CN110070996A - Nickel sulfide/graphene composite material preparation method and application - Google Patents
Nickel sulfide/graphene composite material preparation method and application Download PDFInfo
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- CN110070996A CN110070996A CN201910451060.8A CN201910451060A CN110070996A CN 110070996 A CN110070996 A CN 110070996A CN 201910451060 A CN201910451060 A CN 201910451060A CN 110070996 A CN110070996 A CN 110070996A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- -1 graphene compound Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010008 shearing Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 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
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses the preparation methods and application of a kind of nickel sulfide/graphene composite material, are related to electrochemical material field, are effectively removed graphite for graphene by physics liquid phase stripping means, then grow nickel sulfide on the surface of graphene by microwave method.Nanometer nickel sulfide structure is evenly distributed on the surface of graphene in the composite material of preparation, is completely embedded with graphene sheet layer, stable structure.The electrochemical test data of the composite material shows the synergistic effect of nickel sulfide and graphene so that composite material has played the advantage of the two, to obtain having many advantages, such as the electrode material for super capacitor that impedance is small, specific capacitance is high and cyclical stability is strong.Electrode material preparation efficiency of the invention is high, and simple process, safety and environmental protection has potential application in industrialized production supercapacitor.
Description
Technical field
The present invention relates to the technical fields of electrochemical material, refer in particular to a kind of system of nickel sulfide/graphene composite material
Preparation Method and application.
Background technique
With the continuous research and development of various advanced electronic products, cleaning, energy storage efficiently, Ke Xunhuanliyong and converting means
The exploitation set has received more and more attention.Supercapacitor is as one kind between traditional capacitor and chemical cell
Novel energy storage apparatus, because of its high power density, fast charging and discharging characteristic, the advantages such as long circulation life and high security are in electronics
The fields such as electric power have huge application potential.
The core of supercapacitor is mainly made of electrode material, collector, electrolyte and diaphragm, and wherein electrode material is
Influence one of chemical property and the most critical factor of cost.Currently, common electrode material for super capacitor includes carbon substrate
Material, transition metal nitrogen/oxygen/phosphorus/sulphur/hydroxide, conducting polymer etc..The one kind of graphene as carbon-based material, solely because of it
Special single layer of carbon atom structure and to have high mechanical strength, large specific surface area, good conductivity and cyclical stability height etc. excellent
Performance, energy stores and release are completed by the double electrical layers between electrode surface and electrolyte.And transition is golden
Belonging to sulfide, there are excellent performance, the energy stores such as abundance, theoretical specific capacitance height, energy density height to be then with release
It is completed by the reversible redox reaction in electrode surface or its quasi- two-dimensional space.
In general, the specific capacitance and energy density of transient metal sulfide are higher than graphene, but material electric conductivity is low,
Cause forthright again and cyclical stability poor.In addition, be easy to stack between graphene sheet layer, and nickel sulfide is easy to reunite, and causes
Specific surface area utilization rate is low, is unfavorable for the infiltration of electrolyte and then influences chemical property.To sum up reason, the electrode of single kind
Material will receive limitation in the practical application of supercapacitor.
Existing graphene/vulcanization nickel composite material applies the related work in supercapacitor, but its preparation side at present
Fado is that oxidation-reduction method prepares graphene, then loads nickel sulfide by hydro-thermal or electrochemical deposition method, usually to material
Regulate and control interact between not in place, each ingredient it is undesirable or can not volume production.Therefore it is necessary to invent it is a kind of it is simple and easy,
It can improve to economical and efficient the preparation method of graphene/vulcanization nickel composite material chemical property.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology with it is insufficient, propose a kind of simple and easy, safety and environmental protection,
The preparation method and application of reliable nickel sulfide/graphene composite material, it is compound can to improve to economical and efficient graphene/nickel sulfide
The chemical property of material.
To achieve the above object, technical solution provided by the present invention are as follows: nickel sulfide/graphene composite material preparation side
Method, comprising the following steps:
1) by expanded graphite progress high-temperature expansion obtain graphite worm, then by graphite worm in deionized water successively into
Row shearing, it is high-pressure homogeneous, graphene slurry is obtained, is freeze-dried to obtain graphene powder with freeze drier；
2) Nickel dichloride hexahydrate is dissolved in deionized water and is configured to solution, the graphene powder in step 1) is added,
It stirs, obtains dispersion liquid；Thiocarbamide is added in dispersion liquid again, continues to stir evenly, obtains mixed liquor；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, after carrying out microwave reaction, it is multiple to be washed with deionized product, finally dries the product to obtain nickel sulfide/graphene multiple
Condensation material, obtained nickel sulfide/graphene composite material exterior appearance are that nickel sulfide cube is evenly distributed in graphene
Sheet surfaces, specific surface area are 150~520m2/g。
In step 1), the expansion rate of expanded graphite is 300~1500, and thermal expansion temperature is 800~1200 DEG C.
