capacitance, particularly the nickel-cobalt ratio is 1: the electrochemical performance of the electrode material prepared under the condition of 1 is the most excellent, and the current density of the electrode material is 2mA cm‑2Under the condition, the specific capacitance can be as high as 8.85F cm‑2。
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials of supercapacitors, in particular to a flexible cotton cloth loaded metal selenide NixCo9-xAn electrode material of a Se super capacitor, a preparation method and application thereof.
Background
With the rapid development of a new generation of flexible electronic industries, such as wearable portable electronic devices, implantable medical products, conformal health sensors, etc., power supply devices thereof need to be mechanically more flexible and at the same time capable of providing high energy, high power and long lifetime. Carbon cloth is widely applied to flexible electronic devices, has the advantages of high temperature resistance, corrosion resistance, electric conduction, heat transfer, small thermal expansion coefficient and the like, and has the defects of poor mechanical property, complex stress calculation during processing, high cost and the like. The nickel cloth maintains the advantages of the carbon cloth, has the properties of good flexibility and mechanical property, light weight, low cost and the like, and can be used as a substrate of a flexible supercapacitor electrode material.
The literature reports that the electrode material prepared by the bimetallic nickel-cobalt selenide NiCoSe can provide 2.33F cm-2The capacitance of the double metal selenide super capacitor is also reported in relevant documents,such as CuxMoySezHas excellent specific capacitance and stability (CN106783202A), and is three-dimensionally porous Ni0.85Se/Co9Se8The nano composite material also has good electrochemical performance (CN106057480A), and has great development potential in the field of super capacitors, but the electrochemical activity of the electrode materials is still not ideal enough, and a novel electrode material is still required to be developed to further improve the electrochemical performance of the super capacitors.
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 provides a flexible cotton cloth loaded metal selenide NixCo9-xAn electrode material of a Se super capacitor, a preparation method and application thereof.
In order to achieve the first object of the present invention, the inventor develops a flexible cotton cloth supported metal selenide Ni through a large amount of experimental researchxCo9-x-Se supercapacitor electrode material, said NixCo9-xin-Se, x is 0-9.
Furthermore, the Ni in the technical schemexCo9-xin-Se, x is preferably 4.5 or 9, and x is more preferably 4.5.
The second purpose of the invention is to provide the flexible cotton cloth loaded with metal selenide NixCo9-xThe preparation method of the electrode material of the Se super capacitor takes pure cotton cloth as a substrate, and sequentially carries out oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on the substrate, and the method specifically comprises the following steps:
(1) oil removal: the method comprises the steps of soaking a base material in degreasing liquid for 5-30 min at the temperature of 30-40 ℃, and then washing the base material with deionized water to obtain the degreased base material, wherein the degreasing liquid is an aqueous solution of triton, and the concentration of the triton in the degreasing liquid is 1-5%.
(2) Sensitization: soaking the deoiled substrate material obtained in the step (1) in a sensitizing solution for 5-30 min at the temperature of 30-40 ℃, and then washing with deionized water to obtain the sensitized substrate material, wherein the sensitizing solution is a mixed solution composed of stannous chloride and hydrochloric acid, the concentration of the stannous chloride in the sensitizing solution is 10-20 g/L, and the concentration of the hydrochloric acid is 0.1-0.2M;
(3) and (3) activation: soaking the sensitized substrate material obtained in the step (2) in an activating solution at the temperature of 30-40 ℃ for 5-20 min, and then washing with deionized water to obtain an activated substrate material, wherein the activating solution is a mixed solution composed of palladium chloride and hydrochloric acid, the concentration of the palladium chloride in the activating solution is 0.1-0.2 g/L, and the concentration of the hydrochloric acid is 0.02-0.05M;
(4) chemical nickel plating: placing the activated substrate material obtained in the step (3) into a chemical plating solution to react for 5-20 min at the temperature of 30-40 ℃, so as to plate a metal nickel layer on the surface of the substrate, wherein the chemical plating solution is a mixed solution composed of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of nickel sulfate in the chemical plating solution is 10-30 g/L, the concentration of trisodium citrate is 5-15 g/L, the concentration of sodium hypophosphite is 20-40 g/L, the concentration of ammonium chloride is 20-40 g/L, and the pH value of the chemical plating solution is 8.5-9.5;
(5) preparing a precursor: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at the temperature of 100-200 ℃ for hydrothermal reaction for 5-24 h, taking out, washing with deionized water and absolute ethyl alcohol, and drying to obtain the precursor, wherein the mixed solution is composed of any one or two of nickel chloride hexahydrate and cobalt chloride hexahydrate, urea and deionized water, and the molar ratio of the nickel chloride hexahydrate to the cobalt chloride hexahydrate is 0-9: 9-0, wherein the ratio of urea to deionized water is (10-20) mmol: (50-70) mL;
(6) selenizing: and (3) placing the precursor material prepared in the step (5) in a selenizing solution at 120-220 ℃ for hydrothermal reaction for 5-24 h, taking out, washing with deionized water and absolute ethyl alcohol, and drying to obtain the selenide, wherein the selenizing solution is composed of selenium powder, sodium borohydride, absolute ethyl alcohol and deionized water, and the molar ratio of the selenium powder to the sodium borohydride is 1: 1, the volume ratio of the selenium powder to the deionized water is 2 mmol: 50 mL.
