CN109755036B - Preparation method and application of nickel sulfide/sulfur cobalt nickel/carbon nanotube foam - Google Patents
Preparation method and application of nickel sulfide/sulfur cobalt nickel/carbon nanotube foam Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000006260 foam Substances 0.000 title claims abstract description 78
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 21
- 239000011593 sulfur Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 15
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 15
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 20
- 238000004073 vulcanization Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 21
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 17
- -1 Transition metal sulfides Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method of volume-shrinkage nickel sulfide/sulfur cobalt nickel/carbon nanotube foam, which comprises the following specific steps: (a) preparing a carbon nanotube solution by carrying out acid washing and reflux treatment on the single-walled carbon nanotube; (b) cleaning polyurethane foam, coating a carbon tube and preparing carbon nanotube foam through a fire burning process; (c) putting the carbon nano tube foam into a mixed solution of nickel chloride, cobalt chloride, urea, distilled water and methanol, performing hydrothermal reaction, drying, and then putting into a tubular furnace for heat treatment to obtain nickel cobaltate foam; (d) putting the nickel cobaltate foam into a sodium sulfide solution for hydrothermal treatment to obtain the composite material; the mass capacitance of the composite material after vulcanization treatment is greatly improved, and the volume of the composite material is reduced to one tenth of the original volume, so that the composite material can obtain ultrahigh area capacitance and volume capacitance; the composite material can be suitable for the current wearable and portable energy storage equipment.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a preparation method and application of volume-shrinkage nickel sulfide/sulfur cobalt nickel/carbon nano tube foam.
Background
Carbon nanotubes were discovered by rice island bod of japan electronics corporation (NEC) in 1991 and have attracted much attention because of their light weight and excellent mechanical, electrical, and chemical properties. In the electrochemical field, carbon nanotubes are often added to improve the overall conductivity of the material. The three-dimensional carbon nanotube foam has high density, high elasticity and high conductivity, and is widely applied to self-supporting electrode substrates of electrochemical energy storage devices, and the inherent holes of the material provide fast channels for the transportation of electron ions, so that the good rate performance of the electrode material can be ensured.
Transition metal sulfides have higher electrochemical activity and conductivity than their corresponding transition metal oxides and are readily prepared by oxide conversion and are of great interest. Ni-Co-S has good capacitance performance as ternary transition metal sulfide, and has more abundant oxidation-reduction reaction and higher capacitance compared with binary transition metal sulfide and ternary transition metal oxide.
At present, wearable and portable devices are rapidly developed, and therefore, electrode materials are required to have characteristics of miniaturization, elasticity and the like.
The large surface area or no elasticity of substrates such as carbon cloth and nickel mesh limits the development of miniaturization and portability, and the low area-specific capacitance and volume-specific capacitance are also a limiting factor. Professor Yang Kanhong of Tianjin university aims at preparing volume-shrinkage graphene gel (Y.Tao, X.Xie, W.Lv, D.M.Tang, D.Kong, Z.Huang, H.Nishihara, T.Ishii, B.Li, D.Golberg, F.kang, T.Kyotani and Q.H.Yang, Sci Rep 2013,3,2975.) by an evaporation drying method, and the volume specific capacitance of the graphene gel reaches 376F cm-3The combination of the pseudo-capacitance material with high specific capacitance is avoided, so that the capacitance of the capacitor is further improved. At present, no report is found on a method for preparing a supercapacitor electrode material with small volume by compounding three-dimensional carbon nanotube foam and Ni-Co-S.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing a nickel sulfide/sulfur cobalt nickel/carbon nano tube foam electrode by compounding carbon nano tube foam and nickel cobaltate and then vulcanizing the nickel cobaltate into nickel sulfide/sulfur cobalt nickel in one step through sodium sulfide. The method utilizes sodium sulfide to carry out vulcanization, and forms carbon-sulfur bonds in the process to enhance the acting force between carbon tubes, so that the volume of the carbon nanotube foam is greatly shrunk, and the aim of preparing the electrode material with small volume is fulfilled.
