CN105914056A - Quick preparation method for graphene/foamed nickel composite material electrode - Google Patents
Quick preparation method for graphene/foamed nickel composite material electrode Download PDFInfo
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- CN105914056A CN105914056A CN201610246826.5A CN201610246826A CN105914056A CN 105914056 A CN105914056 A CN 105914056A CN 201610246826 A CN201610246826 A CN 201610246826A CN 105914056 A CN105914056 A CN 105914056A
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- graphene oxide
- foam composite
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000012360 testing method Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- 238000003197 gene knockdown Methods 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 239000003990 capacitor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 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
- H01G11/84—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
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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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 belongs to the technical field of supercapacitors, and relates to a quick preparation method for a graphene/foamed nickel composite material electrode for a supercapacitor. The method can quickly prepare a high-performance graphene/foamed nickel composite material electrode with a high specific surface area and high porosity. The method comprises the specific steps: (1), the oxidation of flaky graphite; (2), the washing and drying of the oxidized flaky graphite; (3), the preprocessing of foamed nickel; (4), the preparing of an oxidized graphene/foamed nickel composite material; (5), the preparing of the graphene/foamed nickel composite material electrode; (6), the preparing and testing of the supercapacitor. The method is simple and convenient in operation, is simple in process, and is small in used time. The condition is easy to control, and the method is environment friendly.
Description
Technical field:
The invention belongs to supercapacitor technologies field, relate to a kind of stone for ultracapacitor
The fast preparation method of ink alkene/nickel foam composite electrode, and at symmetrical expression super capacitor
Device is applied.
Background technology:
Ultracapacitor, as a kind of Novel energy storage apparatus, has power density height, charging interval
The features such as short, length in service life, good temp characteristic, the saving energy and environmental protection, from structure
On see, it is mainly made up of electrode, electrolyte, barrier film, end plate, lead-in wire and encapsulating material,
Wherein composition and the quality of electrode, electrolyte and barrier film plays decision to the performance of ultracapacitor
The impact of property, uses which kind of battery lead plate and electrolyte will substantially to determine the type of final products
With characteristic.Owing to Graphene (graphene) has the highest theoretical specific surface area, good
Electric conductivity and the speciality such as excellent mechanical property, attracted the wide of supercapacitor applications field
General research interest；Theoretically, the gravimetric capacitance (Cg) of pure Graphene can reach
To 550Fg-1, it is far superior to other material with carbon elements.In prior art, research worker has been prepared for
Disclosed in graphite thiazolinyl ultracapacitor, such as Chinese patent ZL201310203648.4
A kind of preparation method based on functional type Graphene electrode of super capacitor, Chinese patent
The preparation of a kind of amorphous carbon disclosed in ZL201510780169/vertical graphene combination electrode material
Method, a kind of graphene film, Graphene surpass disclosed in Chinese patent ZL201410119589
Level capacitor and preparation method thereof, a kind of 3D bowl disclosed in Chinese patent ZL201410583167
Preparation method of dress mixing nanostructured Graphene electrode material for super capacitor etc.；But,
Owing to the accumulation of graphene sheet layer greatly reduces its effective surface area, cause it than electric capacity, energy
Metric density and power density are below desired value.
At present, the method preventing graphene sheet layer from assembling is roughly divided into three classes, adds interlayer method (example
As added surfactant, nanoparticle and polymer etc.), template aid growth and fold stone
Ink alkene sheet method, and build and do not use the three-dimensional grapheme macrostructure at interval or template to be increasingly becoming
A kind of new methods.During building graphene three-dimensional structure, first rely on oxidation
The good dispersion of Graphene obtains the graphene oxide dispersion of high concentration, then by different
Graphene oxide is reduced by reduction means (such as hydro-thermal method), realizes stone in reduction process
The assembling of ink alkene macrostructure and structure；But said process is the slowest, and liquid phase
Three dimensional structure the most destroyed during desiccation so that forming irreversible stacking,
Lose the high-specific surface area obtained.Adopt to maintain the space structure of macroscopic body to have in research
With freeze-drying to remove moisture removal, but this measure adds complexity and the preparation of operation
Cost, and effect inconspicuous.
In general, high-specific surface area and relatively low ion transport resistance are high density electrochemistry electricity
Hold two key factors that energy storage realizes.Therefore, preparation one has bigger ion accessible surface
The three-dimensional grapheme macrostructure of long-pending multiple aperture, remains ultracapacitor field institute face at present
The huge challenge faced；It is multiple that research design of the present invention goes out a kind of novel Graphene/nickel foam
The fast preparation method of condensation material electrode, it is possible to quickly prepare and there is high-specific surface area and high hole
The High-performance graphene of gap rate/nickel foam composite electrode, have preferable application prospect and
Scientific research value.