Further, in the chemical plating solution in the step (4) of the technical scheme, the concentration of nickel sulfate is 20g/L, the concentration of trisodium citrate is 10g/L, the concentration of sodium hypophosphite is 30g/L, and the concentration of ammonium chloride is 30 g/L.
Further, the hydrothermal reaction time in the step (5) of the above technical means is preferably 10 hours.
Further, the molar ratio of the nickel chloride hexahydrate and the cobalt chloride hexahydrate in the step (5) of the technical scheme is 1: 1 or 9: 0, more preferably 1: 1.
further, in the step (5) of the technical scheme, the ratio of the urea to the deionized water is 12 mmol: 60 mL.
Further, in the step (6) of the technical scheme, the volume ratio of the absolute ethyl alcohol to the deionized water is (1-5): 50.
the third purpose of the invention is to provide the flexible cotton cloth loaded with the metal selenide Ni prepared by the methodxCo9-xApplication of Se electrode material, can be used for super capacitor.
Compared with the prior art, the flexible cotton cloth loaded with metal selenide NixCo9-xThe electrode material of the-Se super capacitor, the preparation method and the application thereof have the following beneficial effects:
(1) the invention adopts a simple hydrothermal method, and realizes Ni with different nickel-cobalt doping amounts by adjusting the composition ratio of reactants and solventxCo9-xControllable synthesis of Se electrode material, the reagent used in the method is common, cheap and low in cost; the preparation steps are simple, and the industrial production is easy to realize; the product prepared by the method has controllable shape, high purity and good crystallinity, and the synthesized Ni with different cobalt doping amountsxCo9-x-Se material can be used in supercapacitors;
(2) ni prepared by the inventionxCo9-xThe Se electrode material is applied to a super capacitor, and test results show that the electrode material of the invention has high-efficiency pseudocapacitance performance and specific capacitance,particularly, the nickel-cobalt ratio is 1: 1, the electrochemical performance of the electrode material prepared under the condition is most excellent: it has a current density of 2mA cm-2Under the condition, the specific capacitance can be as high as 8.85F cm-2；
(3) The super capacitor prepared by the electrode material has small interface internal resistance, high energy density and high pseudocapacitance, and the electrode material adopts a flexible substrate, so that the super capacitor has better processing performance compared with the traditional metal foil;
(4) the preparation method has simple process, easy operation and low cost, and is suitable for industrial large-scale production.
Drawings
FIG. 1 shows that the flexible cotton cloth of the invention is loaded with metal selenide NixCo9-xA schematic process diagram of a preparation process of the electrode material of the Se super capacitor;
fig. 2 shows that the nickel-cobalt ratio in embodiment 4 of the present invention is 1: 1, preparing an SEM image of the precursor obtained under the condition of 1 ten thousand times;
fig. 3 shows that the nickel-cobalt ratio in embodiment 4 of the present invention is 1: 1, preparing an SEM image of the precursor prepared under the condition of 1 ten thousand times after selenization treatment;
FIG. 4 shows metal selenide Ni loaded on cotton cloth prepared under different Ni-Co ratios in examples 1 to 7 of the present inventionxCo9-x-Se composite electrode at 5mV s-1A comparison plot of cyclic voltammograms at scan rate;
FIG. 5 shows metal selenide Ni loaded on cotton cloth prepared under different Ni-Co ratios in examples 1 to 7 of the present inventionxCo9-x-specific capacitance curve versus graph for Se composite electrode;
FIG. 6 shows metal selenide Ni loaded on cotton cloth prepared under different Ni-Co ratios in examples 1 to 7 of the present inventionxCo9-x-specific capacitance value comparison graph of Se composite electrode under different current density conditions.
