CN111146016A - Flaky nickel sulfide/nickel-vanadium double hydroxide/graphene composite material for super capacitor and preparation method thereof - Google Patents
Flaky nickel sulfide/nickel-vanadium double hydroxide/graphene composite material for super capacitor and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 27
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 22
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005234 chemical deposition Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 12
- 238000004146 energy storage Methods 0.000 abstract description 5
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 abstract 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- GGVOVPORYPQPCE-UHFFFAOYSA-M chloronickel Chemical compound [Ni]Cl GGVOVPORYPQPCE-UHFFFAOYSA-M 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009862 microstructural analysis Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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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- 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
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Abstract
A flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for a super capacitor and a preparation method thereof belong to the field of energy storage materials, and aim at providing a sulfide and metal double hydroxide combined composite material with high specific capacitance and good stability and a preparation method thereof2·6H2O、NH4VO3、NH4F and CO (NH)2)2Dissolving in deionized water, stirring, pouring into a reaction kettle, reacting at 180 ℃ for 8 hours to obtain NiV/rGO/NF, putting a precursor nickel vanadium double hydroxide into a sodium sulfide solution, reacting at 120 ℃ to obtain Ni3S2/NiV‑LDH/rGO/NF. The method is simple, easy to control and low in cost, and the prepared electrode material has high specific capacitance, good rate performance and cycling stability, shows high power density and energy density when being manufactured into a device, and can be used as an excellent electrode material of a super capacitor.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a flaky nickel sulfide/nickel-vanadium double hydroxide/graphene composite material for a super capacitor and a preparation method thereof.
Background
With the rapid development of scientific technology, the large-scale use of fossil fuels and serious environmental problems, high-efficiency energy storage devices have been receiving more and more attention from researchers in recent years. Among currently used energy storage devices, a super capacitor has the advantages of a conventional capacitor and a secondary battery, has the advantages of long service life, high charging and discharging speed, high power density, safety, reliability and the like, and is considered to be a promising energy storage device. The performance of supercapacitors depends mainly on the electrode material. The currently studied electrode materials of supercapacitors mainly include: carbon-based material of electric double layer and pseudocapacitance material. Among these electrode materials, Layered Double Hydroxides (LDHs) have received general attention due to excellent redox activity, environmental protection, high surface area, and unique structural properties. Vanadium has the advantages of multiple oxidation states, high energy density, abundant resources, low cost and the like, and is widely applied to mixed metals.
The synergistic effect is one of the main factors for improving the electrochemical performance of the electrode. A new strategy for combining transition metal double hydroxides with sulphides obtained by in situ sulphidation is thus proposed, taking full advantage of the advantages of the components and the synergistic effects between different materials. The introduction of the graphene improves the electrochemical performance of the electrode, and simultaneously avoids the aggregation phenomenon of the double hydroxide in the charging and discharging processes, and by combining the advantages, the prepared composite material is used as the electrode material of the supercapacitor, so that the reasonable utilization of the material performance and the cost can be realized, the composite material has excellent performance which is not possessed by a single material, and the application prospect is very wide.
Disclosure of Invention
The invention aims to provide a composite material combining sulfide and metal double hydroxide with high specific capacitance and good stability and a preparation method thereof.
The invention adopts the following technical scheme:
a flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for a super capacitor has a chemical general formula of Ni3S2the/NiV-LDH/rGO/NF-X represents different vulcanization time, wherein the value of X is more than or equal to 1 and less than or equal to 7.
