CN109003827A - A kind of preparation method and application of spongy graphene/nickel cobalt sulfide composite material - Google Patents
A kind of preparation method and application of spongy graphene/nickel cobalt sulfide composite material Download PDFInfo
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- CN109003827A CN109003827A CN201810842895.1A CN201810842895A CN109003827A CN 109003827 A CN109003827 A CN 109003827A CN 201810842895 A CN201810842895 A CN 201810842895A CN 109003827 A CN109003827 A CN 109003827A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 56
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 238000013019 agitation Methods 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 5
- 229920006362 Teflon® Polymers 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000007781 pre-processing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 3
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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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- 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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- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to nano materials and electrochemical field, and in particular to a kind of preparation method of spongy graphene/nickel cobalt sulfide composite material.Using deionized water and normal octane as solvent, using sulphur, nickel nitrate and cobalt nitrate as sulphur source, nickel source and cobalt source, neopelex is surfactant, in stainless steel autoclave and provide magnetic agitation, reaction a period of time obtains spongy graphene/nickel cobalt sulfide composite material under certain temperature, and it is coated onto foam nickel surface, electrode material is pressed into after vacuum dried.The present invention passes through the pattern of regulation composite material, so that obtained graphene/nickel cobalt sulfide composite material as combination electrode material there is bigger specific surface area to substantially increase chemical property so that it be made to come into full contact with electrolyte.
Description
Technical field
The invention belongs to nano materials and electrochemical field, and in particular to a kind of spongy graphene/nickel cobalt sulfide is multiple
The preparation method and application of condensation material.
Background technique
In 21 century, " energy " has become the focus competed between country.In face of upcoming energy crisis, attempting
While finding new energy, scientists just actively research and development energy conservation, efficient energy storage device.It is super in new type of energy storage device
Capacitor is just received more and more attention because of the advantages that its power density is big, charge/discharge speed is fast and has extended cycle life.Super
In numerous component parts of grade capacitor, the characteristic of electrode material and combination have a significant impact to the performance tool of supercapacitor.
Graphene is the two-dimentional allotrope of carbon, integrates numerous good characteristics, such as high theoretical specific surface area, high
Carrier mobility, good translucency, high heat conductance, high mechanical strength and high electrochemical stability etc..Wherein, most peculiar
Place is the electric property that the unique electronic structure of graphene is shown, electron-trajectory transport such as at room temperature, unusual amount
Sub- Hall effect and quantum tunneling effect etc..But using simple graphene as when electrode material for super capacitor, performance
It is unable to satisfy the requirement of people, on the one hand, the graphene of chemical method preparation leads to it since the π-π active force of piece interlayer is easy to reunite
Specific surface area reduces；On the other hand, it is limited to electric double layer capacitance mechanism, the specific capacitance shown can not be with pseudo capacitance
It compares.Therefore, the reunion of graphene is reduced by preparation spongy graphene, while introduces pseudo capacitance and promotes material
The electrochemical capacitance characteristic of material is particularly important.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, to provide a kind of spongy graphene/nickel cobalt sulfide compound
The preparation method and application of material.The present invention passes through the pattern of regulation composite material, so that obtained graphene/nickel cobalt vulcanizes
Object composite material as combination electrode material there is bigger specific surface area to mention significantly so that it be made to come into full contact with electrolyte
High chemical property.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of spongy graphene/nickel cobalt sulfide composite material, comprising the following steps:
(1) it weighs graphene oxide and neopelex dissolves in deionized water respectively, the two is mixed into simultaneously ultrasound；
(2) sulphur ultrasonic disperse is weighed in normal octane, obtains normal octane mixed liquor, obtained normal octane mixed liquor is added drop-wise to
In the solution that step (1) obtains, and magnetic agitation；
(3) nickel nitrate and cobalt nitrate dissolution are weighed in deionized water, and is added dropwise to the mixed solution that step (2) obtains
In, and magnetic agitation；
(4) mixture that step (3) obtains is transferred in the stainless steel autoclave of Teflon liner, then be placed on
It is reacted in oil bath pan, and along with magnetic agitation；
(5) after step (4) being reacted products therefrom cooled to room temperature, then through centrifugation, washing, vacuum drying, final high temperature
Spongy graphene/nickel cobalt sulfide composite material is obtained after calcining.
It counts in mass ratio, graphene oxide: sulphur: neopelex=1:3:(5 ~ 10).