Detailed Description
The following is a detailed description of embodiments of the invention. The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
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.
Example 1
The flexible cotton cloth loaded with metal selenide Ni of the embodiment0Co9The electrode material of the Se super capacitor is prepared by taking pure cotton cloth as a substrate, sequentially carrying out oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on the substrate, and as shown in figure 1, the method specifically comprises the following steps:
(1) oil removal: and (2) soaking the substrate material in deoiling liquid for 10min at the temperature of 35 ℃, and then washing with deionized water to obtain the deoiled substrate material, wherein the deoiling liquid is an aqueous solution of triton, and the concentration of the triton in the deoiling liquid is 2%.
(2) Sensitization: soaking the deoiled substrate material obtained in the step (1) in a sensitizing solution for 10min at 35 ℃, and then washing with deionized water to obtain the sensitized substrate material, wherein the sensitizing solution is a mixed solution composed of stannous chloride and hydrochloric acid, the concentration of the stannous chloride in the sensitizing solution is 15g/L, and the concentration of the hydrochloric acid is 0.15M;
(3) and (3) activation: soaking the sensitized substrate material obtained in the step (2) in an activating solution at 35 ℃ for 10min, and then washing with deionized water to obtain an activated substrate material, wherein the activating solution is a mixed solution composed of palladium chloride and hydrochloric acid, the concentration of the palladium chloride in the activating solution is 0.15g/L, and the concentration of the hydrochloric acid is 0.03M;
(4) chemical nickel plating: placing the activated substrate material obtained in the step (3) into chemical plating solution to react for 10min at 35 ℃ to plate a metal nickel layer on the surface of the substrate, wherein the chemical plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the chemical plating solution is 20g/L, the concentration of the trisodium citrate is 10g/L, the concentration of the sodium hypophosphite is 30g/L, the concentration of the ammonium chloride is 30g/L, and the pH value of the chemical plating solution is 8.5-9.5;
(5) preparing a precursor: and (3) placing the substrate material plated with the metal nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 120 ℃ for hydrothermal reaction for 10h, taking out, washing and drying with deionized water and absolute ethyl alcohol to obtain the precursor, wherein the mixed solution is composed of cobalt chloride hexahydrate, urea and deionized water, the dosage of the cobalt chloride hexahydrate is 9mmol, the dosage of the urea is 12mmol, and the dosage of the deionized water is 60 mL.
(6) Selenizing: and (3) placing the precursor material prepared in the step (5) in a mixed solution at 180 ℃ for hydrothermal reaction for 12h, taking out, washing with deionized water and absolute ethyl alcohol, and drying to obtain the selenide, wherein the mixed solution is composed of selenium powder, sodium borohydride, absolute ethyl alcohol and deionized water, the dosages of the selenium powder and the sodium borohydride are both 2mmol, and the dosages of the absolute ethyl alcohol and the deionized water are respectively 3mL and 50 mL.
The chemical plating solution in the step (4) of the technical scheme is prepared by the following method:
(i) weighing raw materials of each component according to a ratio, uniformly dispersing the raw materials in deionized water, and filtering to obtain a single-component concentrated solution;
(ii) adding a concentrated trisodium citrate solution into a chemical plating bath, diluting, then sequentially adding a concentrated ammonium chloride solution, a concentrated nickel sulfate solution and a concentrated sodium hypophosphite solution under the condition of stirring, uniformly stirring, diluting to a specified volume, and finally adjusting the pH value of the chemical plating bath by using a sodium hydroxide solution.
In the technical scheme, the selenizing solution in the step (6) is prepared by the following method:
weighing selenium powder and sodium borohydride according to a ratio, placing the selenium powder and the sodium borohydride in a polytetrafluoroethylene inner container, then adding deionized water and absolute ethyl alcohol according to a ratio, and obtaining the solution after the solution is reacted from black to red.
Example 2
The flexible cotton cloth loaded with metal selenide Ni of the embodiment1.5Co7.5An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 1, and is different from the electrode material of the Se super capacitor only in that: the mixed solution in the step (5) is composed of nickel chloride hexahydrate, cobalt chloride hexahydrate, urea and deionized water, wherein: the amount of nickel chloride hexahydrate was 1.5mmol and the amount of cobalt chloride hexahydrate was 7.5 mmol.