Summary of the invention:
The goal of the invention of the present invention is to overcome the shortcoming of prior art, seeks to design a kind of graphite
The fast preparation method of alkene/nickel foam composite electrode, has easy and simple to handle, and process is simple,
The features such as condition is easily-controllable.
To achieve these goals, the Graphene that the present invention relates to/nickel foam composite electrode
Fast preparation method specifically include following steps:
(1) oxidizing process of flaky graphite: first native graphite is placed in P2O5With 80 DEG C
Under the conditions of concentrated sulphuric acid mixed liquor in pre-oxidize 6 hours, will pre-oxidation graphite filter, washing,
Continue oxidation 3 hours with potassium permanganate after drying, be subsequently adding deionized water and make solution exist
Stir 2 hours under 35 DEG C of constant temperatures, be eventually adding the dioxygen that mass fraction is 30% water-soluble
Liquid and unreacted potassium permanganate are neutralized reaction, until the color of whole mixed liquor becomes bright
Yellow；
(2) graphene oxide washing and be dried: the glassy yellow liquid that will obtain in step (1)
Body is centrifuged 10-30 minute under the rotating speed of 3000-5000 rev/min, by gained precipitate quality
Mark is to remove settled solution after the aqueous hydrochloric acid solution dispensing laundry of 0.8%-1.5%, centrifugal treating,
Repeat above-mentioned dispensing laundry, centrifugal treating three times；Then gained precipitate is distributed to quality divide
Number be 99.9% methanol in and centrifugal treating, repeat above-mentioned dispersion, centrifugal treating three times,
After gained is centrifuged product to be vacuum dried 24 in vacuum drying oven under the conditions of 30-60 DEG C little
Time, obtain being dried graphene oxide solid；
(3) pretreatment of nickel foam: the nickel foam that thickness is 0.5-5mm is immersed in mole
Concentration be 0.5mol/L diluted hydrochloric acid aqueous solution in supersound process 15 minutes, then divide by quality
The acetone rinsing of several 99.9% 5 times, then by supersound process after deionized water washing by soaking 15 points
More than clock, it is then placed in vacuum drying oven drying for standby under the conditions of 50 DEG C；
(4) preparation of graphene oxide/nickel foam composite: will prepare in step (2)
Graphene oxide solid be distributed in distilled water be configured to mass concentration be 10-50mg/mL's
Graphene oxide dispersion, then by graphene oxide dispersion uniform application in step (3)
In pretreated nickel foam surface, put into baking oven after scraping unnecessary graphene oxide dispersion
In under the conditions of 30-60 DEG C be dried 5 hours, prepare graphene oxide/nickel foam composite；
(5) preparation of Graphene/nickel foam composite electrode: by preparation in step (4)
Graphene oxide/nickel foam composite be placed in the 1-600 second on the flame of the alcohol burner lighted,
Until the graphene oxide of brown color/nickel foam composite is the most expanded and becomes atrous,
Prepare redox graphene/nickel foam composite after knock down the flame and be Graphene/nickel foam
Composite electrode；
(6) preparation of ultracapacitor and test: the reduction-oxidation that will prepare in step (5)
Graphene/nickel foam composite is pressed into thin slice under 1-10Mpa pressure, using as electrode
Sheet, then the sodium hydrate aqueous solution with molar concentration as 6mol/L is as electrolyte, with glass
Fiber filter paper is that barrier film is assembled into symmetrical expression ultracapacitor in a conventional manner.
The present invention compared with prior art has the following advantages and improves: the first, use improvement
Hummer method prepares graphene oxide, utilizes strong oxidizer with natural flaky graphite for raw material
Graphene oxide is prepared by expansion principle under effect；The second, graphene oxide is optimized
Washing step so that originally occupied the washing operation of most of the time foreshorten to 3 hours it
In, and can reach to remove completely the metal that may participate in graphene oxide preparation process from
Son；3rd, the mode using flame heating carries out fast restore to graphene oxide, it is achieved that
Reduction process and structure porous three-dimensional structure complete the most simultaneously, enormously simplify electricity
Pole manufacturing process；4th, prepared redox graphene/nickel foam composite, nothing
Need post processing can use directly as electrode of super capacitor, use reducing agent compared to tradition
The method of redox graphene, eliminates the washing step of electrode material；5th, bubble is utilized
The intrinsic three-dimensional foam structure of foam nickel self is skeleton, by being uniformly coated with oxidation stone on its surface
Restore after ink alkene, be effectively utilized the surface area within nickel foam, flame treatment step afterwards
In Zhou, the rapid expanded hole increasing graphene film interlayer of volume, not only achieves increase stone
The effect of the specific surface area of ink alkene structure, and beneficially the quick of ion is spread, it is achieved superelevation
Speed discharge and recharge；6th, as the electrode in ultracapacitor, not only superior performance, be applicable to
Ultrahigh speed discharge and recharge, and preparation process is simple to operate, time saving and energy saving, is therefore very suitable for work
Prepared by industry large-scale production, have broad application prospects；The method is easy and simple to handle, process
Simply, the used time is short of, and condition is easily-controllable, environmental friendliness.