A preparation method of a flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for a super capacitor comprises the following steps:
firstly, growing reduced graphene oxide on a foamed nickel substrate by a chemical deposition method: adding graphene oxide into deionized water according to a ratio, performing ultrasonic dispersion to obtain a brown dispersion liquid, adding a reducing agent into the dispersion liquid, uniformly stirring to obtain a mixed solution, immersing a foamed nickel substrate cleaned by acetone, hydrochloric acid and absolute ethyl alcohol into the mixed solution, performing hydrothermal bath reduction for 6 hours at 90 ℃, taking out the foamed nickel substrate, washing residues, placing the foamed nickel substrate in a drying oven, and drying for 12 hours at 60 ℃ to obtain the foamed nickel substrate with reduced graphene oxide, wherein the foamed nickel substrate is marked as rGO/NF;
in the second step, nickel chloride (NiCl)2·6H2O), ammonium metavanadate (NH)4VO3) Ammonium fluoride (NH)4F) And urea (CO (NH)2)2) Dissolving in deionized water, stirring at room temperature until a uniform light green precursor solution is formed, pouring the precursor solution into a hydrothermal reaction kettle with the capacity of 100ml, putting rGO/NF into the reaction kettle, keeping the temperature at 180 ℃ for 8 hours, taking out and cleaning to obtain a composite material NiV/rGO/NF;
thirdly, sulfurizing NiV/rGO/NF by hydrothermal method, proportionally mixing Na2S·9H2Dissolving O in deionized water, stirring for dissolving, transferring to a reaction kettle, placing NiV/rGO/NF into the reaction kettle, keeping at 120 deg.C for 1-7h, taking out, cleaning, and drying to obtain Ni with chemical formula3S2/NiV-LDH/rGONF-X composite material.
In the first step, the mass-to-volume ratio of the graphene oxide to the water is 1mg:3mL, the reducing agent is ascorbic acid, and the mass ratio of the graphene oxide to the reducing agent is 1: 3.
In the second step, the ratio of the nickel chloride to the deionized water is 0.9mmol to 70mL, the ratio of the ammonium metavanadate to the deionized water is 0.3mmol to 70mL, the ratio of the ammonium fluoride to the deionized water is 4mmol to 70mL, and the ratio of the urea to the deionized water is 5mmol to 70 mL.
In the third step, Na is described2S·9H2The ratio of O to deionized water was 1 mmol:70 mL.
The invention has the following beneficial effects:
graphene has an ultrahigh theoretical surface area as a novel carbon material, is applied to novel composite materials and construction of high-performance electrochemical new energy devices, combines the characteristics of cobalt molybdenum sulfide and graphene, and can be used as an electrode material of a supercapacitor, so that reasonable utilization of material performance and cost can be realized, excellent performance which is not possessed by a single material is realized, and the application prospect is very wide.
The vulcanization time in the invention has obvious influence on the specific capacitance of the super capacitor. When the sulfuration reaction is carried out for 3 hours, the prepared nickel sulfide/nickel vanadium double hydroxide has larger specific capacitance (3004 Fg) when being used as the electrode material of the super capacitor-1) And excellent cycle stability (the capacity retention rate is 92.2 percent after 5000 charge-discharge cycles), the nickel sulfide/nickel vanadium double hydroxide prepared by taking reduced graphene oxide supported by foamed nickel as a current collector is taken as a positive electrode material, and a super capacitor device assembled by taking activated carbon as a negative electrode material has the volume of 59.4 Wh kg-1The energy density of the super capacitor can be used as a positive electrode material of the super capacitor.
Drawings
FIG. 1 shows the NiV/rGO/NF and Ni obtained in examples 2 to 63S2XRD curves of/NiV-LDH/rGO/NF vulcanized at different times;
wherein: a is NiV/rGO/NF;
b is Ni3S2/NiV-LDH/rGO/NF-1；
c is Ni3S2/NiV-LDH/rGO/NF-3；
d is Ni3S2/NiV-LDH/rGO/NF-5；
e is Ni3S2/NiV-LDH/rGO/NF-7。
FIG. 2 is a scanning electron micrograph of nickel sulfide/nickel vanadium double hydroxide from example 4 taken at different magnifications.
FIG. 3 is a plot of the voltammetric cycling profile of the electrode material prepared in example 4 in a 2mol/L KOH solution.
FIG. 4 is a constant current charge and discharge curve diagram of the electrode material prepared in example 4 in 2mol/L KOH solution.
Fig. 5 is a graph of energy density versus power density for the supercapacitor device prepared in example 7.
Detailed Description
Detecting, analyzing and characterizing the microstructure and the electrochemical performance of the prepared composite material:
microstructural analysis was performed with a scanning electron microscope, model MIRA 3;
electrochemical performance testing was performed with CHI660E electrochemical workstation.