In step 1), graphite worm and deionized water according to 1~20:50~99 mass ratio revolving speed 1200~
High speed shear is carried out under 2500rpm tentatively to remove, shear time is 40~120min, then 400 are set as by pressure~
The high pressure homogenizer of 1600bar carries out homogeneous removing into graphene slurry, and homogenizing time is 30~80min.
In step 1), graphene slurry freeze-drying time is 3~6h, and cryogenic temperature is -46~-42 DEG C, vacuum drying
Time is 12~72h.
In step 2), the concentration of Nickel dichloride hexahydrate is 0.05~0.2mol/L；Nickel dichloride hexahydrate, thiocarbamide and graphite
The ratio between amount of substance of alkene is 1:1~4:0.5~2.
In step 2), mixing time is all 20min, stirring rate 800rpm twice；
In step 3), microwave reaction temperature is 150~220 DEG C, and reaction power is 800~1300W, reaction time 30
~90min.
Nickel sulfide/graphene composite material application made from the above method, specially nickel sulfide/graphene composite material
Application in electrode of super capacitor, wherein by nickel sulfide/graphene composite material in supercapacitor three-electrode system
Survey constant current charge-discharge test is carried out, it is Pt to electrode that the reference electrode used, which is Ag/AgCl, and electrolyte is 3M KOH solution, is surveyed
The voltage window tried out is 0.8~1.2V, and specific capacitance can reach 845-1464F/g under the current density of 1A/g.
Further, the preparation of the electrode of super capacitor includes the following steps:
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on flexible conductive substrates, it is dry in 80 DEG C of baking ovens.
Further, the flexible conductive substrates are nickel foam, aluminium foil, titanium foil, copper foil, stainless steel substrates, carbon cloth, PET/ITO
In any one.
Compared with prior art, the present invention have the following advantages that with the utility model has the advantages that
1, the graphene and nickel sulfide that the present invention for the first time removes physics liquid phase are carried out compound by microwave method.
2, whole flow process of the present invention is simple and easy, safety and environmental protection, economical and efficient.Physics liquid phase stripping method and prior art phase
Than being easier to industrial volume production, microwave method compared to the prior art efficiently by change the temperature power time to composite material into
Row regulation, makes the morphology controllable of nickel sulfide, and be completely embedded with graphene sheet layer, stable structure.
3, the graphene and nickel sulfide that the present invention for the first time removes physics liquid phase are carried out compound by microwave method.This composite wood
Graphene forms conductive network as electron propagation ducts wherein in material, and prevents nickel sulfide from reuniting；Nickel sulfide is wherein
More electro-chemical activity sites are provided, and prevent graphene from stacking.
4, the magnetic agitation of the invention involved in microwave reaction, therefore, nickel sulfide is upper on the surface of graphene to be had more evenly
Distribution.
5, this composite material preparation electrode of super capacitor because the synergistic effect of graphene and nickel sulfide realize advantage it is mutual
It mends, has that Low ESR, high specific capacitance, high power be forthright concurrently and the advantages such as long circulation life.
Detailed description of the invention
Fig. 1 is that constant current charge-discharge of the nickel sulfide/graphene composite material of the preparation of embodiment 1 under different current densities is surveyed
Try curve.
Fig. 2 is that specific capacity of the nickel sulfide/graphene composite material of the preparation of embodiment 1 under different current densities changes song
Line.
Specific embodiment
Below with reference to multiple specific embodiments, the invention will be further described.
Embodiment 1
1) expanded graphite that expansion rate is 1000 is subjected to the progress high-temperature expansion at 900 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 10:90 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 2200rpm
Removing, shear time 50min.Homogeneous removing, homogenizing time are carried out by the high pressure homogenizer that pressure is set as 800bar again
For 60min, graphene slurry is obtained.Graphene slurry is put into freeze drier and freezes 4h, cryogenic temperature is -45 DEG C, then
Vacuum drying 48h, obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.05mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.3mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 220 DEG C, reaction power 900W, with this condition carry out microwave reaction 60min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on carbon cloth substrate, it is dry in 80 DEG C of baking ovens.The electrode prepared is existed
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.Constant-current charge of the electrode under different current densities puts curve such as Fig. 1, the voltage tested out
Window is 1.2V, and specific capacitance can achieve 1464F/g under the current density of 1A/g.5A/g is increased to by 1A/g in current density
When, as shown in Fig. 2, specific capacity conservation rate is 78%, embody good high rate performance.