Example 3
The flexible cotton cloth loaded with metal selenide Ni of the embodiment3Co6An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 2, and is different from the electrode material of the embodiment only in that: in the step (5), the dosage of the nickel chloride hexahydrate is 3mmol, and the dosage of the cobalt chloride hexahydrate is 6 mmol.
Example 4
The flexible cotton cloth loaded with metal selenide Ni of the embodiment4.5Co4.5An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 2, and is different from the electrode material of the embodiment only in that: in the step (5), the dosage of the nickel chloride hexahydrate is 4.5mmol, and the dosage of the cobalt chloride hexahydrate is 4.5 mmol.
Example 5
The flexible cotton cloth loaded with metal selenide Ni of the embodiment6Co3An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 2, and is different from the electrode material of the embodiment only in that: in the step (5), the dosage of the nickel chloride hexahydrate is 6mmol, and the dosage of the cobalt chloride hexahydrate is 3 mmol.
Example 6
The flexible cotton cloth loaded with metal selenide Ni of the embodiment7.5Co1.5An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 2, and is different from the electrode material of the embodiment only in that: in the step (5), the dosage of the nickel chloride hexahydrate is 7.5mmol, and the dosage of the cobalt chloride hexahydrate is 1.5 mmol.
Example 7
The flexible cotton cloth loaded with metal selenide Ni of the embodiment9Co0An electrode material of a Se super capacitor, which is basically the same as the preparation method of the electrode material of the embodiment 1, and is different from the electrode material of the Se super capacitor only in that: the mixed solution in the step (5) is composed of nickel chloride hexahydrate, urea and deionized water, wherein: the amount of nickel chloride hexahydrate was 9 mmol.
Example 8
The flexible cotton cloth loaded with metal selenide Ni of the embodiment4.5Co4.5The preparation method of the electrode material of the Se super capacitor takes pure cotton cloth as a substrate, and sequentially carries out oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on the substrate, and the method specifically comprises the following steps:
(1) oil removal: soaking the substrate material in deoiling liquid for 30min at the temperature of 30 ℃, and then washing with deionized water to obtain the deoiled substrate material, wherein the deoiling liquid is an aqueous solution of triton, and the concentration of the triton in the deoiling liquid is 1%;
(2) sensitization: soaking the deoiled substrate material obtained in the step (1) in a sensitizing solution for 30min at the temperature of 30 ℃, and then washing with deionized water to obtain the sensitized substrate material, wherein the sensitizing solution is a mixed solution composed of stannous chloride and hydrochloric acid, the concentration of the stannous chloride in the sensitizing solution is 10g/L, and the concentration of the hydrochloric acid is 0.1M;
(3) and (3) activation: soaking the sensitized substrate material obtained in the step (2) in an activating solution at 30 ℃ for 20min, and then washing with deionized water to obtain an activated substrate material, wherein the activating solution is a mixed solution composed of palladium chloride and hydrochloric acid, the concentration of the palladium chloride in the activating solution is 0.1g/L, and the concentration of the hydrochloric acid is 0.02M;
(4) chemical nickel plating: placing the activated substrate material obtained in the step (3) into chemical plating solution to react for 20min at the temperature of 30 ℃, so that a metal nickel layer is plated on the surface of the substrate, wherein the chemical plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of nickel sulfate in the chemical plating solution is 10g/L, the concentration of trisodium citrate is 5g/L, the concentration of sodium hypophosphite is 20g/L, the concentration of ammonium chloride is 20g/L, and the pH value of the chemical plating solution is 8.5;
(5) preparing a precursor: placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 200 ℃ for hydrothermal reaction for 5 hours, taking out the substrate material, washing the substrate material with deionized water and absolute ethyl alcohol, and drying the substrate material to obtain the precursor, wherein the mixed solution consists of nickel chloride hexahydrate, cobalt chloride hexahydrate, urea and deionized water, the usage amount of the nickel chloride hexahydrate and the cobalt chloride hexahydrate is 4.5mmol, the usage amount of the urea is 10mmol, and the usage amount of the deionized water is 50 mL;
(6) selenizing: and (3) placing the precursor material prepared in the step (5) in a selenizing solution for hydrothermal reaction for 5h at 220 ℃, taking out, washing and drying with deionized water and absolute ethyl alcohol to obtain the selenide, wherein the selenizing solution is composed of selenium powder, sodium borohydride, absolute ethyl alcohol and deionized water, the dosage of the selenium powder and the sodium borohydride is respectively 2mmol, the dosage of the absolute ethyl alcohol is 1mL, and the dosage of the deionized water is 50 mL.