The invention is realized by the following technical scheme:
a preparation method of volume-shrinkage nickel sulfide/sulfur cobalt nickel/carbon nanotube foam comprises the following specific steps:
(a) dissolving the single-walled carbon nanotube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid, refluxing for 2h at 70 ℃, adding distilled water, performing suction filtration (continuously washing with distilled water in the suction filtration process), cleaning until filter residue is neutral, and adding distilled water to obtain an acidified single-walled carbon nanotube dispersion solution;
(b) cleaning polyurethane foam, drying, immersing in the acidified single-walled carbon nanotube dispersion liquid obtained in the step (a), extruding for 3-5s by using forceps to fully coat the carbon nanotube solution on the surface of the foam, taking out, placing in a 70 ℃ oven, drying for 12h, repeating the immersion drying step twice, and finally obtaining the polyurethane foam coated with the carbon tubes; and (3) placing the polyurethane foam coated with the carbon tube on an alcohol lamp, burning for 15-20s, burning off the polyurethane (the minimum 15s ensures that the polyurethane can be completely removed, and the carbon nanotube foam can be damaged if the time exceeds 20 s), and obtaining the carbon nanotube foam. The specific steps of coating carbon tube and firing can also be found in the disclosure of Chinese patent CN 108163837A.
(c) Dissolving nickel chloride, cobalt chloride and urea in a methanol water solution (the volume ratio of methanol to water is 6:1), and fully stirring to obtain a pink solution; in the pink solution, the concentrations of nickel chloride, cobalt chloride and urea are 0.005mol L in sequence-1、0.01mol L-1、0.4mol L-1(ii) a Transferring the pink solution into a 50mL polytetrafluoroethylene reaction kettle, immersing carbon nano tube foam in the kettle, carrying out hydrothermal reaction for 6h at 120 ℃, then cooling to room temperature, taking out a sample, sequentially washing the sample with distilled water and absolute ethyl alcohol, drying the sample, placing the dried sample in a tubular rapid heating furnace, and calcining the sample for 2h at the constant temperature of 300 ℃ in air to obtain nickel cobaltate loaded on the carbon nano tube foam;
(d) dissolving sodium sulfide in distilled water to obtain a solution with a concentration of 0.003-0.012mol L-1Transferring the solution into a 50mL polytetrafluoroethylene reaction kettle, and immersing the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (c) into the solutionAnd carrying out hydrothermal reaction at 120 ℃ for 8h in the solution, cooling to room temperature, taking out the sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the volume-shrunk nickel sulfide/sulfur cobalt nickel/carbon nanotube foam.
Further, in the preparation method of the volume-shrunk nickel sulfide/nickel cobalt sulfide/carbon nanotube foam, in the step (a), the volume ratio of concentrated sulfuric acid (mass fraction 95.0-98.0%) to concentrated nitric acid (mass fraction 65.0-68.0%) in the mixed solution is 3: 1; the concentration of the obtained single-walled carbon nanotube solution was about 1mg mL-1(too low concentration, repeated steps of coating the carbon tube on the polyurethane foam, time waste, and uneven coating caused by too high concentration).
Further, in the method for preparing the volume-shrunk nickel sulfide/nickel cobalt sulfide/carbon nanotube foam, the step (b) of cleaning and drying the polyurethane foam refers to: cutting polyurethane foam to 1cm-3And washing the square blocks with washing powder, distilled water and absolute ethyl alcohol in sequence, and drying the square blocks at the temperature of 60 ℃ for 12 hours.
In addition, the invention also uses the application of the nickel sulfide/sulfur cobalt nickel/carbon nanotube foam with the contracted volume as the electrode of the super capacitor.
The volume-shrinkage nickel sulfide/sulfur cobalt nickel/carbon nanotube foam composite material prepared by the method structurally takes carbon nanotube foam as a framework, a three-dimensional nano array of nickel sulfide/sulfur cobalt nickel is loaded on the upper side, the nickel sulfide/sulfur cobalt nickel array which is mutually crosslinked and partially collapsed increases the contact area with a foam substrate, the conductivity of the material is improved, in addition, the contact between an active material and an electrolyte is increased through holes on a nickel sulfide/sulfur cobalt nickel nanosheet, the transfer of electrons and ions is convenient, and the better rate-doubling performance of the material can be ensured.
In the vulcanizing step, nickel cobaltate nanosheets can be converted into nickel sulfide/nickel cobalt sulfide nanosheets, carbon-sulfur bonds are formed in the process, so that the acting force between carbon tubes is enhanced, the volume of the carbon tubes is greatly reduced, the miniaturization of electrodes is realized, and the area specific capacitance and the volume specific capacitance of electrode materials are greatly improved. In addition, certain damage to the nickel sulfide/sulfur cobalt nickel nanosheet is caused, contact between the nanosheet and the substrate is increased, overall conductivity of the material is increased, and holes in the nanosheet caused in the vulcanization process increase contact between the active material and the electrolyte, so that transmission of electronic ions is facilitated.