Example 1
Nickel chloride (NiCl) in a molar amount of 0.9mmol2·6H2O) and 0.3mmol of ammonium metavanadate (NH)4VO3) 4mmol of ammonium fluoride (NH)4F) And 5mmol of urea (CO (NH)2)2) Dissolved in 70mL of deionized water and stirred at room temperature until a homogeneous greenish precursor solution is formed. Putting the precursor solution and the cleaned NF into a reaction kettle, keeping the reaction kettle at 180 ℃ for 8 hours, and taking out the reaction kettle to obtain a material NiV-LDH/NF; the prepared NiV-LDH/NF is used as the anode material of the super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2mol/L KOH), and the specific capacitance is 979F g-1。
Example 2
Ultrasonically decomposing 10mg of graphene oxide into 30mL of distilled waterAfter a uniform brown solution is formed, adding 30mg of ascorbic acid, carrying out ultrasonic stirring uniformly, placing foamed nickel cleaned by acetone, hydrochloric acid and absolute ethyl alcohol into the dispersion liquid, depositing for 6 hours at the temperature of 90 ℃ in a water bath kettle, washing the surface of a sample by deionized water, and drying for 12 hours at the temperature of 70 ℃ to obtain rGO/NF. Nickel chloride (NiCl) in a molar amount of 0.9mmol2·6H2O) and 0.3mmol of ammonium metavanadate (NH)4VO3) 4mmol of ammonium fluoride (NH)4F) And 5mmol of urea (CO (NH)2)2) Dissolved in 70mL of deionized water and stirred at room temperature until a homogeneous greenish precursor solution is formed. Putting the precursor solution and the rGO/NF into a reaction kettle, keeping the reaction kettle at 180 ℃ for 8 hours, taking out and cleaning to obtain a composite material NiV/rGO/NF; the prepared NiV/rGO/NF composite material is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (electrolyte is 2mol/L KOH), and the specific capacitance is 1818F g-1。
Example 3
Adding 1mmoL Na2S·9H2O is dissolved in 70mL of deionized water, stirred and dissolved, then transferred to a reaction kettle, and NiV/rGO/NF prepared in example 2 is placed in the reaction kettle, kept at 120 ℃ for 1 hour, the surface of the sample is washed by the deionized water, and the sample is dried overnight at 60 ℃. The prepared composite is named as Ni3S2The NiV-LDH/rGO/NF-1 is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (2 mol/L KOH electrolyte), and the specific capacitance is 2534F g-1。
Example 4
Adding 1mmoL Na2S·9H2O is dissolved in 70mL of deionized water, stirred and dissolved, then transferred to a reaction kettle, and NiV/rGO/NF prepared in example 1 is placed in the reaction kettle, kept at 120 ℃ for 3 hours, the surface of the sample is washed by the deionized water, and dried at 60 ℃ for one night. The prepared composite is named as Ni3S2NiV-LDH/rGO/NF-3 as the anode material of a super capacitor in a three-electrode system (electrolyte is 2mol/L KOH)The specific capacitance of the test piece is 3004F g-1。
Example 5
Adding 1mmoL Na2S·9H2O is dissolved in 70mL of deionized water, stirred and dissolved, then transferred to a reaction kettle, and NiV/rGO/NF prepared in example 1 is placed in the reaction kettle, kept at 120 ℃ for 5 hours, the surface of the sample is washed by the deionized water, and dried at 60 ℃ for one night. The prepared composite is named as Ni3S2The NiV-LDH/rGO/NF-5 is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (2 mol/L KOH electrolyte), and the specific capacitance of the material is 2445F g-1。
Example 6
Adding 1mmoL Na2S·9H2O was dissolved in 70mL of deionized water, stirred and dissolved, and transferred to a reaction vessel, and NiV/rGO/NF obtained in example 1 was placed therein, and kept at 120 ℃ for 7 hours, and the surface of the sample was washed with deionized water and dried overnight at 60 ℃. The prepared composite is named as Ni3S2The NiV-LDH/rGO/NF-7 is used as a positive electrode material of a super capacitor to carry out electrochemical performance test in a three-electrode system (2 mol/L KOH electrolyte), and the specific capacitance is 2261F g-1。
Example 7
Mixing acetylene black, active carbon and polyvinylidene fluoride according to the mass ratio of 8:1:1, uniformly grinding, coating on foamed nickel, drying at 60 ℃ for 12h to serve as a negative electrode material, and taking Ni as a negative electrode material3S2the/NiV-LDH/rGO/NF-3 is used as an anode material to be assembled into an asymmetric super capacitor device, and electrochemical performance test is carried out on the asymmetric super capacitor device; the power density of the prepared asymmetric device of the super capacitor is 852.3W kg-1It was shown to be as high as 59.4 Wh kg-1The energy density of (1).