Accompanying drawing illustrates:
Fig. 1 is the quickly side of preparation of the Graphene/nickel foam composite electrode that the present invention relates to
The process flow diagram of method.
Fig. 2 is the Graphene/nickel foam composite electrode structure section view of preparation in the present invention
Figure；Wherein 1-nickel foam, 2-graphene sheet layer.
Fig. 3 is that the Graphene/nickel foam composite electrode structure prepared in the present invention is in charge and discharge
Electrons spread behavior principle schematic in electric process；Wherein 1-nickel foam, 2-graphene sheet layer；
3-cation；4-anion.
Fig. 4 is the electric current of the symmetrical expression ultracapacitor testing gained in embodiments of the invention 1
Density and the relation schematic diagram of voltage scan rate；Wherein abscissa is voltage (V), vertical coordinate
For electric current density (A/g).
Fig. 5 is the quality of the symmetrical expression ultracapacitor testing gained in embodiments of the invention 1
Than electric capacity at the situation of change schematic diagram of different voltage scan rate；Wherein abscissa is scanning speed
Degree (mV/s), vertical coordinate is that quality is than electric capacity (F/g).
Fig. 6 is that the symmetrical expression ultracapacitor testing gained in embodiments of the invention 2 is in difference
Discharge and recharge time change schematic diagram under charging and discharging currents density；Wherein abscissa is the time
(sec), vertical coordinate is voltage (V).
Fig. 7 is that the symmetrical expression ultracapacitor testing gained in embodiments of the invention 3 is in difference
Quality under charging and discharging currents density is than capacitance variations schematic diagram；Wherein abscissa is that electric current is with close
Degree (A/g), vertical coordinate is that quality is than electric capacity (F/g).
Detailed description of the invention:
Below by embodiment and combine accompanying drawing the present invention is described in further detail, but this
Bright it is not limited to implementation below.
Embodiment 1:
The fast preparation method of the Graphene related in the present embodiment/nickel foam composite electrode
Concretely comprise the following steps:
(1) oxidizing process of flaky graphite: natural flaky graphite (4g) is distributed to molten
There is P2O5(1g) the dense H of 80 DEG C2SO4(10mL) in solution, after stirring 6 hours
Reaction obtain bottle green mixture, bottle green mixture is filtered and is washed with deionized until
The pH of eluate becomes neutral (pH=7), then filtration products therefrom is vacuum dried 15 little
Time remove after excessive moisture in case aoxidizing further；Dry pre-oxidation graphite is joined 50
The dense H of mL2SO4In, then under condition of ice bath, (0-5 DEG C) is slowly added to 6g potassium permanganate
And continuously stirred 3 hours, add 400mL deionized water and make solution be maintained at 35 DEG C
Under the conditions of stir 2 hours, be eventually adding the hydrogen peroxide solution (5mL) of mass fraction 30%
Neutralize unreacted potassium permanganate, until the color of whole mixed liquor becomes bright orange i.e. shows graphite
The most oxidized；
(2) graphene oxide washing and be dried: the glassy yellow liquid that will obtain in step (1)
Body centrifugal treating or stand after layering to be precipitated in 6 hours, goes the supernatant with mass fraction to be again
Hydrochloric acid solution (100-400mL) the dispersion precipitate of 0.8%-1.5%, 3000 after stirring
Rev/min rotating speed under outwell upper strata settled solution after centrifugal 10 minutes, repeat above-mentioned dispersion, from
The heart operates 2-3 time；Gained precipitate is distributed to the methanol (200-400 that mass fraction is 99.9%
ML) in and carry out centrifugal treating, above-mentioned dispersion, centrifugal treating three times are repeated, finally will be from
Heart product is vacuum dried 24 hours in 40 DEG C of vacuum drying ovens, obtains being dried graphene oxide
Solid；
(3) pretreatment of nickel foam: by nickel foam of the prior art (thickness 0.5-5mm)
It is immersed in supersound process 15 minutes in the dilute hydrochloric acid that molar concentration is 0.5mol/L, then with third
Ketone (mass fraction 99.9%) rinse 5 times, then with deionized water soak after supersound process 15
More than minute, it is then placed in vacuum drying oven drying for standby under the conditions of 50 DEG C；
(4) preparation of graphene oxide/nickel foam composite: will prepare in step (2)
Graphene oxide solid be distributed in distilled water be configured to the graphene oxide of 10mg/mL and divide
Dissipate liquid；Pretreated nickel foam in step (3) is tiled on the glass sheet, then uses glass
Graphene oxide dispersion uniform application on nickel foam surface, is scraped off unnecessary oxidation stone by glass rod
The nickel foam scribbling graphene oxide dispersion, to reuse, is then put by ink alkene dispersion liquid
Enter in baking oven and be dried 5 hours under the conditions of 30 DEG C, prepare the equally distributed oxygen of graphene oxide
Functionalized graphene/nickel foam composite.