The composite material obtained by the invention has excellent electrochemical performance and good cycle performance as an electrode material, and the electrochemical performance is 1A g-1The mass-to-capacitance, area-to-capacitance, and volume-to-capacitance at current density were 2905F g, respectively-1、10.46F cm-2、1307.25F cm-3(ii) a At 10A g-1The capacity retention rate is still 83% after 10000 cycles of circulation under the current density of (1).
Drawings
FIG. 1 is a graph showing a comparison of the volume of an electrode composite prepared in example 1 of the present invention before and after vulcanization.
Fig. 2 is an XRD pattern of the electrode composite prepared in example 1 of the present invention.
Fig. 3 is an SEM image of the electrode composite prepared in example 1 of the present invention.
FIG. 4 is a cyclic voltammogram of the electrode composite prepared in example 1 of the present invention.
FIG. 5 is a chronopotentiometric graph of the electrode composite prepared in example 1 of the present invention.
Fig. 6 is a cycle life graph of the electrode composite prepared in example 1 of the present invention.
Detailed description of the preferred embodiments
The single-walled carbon nanotubes used in the examples were purchased from Shenzhen nanometer harbor stock Limited (SWNT-2);
the polyurethane foams used in the examples were purchased from Nantong Daiki sponge Co.
The remaining reagents and materials were purchased commercially, unless otherwise specified.
Example 1
(1) Ultrasonically dispersing 200mg of single-walled carbon nanotube into a mixed solution of concentrated sulfuric acid (mass fraction of 98.0%) and concentrated nitric acid (mass fraction of 68.0%) in a volume ratio of 3:1, refluxing at 70 ℃ for 2 hours, adding distilled water for dilution and stirring, performing suction filtration, and using distilled water for filtrationWashing to neutrality, and diluting carbon tube with distilled water to obtain carbon tube with concentration of 1mg mL-1The acidified single-walled carbon nanotube dispersion of (a).
(2) Cutting the polyurethane foam into pieces of 1X 1cm3The cube (in the specific implementation process, foam can be cut into required size and shape according to requirements), washing powder, distilled water and ethanol sequentially by ultrasonic washing (the ultrasonic power is 500W and the time is 20min), drying at 70 ℃ for 12h, immersing into the acidified single-walled carbon nanotube dispersion liquid obtained in the step (1), extruding for 3-5s by using tweezers to fully coat the carbon nanotube solution on the surface of the foam, taking out sponge, placing in a drying oven at 70 ℃ for drying for 12h, immersing into the acidified single-walled carbon nanotube dispersion liquid again, and repeating the immersion-drying step for 1 time (namely, co-soaking-drying for 2 times) to obtain polyurethane foam coated with the single-walled carbon nanotubes;
placing the dried foam compound on alcohol burner flame to burn off polyurethane (about 15s, in specific implementation, the burning time is controlled within 15s-20s, the polyurethane can be burnt off), so as to form elastic nitrogen-doped carbon nanotube foam, and calculating the density of the foam according to the mass weighing and the volume to be 1.5mg cm3。
(3) Dissolving nickel chloride, cobalt chloride and urea in methanol water solution (the volume ratio of methanol to water is 6:1), and fully stirring to form pink solution, wherein the concentrations of nickel chloride, cobalt chloride and urea in the pink solution are 0.005mol L in sequence-1、0.01mol L-1、0.4mol L-1(ii) a Transferring the pink solution into a 50mL polytetrafluoroethylene reaction kettle, immersing the nitrogen-doped carbon nanotube foam obtained in the step (2) in the reaction kettle, and carrying out hydrothermal reaction at 120 ℃ for 6 hours; cooling to room temperature, washing with distilled water and anhydrous ethanol, oven drying at 60 deg.C for 12 hr, placing in a tubular rapid heating furnace, and heating at 1 deg.C for 1 min-1And calcining the mixture at the constant temperature of 300 ℃ for 2 hours to obtain the nickel cobaltate loaded on the carbon nano tube foam.
(4) 0.006mol L of the preparation-1Transferring the sodium sulfide solution into a 50mL polytetrafluoroethylene reaction kettle, and leaching the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3)Putting the mixture into a solution, and carrying out hydrothermal reaction for 8 hours at 120 ℃; and after cooling to room temperature, taking out the sample, washing the sample with distilled water for 2 to 3 times, and drying the sample at the temperature of 60 ℃ for 12 hours to obtain the volume-shrinkage nickel sulfide/sulfur cobalt nickel/carbon nano tube foam.
Fig. 1 is a diagram of a comparison of the volume-shrunk nickel sulfide/nickel cobalt sulfide/carbon nanotube foam prepared in this embodiment before and after vulcanization, in fig. 1, a is an object before vulcanization and b is an object after vulcanization; as can be seen from FIG. 1, the volume ratio of the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam after vulcanization to the nickel cobaltate/carbon nanotube foam before vulcanization is 1:10, which provides the possibility that the electrode material is suitable for miniaturization energy storage devices.