Preparing an asymmetric super capacitor device:
acetylene black, activated carbon and polyvinylidene fluoride are mixed according to the mass ratio of 8:1:1, the mixture is uniformly ground and then coated on foamed nickel, the mixture is dried at 80 ℃ and then used as a negative electrode material, a nickel sulfide/nickel vanadium double hydroxide is used as a positive electrode material, a cellulose film is used as a diaphragm, a KOH alkaline solution is used as an electrolyte to assemble a liquid asymmetric supercapacitor device, and electrochemical performance test is carried out on the liquid asymmetric supercapacitor device.
And (4) conclusion: the specific capacitance of the prepared single nickel-vanadium double hydroxide is 979F g-1(ii) a In addition, the current collector has a great influence on the electrochemical performance of the electrode material, and when the reduced graphene oxide supported by the foamed nickel is used as the current collector, the specific capacitance of the prepared electrode material is greatly improved to 1818 Fg-1(ii) a The specific capacitance of the nickel sulfide/nickel vanadium double hydroxide formed after partial vulcanization of the hydroxide as the anode material of the super capacitor is up to 3004F g-1The energy density of the prepared super capacitor device is as high as 59.4 Wh kg-1。
Claims (5)
1. A flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for a super capacitor is characterized in that: has a chemical formula of Ni3S2the/NiV-LDH/rGO/NF-X represents different vulcanization time, wherein the value of X is more than or equal to 1 and less than or equal to 7.
2. A method for preparing the flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for the supercapacitor according to claim 1, which is characterized in that: the method comprises the following steps:
firstly, growing reduced graphene oxide on a foamed nickel substrate by a chemical deposition method: adding graphene oxide into deionized water according to a ratio, performing ultrasonic dispersion to obtain a brown dispersion liquid, adding a reducing agent into the dispersion liquid, uniformly stirring to obtain a mixed solution, immersing a foamed nickel substrate cleaned by acetone, hydrochloric acid and absolute ethyl alcohol into the mixed solution, performing hydrothermal bath reduction for 6 hours at 90 ℃, taking out the foamed nickel substrate, washing residues, placing the foamed nickel substrate in a drying oven, and drying for 12 hours at 60 ℃ to obtain the foamed nickel substrate with reduced graphene oxide, wherein the foamed nickel substrate is marked as rGO/NF;
secondly, dissolving nickel chloride, ammonium metavanadate, ammonium fluoride and urea in deionized water, stirring at room temperature until a uniform light green precursor solution is formed, pouring the precursor solution into a hydrothermal reaction kettle with the capacity of 100ml, putting rGO/NF into the reaction kettle, keeping the temperature at 180 ℃ for 8 hours, taking out and cleaning to obtain a composite material NiV/rGO/NF;
thirdly, sulfurizing NiV/rGO/NF by hydrothermal method, proportionally mixing Na2S·9H2Dissolving O in deionized water, stirring for dissolving, transferring to a reaction kettle, placing NiV/rGO/NF into the reaction kettle, keeping at 120 deg.C for 1-7h, taking out, cleaning, and drying to obtain Ni with chemical formula3S2The composite material of/NiV-LDH/rGO/NF-X.
3. The preparation method of the flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for the supercapacitor according to claim 2, characterized by comprising the following steps: in the first step, the mass-to-volume ratio of the graphene oxide to the water is 1mg:3mL, the reducing agent is ascorbic acid, and the mass ratio of the graphene oxide to the reducing agent is 1: 3.
4. The preparation method of the flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for the supercapacitor according to claim 2, characterized by comprising the following steps: in the second step, the ratio of the nickel chloride to the deionized water is 0.9mmol to 70mL, the ratio of the ammonium metavanadate to the deionized water is 0.3mmol to 70mL, the ratio of the ammonium fluoride to the deionized water is 4mmol to 70mL, and the ratio of the urea to the deionized water is 5mmol to 70 mL.
5. The preparation method of the flaky nickel sulfide/nickel vanadium double hydroxide/graphene composite material for the supercapacitor according to claim 2, characterized by comprising the following steps: in the third step, Na is described2S·9H2The ratio of O to deionized water was 1 mmol:70 mL.
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