Example 9
The flexible cotton cloth loaded with metal selenide Ni of the embodiment4.5Co4.5Preparation method of-Se supercapacitor electrode materialThe method comprises the following steps of taking pure cotton cloth as a substrate, sequentially carrying out oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on the substrate, wherein the method specifically comprises the following steps:
(1) oil removal: and (2) soaking the base material in deoiling liquid for 5min at the temperature of 40 ℃, and then washing with deionized water to obtain the deoiled base material, wherein the deoiling liquid is an aqueous solution of triton, and the concentration of the triton in the deoiling liquid is 5%.
(2) Sensitization: soaking the deoiled substrate material obtained in the step (1) in a sensitizing solution for 5min at 40 ℃, and then washing with deionized water to obtain the sensitized substrate material, wherein the sensitizing solution is a mixed solution composed of stannous chloride and hydrochloric acid, the concentration of the stannous chloride in the sensitizing solution is 20g/L, and the concentration of the hydrochloric acid is 0.2M;
(3) and (3) activation: soaking the sensitized substrate material obtained in the step (2) in an activating solution at 40 ℃ for 5min, and then washing with deionized water to obtain an activated substrate material, wherein the activating solution is a mixed solution composed of palladium chloride and hydrochloric acid, the concentration of the palladium chloride in the activating solution is 0.2g/L, and the concentration of the hydrochloric acid is 0.05M;
(4) chemical nickel plating: placing the activated substrate material obtained in the step (3) into chemical plating solution to react for 5min at the temperature of 40 ℃, so that a metal nickel layer is plated on the surface of the substrate, wherein the chemical plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of nickel sulfate in the chemical plating solution is 10-30 g/L, the concentration of trisodium citrate is 15g/L, the concentration of sodium hypophosphite is 40g/L, the concentration of ammonium chloride is 40g/L, and the pH value of the chemical plating solution is 9.5;
(5) preparing a precursor: placing the substrate material plated with the metal nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 100 ℃ for hydrothermal reaction for 24 hours, taking out the substrate material, washing the substrate material with deionized water and absolute ethyl alcohol, and drying the substrate material to obtain the precursor, wherein the mixed solution consists of nickel chloride hexahydrate, cobalt chloride hexahydrate, urea and deionized water, the usage amount of the nickel chloride hexahydrate and the cobalt chloride hexahydrate is 4.5mmol, the usage amount of the urea is 20mmol, and the usage amount of the deionized water is 70 mL;
(6) selenizing: and (3) placing the precursor material prepared in the step (5) in a selenizing solution for hydrothermal reaction for 24 hours at 120 ℃, taking out, washing and drying with deionized water and absolute ethyl alcohol to obtain the selenide, wherein the selenizing solution is composed of selenium powder, sodium borohydride, absolute ethyl alcohol and deionized water, the dosage of the selenium powder and the sodium borohydride is respectively 2mmol, the dosage of the absolute ethyl alcohol is 10mL, and the dosage of the deionized water is 50 mL.
Application example 1
The flexible cotton cloth loaded metal selenide prepared in the embodiment 1-7 is applied to an electrode material and packaged into a super capacitor, and the electrochemical performance of the super capacitor is performed in an electrochemical workstation. FIG. 4 shows the metal selenide composite electrode loaded on cotton cloth prepared under the condition of different nickel-cobalt mixture ratios in 5mV s-1As can be seen from FIG. 4, the composite electrodes of the present invention each have two pairs of distinct redox peaks, providing efficient pseudocapacitance performance.
FIG. 5 shows the metal selenide Ni loaded on cotton cloth under different Ni-Co ratio conditionsxCo9-xComparison of the specific capacitance curves of the-Se composite electrode, as can be seen from FIG. 5, at a current density of 2mA cm-2Under the condition, the nickel-cobalt mixture ratio is 1: 1, the specific capacitance of the prepared electrode material can reach 8.85F cm-2。
FIG. 6 shows metal selenide Ni loaded on cotton cloth prepared under different Ni-Co ratios in examples 1 to 7 of the present inventionxCo9-xComparison graph of specific capacitance values of the-Se composite electrode under different current density conditions, as can be seen from FIG. 6, the flexible cotton cloth loaded with metal selenide Ni prepared in examples 4 and 74.5Co4.5-Se、Ni9Co0The current density of the electrode material of the-Se super capacitor is 2-6 mA cm-2The specific capacitance performance is excellent under the condition.