In step (1), the technological parameter of the ultrasound are as follows: ultrasonic power 200W, ultrasonic temperature are 25 DEG C, ultrasonic time
For 1 ~ 2h.
The volume ratio of normal octane described in step (2) and deionized water as described in step (1) is 1:(1 ~ 5).
In step (3), according to the molar ratio, nickel nitrate: cobalt nitrate=1:(0.1 ~ 2).
In step (4), the technological parameter that is reacted in oil bath pan are as follows: oil bath temperature is 160 DEG C ~ 240 DEG C, when heat preservation
Between for 12 ~ for 24 hours.
In step (5), the technological parameter of calcining are as follows: calcination atmosphere is argon gas, and calcination temperature is 500 DEG C, calcination time 1
~3h。
By spongy graphene obtained above/nickel cobalt sulfide composite material and conductive agent acetylene black and binder PVDF
It is uniformly mixed, suitable N-Methyl pyrrolidone (NMP) solvent is then added dropwise, is configured to uniform viscous paste, by it
It is coated in the foamed nickel current collector handled well, is dried in vacuo and tabletted evenly, the work electricity for test can be obtained
Pole；It counts in mass ratio, spongy graphene/nickel cobalt sulfide composite material: conductive acetylene is black: binder PVDF=80:15:5.
The preprocessing process of nickel foam are as follows: the L shape strip of the cm of 1 cm × 1 will be cut into a thickness of the nickel foam of 0.5mm,
Then successively use dilute hydrochloric acid, acetone, ethanol washing, remove the oxide and other pollutants on surface, finally with it is a large amount of go from
Sub- water supersound washing, it is finally 24 hours dry under 60 DEG C of vacuum conditions.
In the present invention, using normal octane as mantle plate, the aggregation fusion of normal octane drop can be reduced by ceaselessly stirring, from
And it is wrapped in graphene oxide uniformly around normal octane, the three-dimensional stacked duct of graphene can be obtained when normal octane evaporates, together
When high temperature and pressure in the environment of be conducive to leave defect on graphene two dimension basal plane.In addition, under the collaboration of surfactant,
Granular nickel cobalt sulfide is grown on graphene basal plane.The electrode obtained has higher specific capacitance, can be used for super capacitor
Device electrode material.
The beneficial effects of the present invention are:
(1) the graphene/nickel cobalt sulfide composite material prepared by the present invention has used solvent-thermal method, using normal octane as mantle
Plate leaves the duct of three-dimensional accumulation after normal octane evaporation, and pore-size distribution is wider, and specific surface area is high, is conducive to and electrolyte
It comes into full contact with；
(2) nickel cobalt sulfide is successfully grown in preparation process of the present invention on graphene basal plane, to introduce the quasi- electricity of faraday
Appearance improves the electrochemical capacitance characteristic of composite material；
(3) pollution of chemical reagent used in preparation process of the present invention is small, and dedoping step is simple, products pure.
Detailed description of the invention
Fig. 1 is spongy graphene/nickel cobalt sulfide composite material XRD spectrum prepared by the present invention；
Fig. 2 is spongy graphene/nickel cobalt sulfide composite material scanning electron microscopic picture prepared by the present invention；
Fig. 3 is spongy graphene/nickel cobalt sulfide composite material Cyclic voltamogram curve graph prepared by the present invention；
Fig. 4 is spongy graphene/nickel cobalt sulfide composite material charging and discharging curve figure prepared by the present invention；
Fig. 5 is spongy graphene/nickel cobalt sulfide composite material specific capacitance and current density relationship prepared by the present invention
Curve graph.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of preparation method of spongy graphene/nickel cobalt sulfide composite material, detailed process is as follows:
