CN111261430B - Nano needle-shaped cobalt nickel sulfide/carbon paper flexible electrode and preparation method thereof - Google Patents
Nano needle-shaped cobalt nickel sulfide/carbon paper flexible electrode and preparation method thereof Download PDFInfo
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- CN111261430B CN111261430B CN202010076212.3A CN202010076212A CN111261430B CN 111261430 B CN111261430 B CN 111261430B CN 202010076212 A CN202010076212 A CN 202010076212A CN 111261430 B CN111261430 B CN 111261430B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 168
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 230000001815 facial effect Effects 0.000 claims abstract description 46
- 238000004140 cleaning Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 35
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 abstract description 14
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 35
- 238000001816 cooling Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 22
- 239000000758 substrate Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 238000003763 carbonization Methods 0.000 description 13
- 238000010586 diagram Methods 0.000 description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 11
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 11
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229940079101 sodium sulfide Drugs 0.000 description 3
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/46—Metal oxides
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Abstract
The invention relates to a nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode and a preparation method thereof, which comprises the step 1 of placing facial tissue in inert gas or N2Carbonizing for 0.5-3 h under the protection of the carbon paper to obtain carbon paper; step 2, according to the following steps of 1: (1-3): (2-4): (0.2-1), dissolving nickel nitrate, cobalt nitrate, urea and hexadecyl trimethyl ammonium bromide in deionized water, uniformly mixing to obtain a mixed system, placing the carbon paper in the mixed system, and carrying out a first-step hydrothermal reaction at 110-130 ℃ to obtain carbon paper with a nickel-cobalt precursor; and 3, cleaning the carbon paper with the nickel-cobalt precursor, placing the carbon paper in a sodium sulfide solution, carrying out a second-step hydrothermal reaction at 140-180 ℃, taking out a product, and then sequentially cleaning and drying to obtain the nano needle-shaped cobalt-nickel sulfide/carbon paper flexible electrode. The invention reduces the whole weight of the electrode material, thereby improving the cycle stability and the energy density of the super capacitor.
Description
Technical Field
The invention relates to the technical field of preparation of a substrate material of a super capacitor, in particular to a nano needle-shaped cobalt nickel sulfide/carbon paper flexible electrode and a preparation method thereof.
Background
The super capacitor is used as an energy storage device, and has wide application prospect in the fields of electronic products and hybrid vehicles due to the unique properties of large power density, long cycle life, capability of realizing rapid charge and discharge, high charge and discharge efficiency, high specific capacity, wide working temperature range, environmental protection and the like. As a novel electronic device, the flexible solid-state supercapacitor receives the attention of more and more researchers in the fields of flexibility, light weight and intelligent wearable energy storage devices, and has very wide market potential.
In order to realize the flexibility of the super capacitor, an electroactive material is generally constructed on the surfaces of materials such as a metal current collector, fabric, paper, polymer and the like, but the improvement of the energy density and the power density of the super capacitor is influenced due to the problems of the weight, the conductivity and the like of the substrates; the performance of the energy storage device can be greatly improved by using high-conductivity carbon fiber cloth, graphene paper, carbon nanotubes and the like as substrate materials, but the high cost and the complexity of the preparation process are not negligible.
Therefore, it is necessary to develop flexible energy storage devices to construct a substrate material with a good balance of cost, conductivity and areal density and to compound the matched electroactive material on the surface.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nano needle-shaped cobalt nickel sulfide/carbon paper flexible electrode and a preparation method thereof, which reduce the overall weight of an electrode material, thereby improving the cycle stability and energy density of a super capacitor.
The invention is realized by the following technical scheme:
a method for preparing a nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode comprises the following steps,
step 1, placing the facial tissue in inert gas or N2Carbonizing for 0.5-3 h under the protection of the carbon paper to obtain carbon paper;
and 3, cleaning the carbon paper with the nickel-cobalt precursor, placing the carbon paper in a sodium sulfide solution, carrying out a second-step hydrothermal reaction at 140-180 ℃, taking out a product, and then sequentially cleaning and drying to obtain the nano needle-shaped cobalt-nickel sulfide/carbon paper flexible electrode.
Preferably, the facial tissue in the step 1 is subjected to ultrasonic cleaning by using acetone and an alcohol organic solvent and then carbonized, wherein the organic solvent is absolute ethyl alcohol or methanol.
Preferably, the carbonization in the step 1 is carried out at 700-1000 ℃.
