CN114429868B - Preparation method of graphene/cobalt tetrasulfide nickel electrode material with sandwich structure - Google Patents
Preparation method of graphene/cobalt tetrasulfide nickel electrode material with sandwich structure Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 239000007772 electrode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 title claims description 6
- 239000010941 cobalt Substances 0.000 title claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 6
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000006249 magnetic particle Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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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Abstract
The invention discloses a preparation method of a sandwich structured graphene/cobaltosic sulfide nickel electrode material, which specifically comprises the following steps: firstly, taking graphite foil as an anode, taking a platinum wire as a cathode, carrying out electrochemical stripping, then dissolving in deionized water, and carrying out suction filtration on formed graphene centrifugate to form a film; then NiCl is added 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, and performing hydrothermal treatment to obtain NiCo (OH) powder; mixing NiCo (OH) powder, thiourea and H 2 O is mixed and subjected to hydrothermal reaction to obtain magnetic NiCo 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the NiCo is prepared 2 S 4 Dissolving in deionized water, pouring on a film formed before, and carrying out suction filtration to form a double-layer film; pouring the graphene centrifugate on the double-layer membrane, performing suction filtration again to form a membrane, and drying. The sandwich structure electrode material promotes the transmission of ions and electrons; niCo 2 S 4 In the middle of the interlayer, partial pseudo-capacitance is provided, and the electrochemical performance of the material is improved.
Description
Technical Field
The invention belongs to the technical field of electrode material preparation, and in particular relates to graphene/tetrasulfide disulfide with a sandwich structureNickel cobalt (NiCo) 2 S 4 ) A preparation method of an electrode material.
Background
With the demand of human society for energy, the development of novel energy storage and conversion devices such as lithium ion batteries, fuel cells, solar cells and supercapacitors is of great importance. Among them, the super capacitor has been receiving a great deal of attention in recent years due to the advantages of both high energy density of the battery and high power density of the conventional capacitor. As an excellent supercapacitor electrode material, graphene has good conductivity, excellent electron mobility and a large specific surface area. However, due to the van der Waals force and pi-pi bond stacking effect, the graphene on the solution or the substrate is easy to irreversibly agglomerate in the processes of preparation, preservation, testing and the like, which is not beneficial to the full utilization of the specific surface area.
The self-supporting graphene (SGr) has good mechanical strength and higher surface energy, so that the generated wrinkle morphology reduces the agglomeration to a certain extent. SCr remains an electric double layer capacitor in nature, which results in a generally smaller capacitance that is difficult to meet in practical applications. Compounding SCr with conductive polymers can significantly improve capacitive performance. The composite material with the sandwich structure obtained by combining graphene and nickel cobalt sulfide is an effective method for preparing the supercapacitor electrode.
Disclosure of Invention
The invention aims to provide a sandwich structure graphene/NiCo 2 S 4 The preparation method of the electrode material solves the problems of low conductivity and poor stability caused by doping of the current collector and the binder in the preparation of the existing electrode material.
The technical scheme adopted by the invention is that the graphene/NiCo with the sandwich structure 2 S 4 The preparation method of the electrode material comprises the following steps:
step 1, using graphite foil as a carbon electrode, namely an anode, and a platinum wire as a cathode, and performing electrochemical stripping of graphite to obtain stripped graphene;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying to obtain NiCo (OH) powder;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
Step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing, pouring the solution on the membrane formed in the step 3 after ultrasonic treatment, and carrying out suction filtration to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material.
The present invention is also characterized in that,
in step 1, specifically: graphite foil and platinum electrode were placed at 0.1M (NH 4 ) 2 SO 4 And then electrochemical stripping is carried out by applying positive voltage of 9.9V to the graphite electrode, after the graphite stripping is finished, the product is subjected to vacuum filtration by deionized water, and a filter membrane with the pore diameter of 0.45 mu m is used for filtration, so that the stripped graphene can be obtained.
In step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 The molar ratio of O to urea is 1:1:3.
in the step 4, the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 150-180 ℃, and the hydrothermal reaction time is 22-26h.
In the step 5, the mass ratio of the NiCo (OH) powder to the thiourea is 1:2.
in the step 5, the ultrasonic treatment time is 10-30min; the hydrothermal reaction temperature is 180-260 ℃ and the hydrothermal reaction time is 8-16h.