Embodiment 2
1) expanded graphite that expansion rate is 300 is subjected to the progress high-temperature expansion at 1200 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 1:99 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 1200rpm
Removing, shear time 40min.Homogeneous removing, homogenizing time are carried out by the high pressure homogenizer that pressure is set as 400bar again
For 30min, graphene slurry is obtained.Graphene slurry is put into freeze drier and freezes 6h, cryogenic temperature is -42 DEG C, then
Vacuum drying 72h, obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.1mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.2mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 150 DEG C, reaction power 1000W, with this condition carry out microwave reaction 90min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly in aluminum substrates, it is dry in 80 DEG C of baking ovens.The electrode prepared is existed
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 0.8V, and specific capacitance can achieve under the current density of 1A/g
845F/g。
Embodiment 3
1) expanded graphite that expansion rate is 1500 is subjected to the progress high-temperature expansion at 800 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 20:50 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 2500rpm
Removing, shear time 120min.Homogeneous removing is carried out by the high pressure homogenizer that pressure is set as 1600bar again, when homogeneous
Between be 80min, obtain graphene slurry.Graphene slurry is put into freeze drier and freezes 3h, cryogenic temperature is -46 DEG C,
Vacuum drying 12h again obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.05mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.05mol/L is added again
Into above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 180 DEG C, reaction power 1200W, with this condition carry out microwave reaction 45min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on titanium foil substrate, it is dry in 80 DEG C of baking ovens.The electrode prepared is existed
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 0.8V, and specific capacitance can achieve under the current density of 1A/g
982F/g。
Embodiment 4
1) expanded graphite that expansion rate is 800 is subjected to the progress high-temperature expansion at 1000 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 1:50 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 1500rpm
Removing, shear time 90min.Homogeneous removing, homogenizing time are carried out by the high pressure homogenizer that pressure is set as 600bar again
For 60min, graphene slurry is obtained.Graphene slurry is put into freeze drier and freezes 5h, cryogenic temperature is -42 DEG C, then
Vacuum drying 48h, obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.2mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.2mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 200 DEG C, reaction power 800W, with this condition carry out microwave reaction 30min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on copper foil substrate, it is dry in 80 DEG C of baking ovens.The electrode prepared is existed
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 0.9V, and specific capacitance can achieve under the current density of 1A/g
1146F/g。
Embodiment 5
1) expanded graphite that expansion rate is 500 is subjected to the progress high-temperature expansion at 1100 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 20:80 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 1200rpm
Removing, shear time 120min.Homogeneous removing is carried out by the high pressure homogenizer that pressure is set as 1200bar again, when homogeneous
Between be 60min, obtain graphene slurry.Graphene slurry is put into freeze drier and freezes 4h, cryogenic temperature is -43 DEG C,
Vacuum drying 36h again obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.1mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.4mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 150 DEG C, reaction power 800W, with this condition carry out microwave reaction 80min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on stainless steel lining bottom, it is dry in 80 DEG C of baking ovens.The electrode that will be prepared
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 1.0V, and specific capacitance can achieve under the current density of 1A/g
1024F/g。
Embodiment 6
1) expanded graphite that expansion rate is 600 is subjected to the progress high-temperature expansion at 1200 DEG C and obtains graphite worm, then
Graphite worm is mixed according to the mass ratio of 4:96 in deionized water, it is preliminary that high speed shear is carried out at revolving speed 1800rpm
Removing, shear time 60min.Homogeneous removing, homogenizing time are carried out by the high pressure homogenizer that pressure is set as 1000bar again
For 45min, graphene slurry is obtained.Graphene slurry is put into freeze drier and freezes 3h, cryogenic temperature is -45 DEG C, then
Vacuum drying 40h, obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.2mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.4mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 160 DEG C, reaction power 1300W, with this condition carry out microwave reaction 30min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on carbon cloth substrate, it is dry in 80 DEG C of baking ovens.The electrode prepared is existed
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 1.2V, and specific capacitance can achieve under the current density of 1A/g
955F/g。
Embodiment 7
1) expanded graphite that expansion rate is 800 is subjected to the progress high-temperature expansion at 800 DEG C and obtains graphite worm, then will
Graphite worm is mixed according to the mass ratio of 10:60 in deionized water, and high speed shear is carried out at revolving speed 2000rpm and is tentatively shelled
From shear time 100min.Homogeneous removing, homogenizing time are carried out by the high pressure homogenizer that pressure is set as 1500bar again
For 50min, graphene slurry is obtained.Graphene slurry is put into freeze drier and freezes 4h, cryogenic temperature is -44 DEG C, then
Vacuum drying 60h, obtains graphene powder；
2) Nickel dichloride hexahydrate is dissolved in the solution for being configured to that concentration is 0.1mol/L in deionized water, is added
Graphene powder in 0.1mol/L step 1) stirs 20min at revolving speed 800rpm.The thiocarbamide of 0.1mol/L is added to again
In above-mentioned dispersion liquid, continue to stir 20min at revolving speed 800rpm to uniform；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic force is added and stirs
Mix son, reaction temperature is set as 220 DEG C, reaction power 1100W, with this condition carry out microwave reaction 45min after, spend from
Sub- water washing product three times, finally dries product to obtain nickel sulfide/graphene composite material.