Further, the carbonization is carried out from room temperature to the temperature, and the heating rate is 1-10 ℃/min.
Preferably, the first step hydrothermal reaction in the step 2 is carried out for 2-4 hours at the temperature.
Preferably, the molar ratio of the sodium sulfide in the sodium sulfide solution in the step 3 to the nickel nitrate in the step 2 is (2-6): 1.
preferably, the second hydrothermal reaction in the step 3 is carried out for 4-8 hours at the temperature.
Preferably, the carbon paper with the nickel-cobalt precursor grown in the step 3 and the product are ultrasonically cleaned by deionized water and an organic solvent, wherein the organic solvent is absolute ethyl alcohol, methanol or acetone.
The nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode is obtained by the preparation method of the nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention takes carbonized facial tissue as the substrate material of the flexible electrode, the main component of the facial tissue is cotton fiber, and the trace additive contains TiO2Cobalt nickel sulfide is selected as an electroactive substance to provide high capacitance, and two-step hydrothermal reaction is carried out to obtain the flexible carbon paper electrode loaded with the cobalt nickel sulfide, so that the overall weight of the electrode material is reduced, and the cycle stability and the energy density of the supercapacitor are improved. The invention uses the facial tissue as the raw material for preparing the electrode substrate, and has the advantages of short preparation process flow, high production rate, high yield,The carbon paper obtained by carbonization serves as a flexible electrode substrate, a slender carbon fiber framework and titanium dioxide on the surface of carbon fibers, so that a foundation is provided for the growth of more electroactive substances, the needle-shaped cobalt nickel sulfide array grown in situ provides a richer storage space for discharge products, the discharge capacity of the supercapacitor is increased, and more active sites are provided for electrode reaction; compared with the traditional coated electrode structure, the nano cobalt nickel sulfide grows on the surface of the carbon fiber in situ, and a conductive agent and a binder are not needed, so that the energy density and the cycling stability of the supercapacitor are improved.
Drawings
FIG. 1a is a pictorial representation of a facial tissue of the present invention prior to treatment.
Fig. 1b is a partial enlarged view of fig. 1 a.
FIG. 2a is a low angle bend of a cobalt nickel sulfide/carbon paper electrode obtained in example 2 of the present invention.
Fig. 2b is a large angle bend of cobalt nickel sulfide/carbon paper electrode obtained in example 2 of the present invention.
Fig. 3a is an SEM image of the carbon paper substrate obtained in example 2 of the present invention.
Fig. 3b is a partial enlarged view of fig. 3 a.
Fig. 4 is an XRD pattern of cobalt nickel sulfide/carbon paper electrode obtained in example 2 of the present invention.
FIG. 5 is an SEM image of a cobalt nickel sulfide/carbon paper electrode obtained in example 2 of the present invention at 50 μm.
Fig. 6a is a partial enlarged view of fig. 5 at 10 μm.
Fig. 6b is a partial enlarged view of fig. 5 at 1 μm.
Fig. 7a is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention continuously supplying power to an electronic watch in an unbent state.
Fig. 7b is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in embodiment 2 of the present invention continuously supplying power to an electronic watch in a state of being bent to 90 degrees.
Fig. 7c is an operation diagram of the flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in embodiment 2 of the present invention continuously supplying power to the electronic watch when the flexible asymmetric supercapacitor is bent to less than 90 degrees.
Fig. 8a is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention, which continuously supplies power to a small LED bulb in an unbent state.
Fig. 8b is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in embodiment 2 of the present invention continuously supplying power to a small LED bulb in a state of being bent to 90 degrees.
Fig. 8c is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention continuously supplying power to a small LED bulb when the flexible asymmetric supercapacitor is bent to less than 90 degrees.
Fig. 9a is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention continuously supplying power to an electronic watch at-22 ℃.
Fig. 9b is an operation diagram of a flexible asymmetric supercapacitor assembled by cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention continuously supplying power to an electronic watch at-20 ℃.
FIG. 9c is a partial physical diagram of a flexible asymmetric supercapacitor assembled from cobalt nickel sulfide/carbon paper electrodes obtained in example 2 of the present invention and continuously frozen at-20 ℃ and-22 ℃.
Fig. 10 is a charge-discharge diagram of cobalt nickel sulfide/carbon paper electrodes prepared after carbonization at different temperatures obtained in example 1, example 2 and example 3 of the present invention.