The beneficial effects of the invention are as follows: the peeled graphene-NiCo with the sandwich structure is prepared by a simple vacuum-assisted suction filtration film forming method 2 S 4 And stripping the composite film of the graphene to obtain the flexible and self-supporting composite electrode material. The membrane electrode material with a sandwich structure is obtained by a simple preparation method, so that the transmission of ions and electrons is promoted; niCo 2 S 4 In the middle of the interlayer, a part of pseudo-capacitor is provided, the overall electrochemical performance is improved, a self-supporting structure without current collector and adhesive is formed, and the self-supporting structure has high conductivity, flexibility and mechanical stability. The prepared exfoliated graphene-NiCo with sandwich structure 2 S 4 Composite film of exfoliated graphene with specific capacity of about 0.0631mF cm as electrode -2 。
Drawings
FIG. 1 shows a sandwich-structured exfoliated graphene-NiCo prepared in examples 1-3 of the present invention 2 S 4 Cyclic voltammetry profile of exfoliated graphene electrode material.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and the accompanying drawings.
The invention relates to a sandwich structure graphene/cobaltosic sulfide nickel (NiCo) 2 S 4 ) The preparation method of the electrode material comprises the following steps:
step 1, using graphite foil as carbon electrode, i.e. anode, platinum wire as cathode for electrochemical stripping of graphite, placing graphite foil and platinum electrode at 0.1M (NH 4 ) 2 SO 4 Then, carrying out electrochemical stripping by applying a positive voltage of 9.9V to a graphite electrode, and after the graphite stripping is finished, carrying out vacuum filtration on a product by using deionized water, and obtaining stripped graphene by using a filter membrane with the pore diameter of 0.45 mu m during filtration;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
the centrifugal speed is 3000r/min, and the centrifugal time is 20min;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying to obtain NiCo (OH) powder;
NiCl 2 ·6H 2 O、CoCl 2 ·6H 2 the molar ratio of O to urea is 1:1:3, a step of;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 150-180 ℃, and the hydrothermal reaction time is 22-26h;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
The mass ratio of the NiCo (OH) powder to the thiourea is 1:2;
the ultrasonic treatment time is 10-30min; the hydrothermal reaction temperature is 180-260 ℃ and the hydrothermal reaction time is 8-16h;
step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing by ultrasonic, pouring on the membrane formed in the step 3, and filtering to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material.
Example 1
graphene/NiCo with sandwich structure 2 S 4 The preparation method of the electrode material comprises the following steps:
step 1, using graphite foil as carbon electrode, i.e. anode, platinum wire as cathode for electrochemical stripping of graphite, placing graphite foil and platinum electrode at 0.1M (NH 4 ) 2 SO 4 Then, carrying out electrochemical stripping by applying a positive voltage of 9.9V to a graphite electrode, and after the graphite stripping is finished, carrying out vacuum filtration on a product by using deionized water, and obtaining stripped graphene by using a filter membrane with the pore diameter of 0.45 mu m during filtration;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
the centrifugal speed is 3000r/min, and the centrifugal time is 20min;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying at 80 ℃ for 12 hours to obtain NiCo (OH) powder;
NiCl 2 ·6H 2 O、CoCl 2 ·6H 2 the molar ratio of O to urea is 1:1:3, a step of;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 24 hours;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
The mass ratio of the NiCo (OH) powder to the thiourea is 1:2;
the ultrasonic treatment time is 30min; the hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 16h;
step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing by ultrasonic, pouring on the membrane formed in the step 3, and filtering to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material. Stripping machineGraphene and NiCo 2 S 4 The molar ratio of the exfoliated graphene is 3:1:3.
example 2
graphene/NiCo with sandwich structure 2 S 4 The preparation method of the electrode material comprises the following steps:
step 1, using graphite foil as carbon electrode, i.e. anode, platinum wire as cathode for electrochemical stripping of graphite, placing graphite foil and platinum electrode at 0.1M (NH 4 ) 2 SO 4 Then, carrying out electrochemical stripping by applying a positive voltage of 9.9V to a graphite electrode, and after the graphite stripping is finished, carrying out vacuum filtration on a product by using deionized water, and obtaining stripped graphene by using a filter membrane with the pore diameter of 0.45 mu m during filtration;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
the centrifugal speed is 3000r/min, and the centrifugal time is 20min;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying to obtain NiCo (OH) powder;
NiCl 2 ·6H 2 O、CoCl 2 ·6H 2 the molar ratio of O to urea is 1:1:3, a step of;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 150 ℃, and the hydrothermal reaction time is 22 hours;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
The mass ratio of the NiCo (OH) powder to the thiourea is 1:2;
the ultrasonic treatment time is 30min; the hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 12 hours;
step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing by ultrasonic, pouring on the membrane formed in the step 3, and filtering to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material. Exfoliated graphene, niCo 2 S 4 The molar ratio of the exfoliated graphene is 2:1:2.