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in molten
In agent ethyl alcohol after ground and mixed 0.5h, it is coated uniformly on nickel foam substrate, it is dry in 80 DEG C of baking ovens.The electrode that will be prepared
Survey constant current charge-discharge test is carried out in supercapacitor three-electrode system, the reference electrode used is Ag/AgCl, is to electrode
Pt, electrolyte are 3M KOH solution.The voltage window tested out is 0.8V, and specific capacitance can achieve under the current density of 1A/g
1285F/g。
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. nickel sulfide/graphene composite material preparation method, which comprises the following steps:
1) expanded graphite progress high-temperature expansion is obtained into graphite worm, then successively cuts graphite worm in deionized water
It cuts, it is high-pressure homogeneous, graphene slurry is obtained, is freeze-dried to obtain graphene powder with freeze drier；
2) Nickel dichloride hexahydrate is dissolved in deionized water and is configured to solution, the graphene powder in step 1) is added, sufficiently
It stirs evenly, obtains dispersion liquid；Thiocarbamide is added in dispersion liquid again, continues to stir evenly, obtains mixed liquor；
3) mixed liquor in step 2) is put into the ptfe autoclave of microwave reactor outfit, magnetic agitation is added
Son, after carrying out microwave reaction, it is multiple to be washed with deionized product, finally dries the product to obtain nickel sulfide/graphene compound
Material, obtained nickel sulfide/graphene composite material exterior appearance are that nickel sulfide cube is evenly distributed in graphene film
Layer surface, specific surface area are 150~520m2/g。
2. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 1)
In, the expansion rate of expanded graphite is 300~1500, and thermal expansion temperature is 800~1200 DEG C.
3. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 1)
In, graphite worm and deionized water carry out high speed according to the mass ratio of 1~20:50~99 at 1200~2500rpm of revolving speed
The preliminary removing of shearing, shear time are 40~120min, then by pressure be set as the high pressure homogenizer of 400~1600bar into
For the removing of row homogeneous at graphene slurry, homogenizing time is 30~80min.
4. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 1)
In, graphene slurry freeze-drying time is 3~6h, and cryogenic temperature is -46~-42 DEG C, and the vacuum drying time is 12~72h.
5. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 2)
In, the concentration of Nickel dichloride hexahydrate is 0.05~0.2mol/L；The ratio between Nickel dichloride hexahydrate, thiocarbamide and amount of substance of graphene
For 1:1~4:0.5~2.
6. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 2)
In, mixing time is all 20min, stirring rate 800rpm twice.
7. the preparation method of nickel sulfide/graphene composite material according to claim 1, it is characterised in that: in step 3)
In, microwave reaction temperature is 150~220 DEG C, and reaction power is 800~1300W, and the reaction time is 30~90min.
8. nickel sulfide/graphene composite material application made from claim 1-7 any one the method, feature exist
In: for application of the nickel sulfide/graphene composite material in electrode of super capacitor, wherein by nickel sulfide/graphene composite wood
Material carries out survey constant current charge-discharge test in supercapacitor three-electrode system, and the reference electrode used is Ag/AgCl, to electrode
For Pt, electrolyte is 3M KOH solution, and the voltage window tested out is 0.8~1.2V, the specific capacitance under the current density of 1A/g
845-1464F/g can be reached.
9. application according to claim 8, it is characterised in that: the preparation of the electrode of super capacitor includes following step
It is rapid:
By nickel sulfide/graphene composite material, conductive black and polyfluortetraethylene of binding element according to mass ratio 8:1:1 in solvent second
In alcohol after ground and mixed 0.5h, it is coated uniformly on flexible conductive substrates, it is dry in 80 DEG C of baking ovens.
10. application according to claim 9, it is characterised in that: the flexible conductive substrates be nickel foam, aluminium foil, titanium foil,
Copper foil, stainless steel substrates, carbon cloth, any one in PET/ITO.
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| CN113299490B (en) * | 2021-05-27 | 2022-05-10 | 辽宁工程技术大学 | Preparation method of nickel-titanium-aluminum hydrotalcite supercapacitor electrode material with porous structure |
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Application publication date: 20190730 |