FIG. 2 is an XRD pattern of the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam composite material prepared in this example, in which part a is NiS2The part b is NiCo2S4Part c is an XRD curve of the nickel sulfide/sulfur cobalt nickel/carbon nanotube foam composite material prepared in the embodiment, and characteristic peaks of the composite material basically compounded with nickel sulfide and sulfur cobalt nickel can be seen from figure 2.
Fig. 3 is SEM images of the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam composite material prepared in this embodiment before and after vulcanization, (a-b) is SEM images of nickel cobaltate/carbon nanotube foams before vulcanization (i.e., the product obtained in step 3) with different magnifications, and (c-f) is SEM images of nickel sulfide/nickel cobalt sulfide/carbon nanotube foams after vulcanization with different magnifications, as can be seen from fig. 3, the skeleton of the carbon nanotube foam after vulcanization is collapsed, the structure of the active material nanosheet is also damaged to some extent, the lamella is thinned, and a hole is formed, which increases the contact between the active material and the foam, increases the overall conductivity of the material, and also increases the contact between the material and the electrolyte, thereby providing a possibility for rapid transmission of electron ions.
The volume-shrunk nickel sulfide/nickel cobalt sulfide/carbon nanotube foam prepared in this embodiment can be used as an electrode material of a supercapacitor, and fig. 4 and 5 are a cyclic voltammogram and a charge-discharge curve of the electrode.
Fig. 4 is a cyclic voltammogram of the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam composite material prepared in this example at different sweep rates, in which relatively symmetric redox peaks are visible, and as the sweep rate increases, the cyclic voltammogram does not change greatly, indicating that the rate capability is relatively good.
Fig. 5 is a charging and discharging curve of the nickel sulfide/sulfur cobalt nickel/carbon nanotube foam composite material prepared in this example under different current densities, and a more obvious charging and discharging platform can be seen from fig. 5, which is generated by the pseudo-capacitance of nickel sulfide/sulfur cobalt nickel; at 1A g-1The mass specific capacitance of the material at current density was 2905F g-1The mass specific capacitance is about 2000F g higher than the conventional mass specific capacitance reported so far-1。
FIG. 6 is a graph of the cycle life of the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam composite prepared in this example at 10A g-1After the current density of the capacitor is circulated for 10000 circles, the capacity retention rate is still 83 percent, and good circulation stability is shown.
In the specific implementation, the mass fraction of the concentrated sulfuric acid is within the range of 95.0-98.0%, and the mass fraction of the concentrated nitric acid is within the range of 65.0-68.0%, so that the purpose of the invention can be achieved.
Example 2
In this example, the steps (1), (2) and (3) are the same as those in example 1, and the step (4) is specifically as follows: taking out the solution with the concentration of 0.006mol L-1And (3) transferring the solution of sodium sulfide into a 50mL polytetrafluoroethylene reaction kettle, soaking the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3) into the solution, carrying out hydrothermal reaction at 100 ℃ for 8h, cooling to room temperature, taking out the sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the nickel sulfide/nickel cobalt sulfide/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1Capacitance of 2307F g-1。
Example 3
In the preparation steps of this example, the steps (1), (2) and (3) are the same as those of example 1, and the step (4) is as follows: taking out the solution with the concentration of 0.006mol L-1The sodium sulfide solution was transferred into 50mL of TeflonAnd (3) soaking the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3) into the solution in a reaction kettle, carrying out hydrothermal reaction for 8h at 110 ℃, taking out a sample after cooling to room temperature, washing the sample with distilled water for 2-3 times, and drying for 12h at 60 ℃ to obtain nickel sulfide/sulfur cobalt nickel/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1The capacitance obtained by the test is 2750F g-1。
Example 4
In the preparation steps of this example, the steps (1), (2) and (3) are the same as those of example 1, and the step (4) is as follows: taking out the solution with the concentration of 0.006mol L-1Transferring the sodium sulfide solution into a 50mL polytetrafluoroethylene reaction kettle, soaking the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3) into the solution, carrying out hydrothermal reaction at 130 ℃ for 8h, cooling to room temperature, taking out a sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the nickel sulfide/nickel cobaltsulfide/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1Capacitance of 2800F g as measured by mass to capacitance-1。
Example 5