example 3
graphene/NiCo with sandwich structure 2 S 4 The preparation method of the electrode material comprises the following steps:
step 1, using graphite foil as carbon electrode, i.e. anode, platinum wire as cathode for electrochemical stripping of graphite, placing graphite foil and platinum electrode at 0.1M (NH 4 ) 2 SO 4 Then, carrying out electrochemical stripping by applying a positive voltage of 9.9V to a graphite electrode, and after the graphite stripping is finished, carrying out vacuum filtration on a product by using deionized water, and obtaining stripped graphene by using a filter membrane with the pore diameter of 0.45 mu m during filtration;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
the centrifugal speed is 3000r/min, and the centrifugal time is 20min;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying to obtain NiCo (OH) powder;
NiCl 2 ·6H 2 O、CoCl 2 ·6H 2 the molar ratio of O to urea is 1:1:3, a step of;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 150 ℃, and the hydrothermal reaction time is 22 hours;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
The mass ratio of the NiCo (OH) powder to the thiourea is 1:2;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 15 hours;
step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing by ultrasonic, pouring on the membrane formed in the step 3, and filtering to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material. Exfoliated graphene, niCo 2 S 4 The molar ratio of the exfoliated graphene is 1:1:1.
the exfoliated graphene-NiCo of the sandwich structure prepared in examples 1-3 2 S 4 Stripping graphene electrode material as self-supporting electrode, PVA/H 3 PO 4 The gel was tested for performance as an electrolyte. The assembled device described above was used for cyclic voltammetry measurements using a coster electrochemical workstation. Fig. 1 is a graph of cyclic voltammetry and specific capacity versus current density, which maintains a good shape as scan rate increases.
Claims (3)
1. The preparation method of the graphene/cobalt tetrasulfide nickel electrode material with the sandwich structure is characterized by comprising the following steps of:
step 1, using graphite foil as a carbon electrode, namely an anode, and a platinum wire as a cathode, and performing electrochemical stripping of graphite to obtain stripped graphene;
step 2, dissolving the peeled graphene in deionized water, performing ultrasonic treatment, and centrifuging to form graphene centrifugate;
step 3, carrying out suction filtration on the graphene centrifugate to form a film;
step 4, niCl 2 ·6H 2 O、CoCl 2 ·6H 2 Mixing O and urea, performing ultrasonic treatment, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain a hydrothermal product; vacuum filtering the hydrothermal product with deionized water, and drying to obtain NiCo (OH) powder;
NiCl 2 ·6H 2 O、CoCl 2 ·6H 2 the molar ratio of O to urea is 1:1:3, a step of;
the ultrasonic treatment time is 25min; the hydrothermal reaction temperature is 150-180 ℃, and the hydrothermal reaction time is 22-26h;
step 5, niCo (OH) powder, thiourea and H 2 O mixing, ultrasonic treatment, transferring into a high-pressure reaction kettle for hydrothermal reaction, and vacuum filtering the obtained hydrothermal product with deionized water to obtain magnetic particles NiCo 2 S 4 ；
The mass ratio of the NiCo (OH) powder to the thiourea is 1:2;
step 6, magnetic particles NiCo 2 S 4 Dissolving in deionized water, uniformly mixing, pouring on the membrane formed in the step 3, and filtering to form a membrane;
step 7, pouring the graphene centrifugate in the step 2 on the film formed in the step 6, performing suction filtration again to form a film, and drying to obtain the peeled graphene-NiCo with the sandwich structure 2 S 4 -exfoliating the graphene electrode material.
2. The preparation method of the sandwich structured graphene/cobalt tetrasulfide nickel electrode material according to claim 1, wherein in the step 1, specifically: graphite foil and platinum electrode were placed at 0.1M (NH 4 ) 2 SO 4 And then electrochemical stripping is carried out by applying positive voltage of 9.9V to the graphite electrode, after the graphite stripping is finished, the product is subjected to vacuum filtration by deionized water, and a filter membrane with the pore diameter of 0.45 mu m is used for filtration, so that the stripped graphene can be obtained.
3. The preparation method of the sandwich structured graphene/cobalt tetrasulfide nickel electrode material according to claim 1, wherein in the step 5, the ultrasonic treatment time is 10-30min; the hydrothermal reaction temperature is 180-260 ℃ and the hydrothermal reaction time is 8-16h.
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