Fig. 11 is a graph showing the magnification of cobalt nickel sulfide/carbon paper electrodes prepared after carbonization at different temperatures obtained in example 1, example 2 and example 3 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
A method for preparing a nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode comprises the following steps,
step 1, pre-treating the facial tissue,
the invention adopts disposable soft cotton clean facial tissue which is made of cotton wings as an example, and the main raw material of the invention is high-quality spunlace non-woven fabric; the cleaning of the facial tissue is specifically that the whole facial tissue is cut into small pieces of (2-10) cm x (2-10) cm and then is sequentially subjected to ultrasonic cleaning by using acetone and absolute ethyl alcohol or methanol;
cleaning and drying the facial tissue in an inert gas such as argon, or N2Under the protection of the carbon paper substrate, high-temperature carbonization treatment is carried out at 700-1000 ℃, and heat preservation is carried out for 0.5-3 hours, so that the content of carbon fibers can be improved, the strength of the fibers tends to be stable, the temperature is raised from room temperature in the carbonization process, the temperature raising rate is 1-10 ℃/min, the tensile strength of the final carbon fibers can be improved, and the carbon paper substrate material is obtained;
and step 3, preparing the electrode,
nickel nitrate hexahydrate, cobalt nitrate hexahydrate, urea, hexadecyl trimethyl ammonium bromide and sodium sulfide nonahydrate are used for obtaining a carbon paper electrode loaded with nano needle-shaped cobalt nickel sulfide through two-step hydrothermal reaction;
specifically, the molar ratio of 1: (1-3): (2-4): (0.2-1) mixing nickel nitrate hexahydrate, cobalt nitrate hexahydrate, urea and hexadecyl trimethyl ammonium bromide with deionized water, placing a carbon paper substrate material in the mixture, reacting at 110-130 ℃ for 2-4 hours, taking hexadecyl trimethyl ammonium bromide as a surfactant to enable electroactive substances to well grow on carbon fibers, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with a nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, methanol or acetone;
and finally, according to the molar ratio of the sodium sulfide nonahydrate to the nickel nitrate hexahydrate of (2-6): 1, dissolving sodium sulfide nonahydrate with deionized water, placing carbon paper loaded with a nickel-cobalt precursor in the carbon paper, transferring the carbon paper to a reaction kettle, carrying out a displacement reaction for 4-8 hours at 140-180 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, methanol or acetone, and carrying out vacuum drying to obtain the nano needle-like cobalt-nickel sulfide/carbon paper flexible electrode material.
Example 1
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 2cm multiplied by 2cm, sequentially ultrasonically cleaning the facial tissue with acetone and absolute ethyl alcohol for three times, and drying the facial tissue in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a tubular furnace, heating to 800 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping at 800 ℃ for 1 hour, naturally cooling to room temperature along with the furnace, and placing the obtained carbon paper in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.075mol/L cobalt nitrate hexahydrate, 0.135mol/L urea and 0.015mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the mixed solution into a reaction kettle, reacting for 3 hours at 120 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.1mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 6h at 160 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 2
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 3cm multiplied by 3cm, sequentially ultrasonically cleaning the small pieces of facial tissue with acetone and absolute ethyl alcohol for three times, and drying the small pieces of facial tissue in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 900 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping at 900 ℃ for 1 hour, naturally cooling to room temperature along with the furnace, taking out and placing in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.075mol/L cobalt nitrate hexahydrate, 0.135mol/L urea and 0.015mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the mixed solution into a reaction kettle, reacting for 3 hours at 120 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.1mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 6h at 160 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 3
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 5cm multiplied by 5cm, sequentially ultrasonically cleaning the small pieces with acetone and absolute ethyl alcohol for three times, and drying the small pieces in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 1000 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping at 1000 ℃ for 1 hour, naturally cooling to room temperature along with the furnace, taking out and placing in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.075mol/L cobalt nitrate hexahydrate, 0.135mol/L urea and 0.015mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the mixed solution into a reaction kettle, reacting for 3 hours at 120 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.1mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 6h at 160 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
FIG. 1a is a pictorial representation of a facial tissue, which is identical everywhere on its surface and is not shown enlarged. Fig. 2a and fig. 2b show physical diagrams of two different bending states of the cobalt nickel sulfide/carbon paper electrode obtained in embodiment 2 of the present invention, which illustrate the advantage of good flexibility of the cobalt nickel sulfide/carbon paper electrode. SEM images of the carbon paper substrate as shown in fig. 3a and 3b, the carbon paper substrate micro-topography is the same everywhere, so no magnification is shown.