In the preparation steps of this example, the steps (1), (2) and (3) are the same as those of example 1. The step (4) is as follows: taking out the solution with the concentration of 0.006mol L-1And (3) transferring the solution of sodium sulfide into a 50mL polytetrafluoroethylene reaction kettle, immersing the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3) into the solution, carrying out hydrothermal reaction at 140 ℃ for 8h, cooling to room temperature, taking out the sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the nickel sulfide/nickel cobalt sulfide/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1Mass specific capacitance of 2645F g-1。
Example 6
In the preparation procedure of this example, step (1)) (2) and (3) are the same as in example 1. The step (4) is specifically as follows: taking out the solution with the concentration of 0.003mol L-1And (3) transferring the solution of sodium sulfide into a 50mL polytetrafluoroethylene reaction kettle, immersing the nickel cobaltate loaded on the carbon nano tube foam obtained in the step (3) into the solution, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling to room temperature, taking out the sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the nickel sulfide/nickel cobalt sulfide/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1The capacitance obtained by the test is 2745F g-1。
Example 7
In the preparation steps of this example, the steps (1), (2) and (3) are the same as those of example 1, and the step (4) is specifically as follows: taking out the solution with the concentration of 0.012mol L-1And (3) transferring the sodium sulfide solution into a 50mL polytetrafluoroethylene reaction kettle, immersing nickel cobaltate loaded on carbon nano tube foam obtained in the step (3) into the solution, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling to room temperature, taking out a sample, washing with distilled water for 2-3 times, and drying at 60 ℃ for 12h to obtain the nickel sulfide/nickel cobalt sulfide/carbon nano tube foam.
Through detection, the nickel sulfide/nickel cobalt sulfide/carbon nanotube foam obtained in the embodiment has a current density of 1A g-1Mass specific capacitance of 2630Fg-1。
Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that modifications can be made to the embodiments of the present invention which are intended to be covered by the scope of the appended claims.
Claims (7)
1. A preparation method of nickel sulfide/sulfur cobalt nickel/carbon nano tube foam comprises the following specific steps:
(a) dissolving the single-walled carbon nanotube in the mixed solution, refluxing for 2h at 70 ℃, performing suction filtration and cleaning until filter residue is neutral, and adding distilled water to obtain an acidified single-walled carbon nanotube dispersion solution; the mixed solution is obtained by mixing concentrated sulfuric acid and concentrated nitric acid;
(b) immersing polyurethane foam into the acidified single-wall carbon nanotube dispersion liquid obtained in the step (a), taking out and drying, and repeating the immersion-drying step twice to obtain polyurethane foam coated with carbon tubes; putting the polyurethane foam coated with the carbon tube on an alcohol lamp, and burning for 15-20s to obtain carbon nanotube foam;
(c) dissolving nickel chloride, cobalt chloride and urea in a methanol aqueous solution to obtain a pink solution, carrying out hydrothermal reaction on the carbon nano tube foam obtained in the step (b) in the pink solution at 120 ℃ for 6 hours, and then calcining at the constant temperature of 300 ℃ for 2 hours to obtain nickel cobaltate loaded on the carbon nano tube foam;
(d) immersing nickel cobaltate on the carbon nano tube foam obtained in the step (c) in a sodium sulfide solution, carrying out hydrothermal reaction for 8h at 120 ℃, washing with distilled water, and drying to obtain the nickel sulfide/nickel cobaltsulfide/carbon nano tube foam;
in the pink solution in the step (c), the concentrations of nickel chloride, cobalt chloride and urea are 0.005mol L in sequence-1、0.01molL-1、0.4molL-1。
2. The method of claim 1, wherein the acidified swnt dispersion of step (a) has a concentration of 1mgmL-1。
3. The method of claim 1, wherein the concentration of the sodium sulfide solution in step (d) is 0.003-0.012mol L-1。
4. The method for preparing nickel sulfide/nickel cobaltous sulfide/carbon nanotube foam according to claim 1, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution in the step (a) is 3: 1.
5. The method for preparing nickel sulfide/nickel cobaltous sulfide/carbon nanotube foam according to claim 1, wherein the polyurethane foam of step (b) is obtained by the following method: the polyurethane foam is washed by washing powder, distilled water and absolute ethyl alcohol in sequence and then dried for 12 hours at the temperature of 60 ℃.
6. The method for preparing nickel sulfide/sulfur cobalt nickel/carbon nanotube foam according to claim 1, wherein in the mixed solution in the step (a), the mass fraction of the concentrated sulfuric acid is 95.0-98.0%, and the mass fraction of the concentrated nitric acid is 65.0-68.0%.
7. Use of the nickel sulphide/nickel cobaltous sulphide/carbon nanotube foam prepared according to any one of claims 1 to 5 as an electrode for a supercapacitor.
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