Example 8-9 Flexible Cotton cloth Supported Metal selenide Ni4.5Co4.5Electricity of-Se super capacitor electrode materialThe chemical properties were substantially the same as those of the electrode material prepared in example 4.
Claims (5)
1. Flexible cotton cloth loaded with metal selenide NixCo9-x-Se supercapacitor electrode material, characterized in that: flexible cotton cloth loaded with metal selenide NixCo9-xThe electrode material of the-Se super capacitor takes pure cotton cloth as a substrate and is loaded with metal selenide NixCo9-x-a Se array structure; wherein: the flexible cotton cloth is loaded with metal selenide NixCo9-xThe electrode material of the Se super capacitor is prepared by sequentially carrying out oil removal, sensitization, activation, chemical nickel plating, precursor preparation and selenylation treatment on a substrate, and specifically comprises the following steps:
(1) oil removal: soaking the base material in degreasing liquid for 5-30 min at the temperature of 30-40 ℃, and then washing with deionized water to obtain the degreased base material, wherein the degreasing liquid is an aqueous solution of triton, and the concentration of the triton in the degreasing liquid is 1-5%;
(2) sensitization: soaking the deoiled substrate material obtained in the step (1) in a sensitizing solution for 5-30 min at the temperature of 30-40 ℃, and then washing with deionized water to obtain the sensitized substrate material, wherein the sensitizing solution is a mixed solution composed of stannous chloride and hydrochloric acid, the concentration of the stannous chloride in the sensitizing solution is 10-20 g/L, and the concentration of the hydrochloric acid is 0.1-0.2M;
(3) and (3) activation: soaking the sensitized substrate material obtained in the step (2) in an activating solution at the temperature of 30-40 ℃ for 5-20 min, and then washing with deionized water to obtain an activated substrate material, wherein the activating solution is a mixed solution composed of palladium chloride and hydrochloric acid, the concentration of the palladium chloride in the activating solution is 0.1-0.2 g/L, and the concentration of the hydrochloric acid is 0.02-0.05M;
(4) chemical nickel plating: placing the activated substrate material obtained in the step (3) into a chemical plating solution to react for 5-20 min at the temperature of 30-40 ℃, so as to plate a metal nickel layer on the surface of the substrate, wherein the chemical plating solution is a mixed solution composed of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of nickel sulfate in the chemical plating solution is 10-30 g/L, the concentration of trisodium citrate is 5-15 g/L, the concentration of sodium hypophosphite is 20-40 g/L, the concentration of ammonium chloride is 20-40 g/L, and the pH value of the chemical plating solution is 8.5-9.5;
(5) preparing a precursor: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at the temperature of 100-200 ℃ for hydrothermal reaction for 5-24 h, taking out, washing with deionized water and absolute ethyl alcohol, and drying to obtain the precursor, wherein the mixed solution is composed of nickel chloride hexahydrate, cobalt chloride hexahydrate, urea and deionized water, and the molar ratio of the nickel chloride hexahydrate to the cobalt chloride hexahydrate is 1: 1, the ratio of urea to deionized water is (10-20) mmol: (50-70) mL;
(6) selenizing: and (3) placing the precursor material prepared in the step (5) in a selenizing solution at 120-220 ℃ for hydrothermal reaction for 5-24 h, taking out, washing with deionized water and absolute ethyl alcohol, and drying to obtain the selenide, wherein the selenizing solution is composed of selenium powder, sodium borohydride, absolute ethyl alcohol and deionized water, and the molar ratio of the selenium powder to the sodium borohydride is 1: 1, the volume ratio of the selenium powder to the deionized water is 2 mmol: 50 mL.
2. The flexible cotton cloth supported metal selenide Ni according to claim 1xCo9-x-Se supercapacitor electrode material, characterized in that: the concentration of nickel sulfate in the chemical plating solution in the step (4) is 20g/L, the concentration of trisodium citrate is 10g/L, the concentration of sodium hypophosphite is 30g/L, and the concentration of ammonium chloride is 30 g/L.
3. The flexible cotton cloth supported metal selenide Ni according to claim 1xCo9-x-Se supercapacitor electrode material, characterized in that: in the step (5), the ratio of the urea to the deionized water is 12 mmol: 60 mL.
4. The flexible cotton cloth supported metal selenide Ni according to claim 1xCo9-x-Se supercapacitor electrode material, characterized in that: in the step (6), the volume ratio of the absolute ethyl alcohol to the deionized water is (1-10): 50.
5. use of the electrode material of any one of claims 1 to 4 in a supercapacitor.
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