From FIG. 4, NiCo can be seen2S4And TiO2It can be seen from fig. 5, fig. 6a and fig. 6b that the nano needle-shaped cobalt nickel sulfide material grows uniformly on the surface of the carbon paper fiber to form a nano needle-shaped array, and the micro-morphology of the cobalt nickel sulfide/carbon paper electrode is the same everywhere, so no enlargement is shown. As shown in fig. 7a, 7b and 7c, 8a, 8b and 8c, and 9a and 9c, the cobalt nickel sulfide/carbon paper electrode grown in situ and the carbon paper electrode coated with activated carbon obtained by the invention are assembled into a flexible asymmetric supercapacitor, and the flexible asymmetric supercapacitor is wrapped by a preservative film and connected by nickel wires, can stably and continuously supply power to an electronic watch and an LED small bulb in different forms, and can continuously supply power to an electronic watch at-20 ℃ and-22 ℃, wherein the temperature measurement is carried out by using a multimeter, and fig. 9c shows that the flexible asymmetric supercapacitor is continuously maintained at the temperature by using a refrigerator.
Difference in carbonization temperature for carbon fiber and TiO2The invention researches and obtains the carbon paper base material processed by the most suitable carbonization temperature and heating rate, the carbon paper carbonized at 900 ℃ in the embodiment 2 has the optimal performance, and the cobalt-nickel sulfide on the surface grows compactly and uniformly. The slender fiber provides more active sites for the growth of active substances, and simultaneously the nanometerThe needle array has increased electrode material's specific surface area to can improve electrode material's specific capacitance, compare with the electrode structure of traditional coating, on carbon paper normal position growth cobalt nickel sulfide, need not to add conductive agent and binder, consequently promoted ultracapacitor system's circulation stability, reduced ultracapacitor system's whole weight, thereby promoted holistic energy density.
The cobalt nickel sulfide/carbon paper electrodes grown in situ in examples 1, 2 and 3 and the carbon paper electrodes coated with activated carbon obtained by the method are assembled into a flexible asymmetric supercapacitor, and electrochemical performance tests are carried out under a three-electrode system, wherein the carbon paper-loaded cobalt nickel sulfide electrodes treated at different carbonization temperatures are covered, as shown in fig. 10 and 11, and 2mA cm can be seen from fig. 10-2The charging and discharging time of the electrode obtained after the carbonization treatment at 900 ℃ is longest. As can be seen from FIG. 11, the specific capacitance of the carbon paper loaded cobalt nickel sulfide electrode obtained after the carbonization treatment at 900 ℃ is the largest under different current densities, and is 1mA cm-2Reaches 3250mF cm at the current density of-2Corresponding to a mass specific capacitance of 2100Fg-1And the specific capacitance of the carbon paper electrode obtained after the treatment at 800 ℃ and 1000 ℃ is only 2600mF cm-2And 1750mF cm-2The carbon paper carbonized at 1000 ℃ has high corresponding conductivity and relatively good rate performance due to high fiber carbonization degree, but the specific capacity of the carbon paper loaded with the cobalt nickel sulfide electrode after being carbonized at 900 ℃ is less than that of the carbon paper loaded with the cobalt nickel sulfide electrode after being carbonized at 900 ℃.