(1) it weighs 0.1g graphene oxide and 1g neopelex is dissolved in respectively in the deionized water of 20mL, by two
Person's mixing and ultrasound, ultrasonic power 200W, ultrasonic temperature are 25 DEG C, ultrasonic time 2h；
(2) 0.3g sulphur ultrasonic disperse is weighed in 20mL normal octane, and obtained normal octane mixed liquor is added drop-wise to step (1) and is obtained
To solution in, and magnetic agitation 60 minutes；
(3) 0.2g nickel nitrate and the dissolution of 0.1g cobalt nitrate are weighed in deionized water, and the mixing for being added dropwise to step (2) is molten
In liquid, and magnetic agitation 30 minutes；
(4) mixture that step (3) obtains is transferred in the stainless steel autoclave of 100mL Teflon liner, then by its
Be placed in oil bath pan, at 180 DEG C oil bath for 24 hours, and along with magnetic agitation；
(5) after taking out autoclave and cooled to room temperature, then the centrifugation of obtained product, washing, vacuum drying exist
The lower 500 DEG C of calcinings 2h of the protective atmosphere of argon gas, obtains spongy graphene/nickel cobalt sulfide composite material；
(6) by the binder of the conductive agent acetylene black and 0.2mg of the spongy graphene of 3.2mg/nickel cobalt sulfide and 0.6mg
PVDF is uniformly mixed in the ratio of 80:15:5, and N-Methyl pyrrolidone (NMP) solvent of a drop is then added dropwise, is configured to
Even viscous paste is uniformly coated in the pre- foamed nickel current collector pre-processed, is dried in vacuo and tabletted, i.e.,
It can obtain the working electrode for test；The preprocessing process of the nickel foam are as follows: will be cut into a thickness of the nickel foam of 0.5mm
The L shape strip of the cm of 1 cm × 1 then successively uses dilute hydrochloric acid, acetone, ethanol washing, removes oxide and other dirts on surface
Object is contaminated, it is finally 24 hours dry under 60 DEG C of vacuum conditions finally with a large amount of deionized water supersound washing.
Embodiment 2
A kind of preparation method of spongy graphene/nickel cobalt sulfide composite material, detailed process is as follows:
(1) it weighs 0.1g graphene oxide and 1g neopelex is dissolved in respectively in the deionized water of 20mL, by two
Person's mixing and ultrasound, ultrasonic power 200W, ultrasonic temperature are 25 DEG C, ultrasonic time 2h；
(2) 0.3g sulphur ultrasonic disperse is weighed in 20mL normal octane, and obtained normal octane mixed liquor is added drop-wise to step (1) and is obtained
To solution in, and magnetic agitation 60 minutes；
(3) 0.15g nickel nitrate and the dissolution of 0.15g cobalt nitrate are weighed in deionized water, and is added dropwise to the mixing of step (1)
In solution, and magnetic agitation 30 minutes；
(4) mixture that step (3) obtains is transferred in the stainless steel autoclave of 100mL Teflon liner, then by its
Be placed in oil bath pan, at 180 DEG C oil bath for 24 hours, and along with magnetic agitation；
(5) after taking out autoclave and cooled to room temperature, then the centrifugation of obtained product, washing, vacuum drying exist
The lower 500 DEG C of calcinings 2h of the protective atmosphere of argon gas, obtains spongy graphene/nickel cobalt sulfide composite material；
(6) by the binder of the conductive agent acetylene black and 0.2mg of the spongy graphene of 3.2mg/nickel cobalt sulfide and 0.6mg
PVDF is uniformly mixed in the ratio of 80:15:5, and suitable N-Methyl pyrrolidone (NMP) solvent is then added dropwise, and is configured to
Even viscous paste is uniformly coated in the pre- foamed nickel current collector pre-processed, is dried in vacuo and tabletted, i.e.,
It can obtain the working electrode for test；The preprocessing process of the nickel foam are as follows: will be cut into a thickness of the nickel foam of 0.5mm
The L shape strip of the cm of 1 cm × 1 then successively uses dilute hydrochloric acid, acetone, ethanol washing, removes oxide and other dirts on surface
Object is contaminated, it is finally 24 hours dry under 60 DEG C of vacuum conditions finally with a large amount of deionized water supersound washing.
Embodiment 3
A kind of preparation method of spongy graphene/nickel cobalt sulfide composite material, detailed process is as follows:
(1) it weighs 0.1g graphene oxide and 1g neopelex is dissolved in respectively in the deionized water of 20mL, by two
Person's mixing and ultrasound, ultrasonic power 200W, ultrasonic temperature are 25 DEG C, ultrasonic time 2h；
(2) 0.3g sulphur ultrasonic disperse is weighed in 20mL normal octane, and obtained normal octane mixed liquor is added drop-wise to step (1) and is obtained
To solution in, and magnetic agitation 60 minutes；
(3) 0.1g nickel nitrate and the dissolution of 0.2g cobalt nitrate are weighed in deionized water, and the mixing for being added dropwise to step (2) is molten
In liquid, and magnetic agitation 30 minutes；
(4) mixture that step (3) obtains is transferred in the stainless steel autoclave of 100mL Teflon liner, then by its
Be placed in oil bath pan, at 180 DEG C oil bath for 24 hours, and along with magnetic agitation；
(5) after taking out autoclave and cooled to room temperature, then the centrifugation of obtained product, washing, vacuum drying exist
The lower 500 DEG C of calcinings 2h of the protective atmosphere of argon gas, obtains spongy graphene/nickel cobalt sulfide composite material；
(6) by the binder of the conductive agent acetylene black and 0.2mg of the spongy graphene of 3.2mg/nickel cobalt sulfide and 0.6mg
PVDF is uniformly mixed in the ratio of 80:15:5, and suitable N-Methyl pyrrolidone (NMP) solvent is then added dropwise, and is configured to
Even viscous paste is uniformly coated in the pre- foamed nickel current collector pre-processed, is dried in vacuo and tabletted, i.e.,
It can obtain the working electrode for test；The preprocessing process of the nickel foam are as follows: will be cut into a thickness of the nickel foam of 0.5mm
The L shape strip of the cm of 1 cm × 1 then successively uses dilute hydrochloric acid, acetone, ethanol washing, removes oxide and other dirts on surface
Object is contaminated, it is finally 24 hours dry under 60 DEG C of vacuum conditions finally with a large amount of deionized water supersound washing.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of spongy graphene/nickel cobalt sulfide composite material preparation method, it is characterised in that: the following steps are included:
(1) it weighs graphene oxide and neopelex dissolves in deionized water respectively, the two is mixed into simultaneously ultrasound；
(2) sulphur ultrasonic disperse is weighed in normal octane, obtains normal octane mixed liquor, obtained normal octane mixed liquor is added drop-wise to
In the solution that step (1) obtains, and magnetic agitation；
(3) nickel nitrate and cobalt nitrate dissolution are weighed in deionized water, and is added dropwise to the mixed solution that step (2) obtains
In, and magnetic agitation；
(4) mixed solution that step (3) obtains is transferred in the stainless steel autoclave of Teflon liner, then is placed
It is reacted in oil bath pan, and along with magnetic agitation；
(5) it after step (4) being reacted products therefrom cooled to room temperature, then through centrifugation, washing, vacuum drying, finally calcines
After obtain spongy graphene/nickel cobalt sulfide composite material.
2. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: count in mass ratio, graphene oxide: sulphur: neopelex=1:3:(5 ~ 10).
3. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: in step (1), the technological parameter of the ultrasound are as follows: ultrasonic power 200W, ultrasonic temperature be 25 DEG C, ultrasonic time be 1 ~
2h。
4. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: the volume ratio of normal octane described in step (2) and deionized water as described in step (1) is 1:(1 ~ 5).
5. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: in step (3), according to the molar ratio, nickel nitrate: cobalt nitrate=1:(0.1 ~ 2).
6. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: in step (4), the technological parameter that is reacted in oil bath pan are as follows: oil bath temperature is 160 DEG C ~ 240 DEG C, and soaking time is
12~24h。
7. spongy graphene according to claim 1/nickel cobalt sulfide composite material preparation method, feature exist
In: in step (5), the technological parameter of calcining are as follows: calcination atmosphere is argon gas, and calcination temperature is 500 DEG C, and calcination time is 1 ~ 3h.
8. a kind of spongy graphene made from preparation method as described in claim 1/nickel cobalt sulfide composite material is super
Application in grade capacitor electrode material.
9. application according to claim 8, it is characterised in that: by spongy graphene/nickel cobalt sulfide composite material with
Conductive agent acetylene black and binder PVDF are uniformly mixed, and N-Methyl pyrrolidone solvent is then added dropwise, and are configured to uniform sticky
Slurry is uniformly coated in the foamed nickel current collector handled well, is dried in vacuo and tabletted, is obtained working electrode
Material；It counts in mass ratio, spongy graphene/nickel cobalt sulfide composite material: conductive agent acetylene black: binder PVDF=80:
15:5。
10. application according to claim 9, it is characterised in that: the preprocessing process of nickel foam are as follows: will be with a thickness of 0.5mm
Nickel foam be cut into the L shape strip of the cm of 1 cm × 1, then successively use dilute hydrochloric acid, acetone, ethanol washing, remove the oxygen on surface
Compound and other pollutants finally use deionized water supersound washing, finally 24 hours dry under 60 DEG C of vacuum conditions.
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