Example 4
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 6cm multiplied by 6cm, sequentially ultrasonically cleaning the small pieces with acetone and absolute ethyl alcohol for three times, and drying the small pieces in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 900 ℃ at the heating rate of 1 ℃/min under the argon atmosphere, keeping at 900 ℃ for 2.5 hours, naturally cooling to room temperature along with the furnace, taking out and placing in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.0375mol/L cobalt nitrate hexahydrate, 0.075mol/L urea and 0.0375mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the carbon paper into a reaction kettle, reacting at 130 ℃ for 2 hours, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.075mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 7 hours at 160 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 5
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 8cm multiplied by 8cm, sequentially ultrasonically cleaning the small pieces with acetone and methanol for three times, and drying the small pieces in a drying box for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, keeping at 900 ℃ for 1.5 hours, naturally cooling to room temperature along with the furnace, taking out and placing in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.1125mol/L cobalt nitrate hexahydrate, 0.15mol/L urea and 0.0075mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the carbon paper into a reaction kettle, reacting for 1h at 120 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and methanol; preparing 80mL of 0.1mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 6h at 140 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and methanol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 6
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 9cm multiplied by 9cm, sequentially ultrasonically cleaning the small pieces of facial tissue with acetone and absolute ethyl alcohol for three times, and drying the small pieces of facial tissue in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 900 ℃ at a heating rate of 10 ℃/min under the nitrogen atmosphere, keeping at 900 ℃ for 0.5 hour, naturally cooling to room temperature along with the furnace, taking out and placing in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.075mol/L cobalt nitrate hexahydrate, 0.1125mol/L urea and 0.0225mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the carbon paper into a reaction kettle, reacting at 110 ℃ for 2.5 hours, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.15mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 6h at 160 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 7
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 10cm multiplied by 10cm, sequentially ultrasonically cleaning the small pieces of facial tissue with acetone and absolute ethyl alcohol for three times, and drying the small pieces of facial tissue in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 700 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping at 700 ℃ for 3 hours, naturally cooling to room temperature along with the furnace, and placing the obtained carbon paper in a vacuum drying oven for later use;
third step, electrode preparation
Preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.09375mol/L cobalt nitrate hexahydrate, 0.135mol/L urea and 0.03mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the mixed solution into a reaction kettle, reacting for 8 hours at 120 ℃, naturally cooling the mixed solution to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and acetone; preparing 80mL of 0.1mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 2h at 170 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and acetone, and drying the carbon paper in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
Example 8
The first step, the pretreatment of the facial tissue,
cutting the facial tissue into small pieces of 4cm multiplied by 4cm, sequentially ultrasonically cleaning the small pieces with acetone and absolute ethyl alcohol for three times, and drying the small pieces in a drying oven for later use after cleaning;
in the second step, the electrode substrate is prepared,
placing the dried facial tissue in a small vacuum tube furnace, heating to 900 ℃ at the heating rate of 3 ℃/min under the argon atmosphere, keeping at 900 ℃ for 2 hours, naturally cooling to room temperature along with the furnace, and placing the obtained carbon paper in a drying box for later use;
in the third step, the preparation of the electrode,
preparing 80mL of mixed solution of 0.0375mol/L nickel nitrate hexahydrate, 0.075mol/L cobalt nitrate hexahydrate, 0.135mol/L urea and 0.015mol/L hexadecyl trimethyl ammonium bromide, placing the carbon paper obtained in the second step into the mixed solution, transferring the mixed solution into a reaction kettle, reacting for 3 hours at 125 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper with the nickel-cobalt precursor, and ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol; preparing 80mL of 0.225mol/L sodium sulfide nonahydrate solution, placing the carbon paper loaded with the nickel-cobalt precursor in the solution, transferring the carbon paper to a reaction kettle, reacting for 4h at 180 ℃, naturally cooling the carbon paper to room temperature after the reaction is finished, taking out the carbon paper loaded with the cobalt-nickel sulfide, ultrasonically cleaning the carbon paper with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the cobalt-nickel sulfide/carbon paper electrode material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (1)
1. A method for preparing a nanometer needle-shaped cobalt nickel sulfide/carbon paper flexible electrode is characterized by comprising the following steps,
step 1, loading TiO2The cotton fiber facial tissue is sequentially cleaned by acetone and alcohol organic solvent in an ultrasonic way and then is put in inert gas or N2Under the protection of (1), carbonizing at 700-1000 ℃ for 1-3 h to obtain carbon paper;
step 2, according to the following steps of 1: (1-3): (2-4): (0.2-1), dissolving nickel nitrate, cobalt nitrate, urea and hexadecyl trimethyl ammonium bromide in deionized water, uniformly mixing to obtain a mixed system, placing the carbon paper in the mixed system, and carrying out a first-step hydrothermal reaction at 110-130 ℃ for 1-8 h to obtain carbon paper with a nickel-cobalt precursor;
and 3, cleaning the carbon paper with the nickel-cobalt precursor, and then placing the carbon paper in a sodium sulfide solution, wherein the molar ratio of sodium sulfide to nickel nitrate in the step 2 is (2-6): 1, carrying out a second-step hydrothermal reaction at 140-180 ℃ for 2-12 h, taking out a product, and then sequentially cleaning and drying to obtain the nano needle-shaped cobalt nickel sulfide/carbon paper flexible electrode.
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