(5) preparation of graphene oxide/nickel foam composite electrode: by step (4)
Graphene oxide/nickel foam the composite of preparation is placed on flame upper 1 second of the alcohol burner lighted,
Eye-observation is the most expanded to brown color composite and after becoming atrous, and knock down the flame prepares
Redox graphene/nickel foam composite, is Graphene/nickel foam composite electrode,
Its structural profile schematic diagram is as shown in Figures 2 and 3；
(6) preparation of ultracapacitor and test: the oxygen reduction that will prepare in step (5)
Functionalized graphene/nickel foam composite depresses to thin slice at the pressure of 1MPa, using as electrode
Sheet, then directly with the sodium hydrate aqueous solution of 6mol/L as electrolyte, filters with glass fibre
Paper is that barrier film is assembled into symmetrical expression ultracapacitor in a conventional manner.
The present embodiment utilize electrochemical workstation (Shanghai occasion China CHI 760D type) not
Under the conditions of same voltage scan range (5-1000mV/s), the symmetrical expression ultracapacitor assembled is entered
Row electrochemical property test, test result is as shown in Figures 4 and 5；According to Fig. 4, sweeping
Retouch CV curve when speed improves constantly and remained in that good rectangular shape, illustrate to sweep at height
Retouch and under speed, remained in that good capacitive properties.According to Fig. 5, the symmetrical expression of assembling
Ultracapacitor is under the scanning speed that voltage scan rate is 5mV/s, and quality is up to than electric capacity
223F/g, along with improving constantly of sweep speed, quality has declined than electric capacity, but in scanning
Speed is to be still above 150F/g during 1V/s.
Embodiment 2:
In the present embodiment, concrete operations order and method are essentially identical with embodiment 1, difference
Place is:
In step (2): the hydrochloric acid solution dispersion precipitate using mass fraction to be 1.0%, stir
Under the rotating speed of 4000 revs/min, upper strata settled solution is outwelled after centrifugal 20 minutes after mixing uniformly；
Utilize methanol dispersion, centrifugal after centrifugal product is vacuum dried in 50 DEG C of vacuum drying ovens 24
Hour, obtain being dried graphene oxide solid；
In step (4): the graphene oxide solid prepared in step (2) is distributed to distillation
Water is configured to the graphene oxide dispersion of 10mg/mL；Nickel foam in step (3) is coated with
After smearing, the nickel foam scribbling graphene oxide dispersion is put in baking oven dry under the conditions of 50 DEG C
Dry 5 hours, prepare the equally distributed graphene oxide of graphene oxide/nickel foam composite；
In step (5): by the graphene oxide/nickel foam composite wood of preparation in step (4)
Material is placed on flame upper 10 second of the alcohol burner lighted, and eye-observation is fast to brown color composite
Speed is expanded and after becoming atrous, and knock down the flame prepares redox graphene/nickel foam and is combined
Material, is Graphene/nickel foam composite electrode；
In step (6): the redox graphene/nickel foam that will prepare in step (5)
Composite depresses to thin slice at the pressure of 5MPa, using as electrode slice, then with sodium hydroxide
Aqueous solution and glass fiber filter paper cooperation are assembled into symmetrical expression ultracapacitor.
The present embodiment utilize electrochemical workstation (Shanghai occasion China CHI 760D type) not
With under the conditions of charging or discharging current density (1-32A/g), the symmetrical expression ultracapacitor assembled is carried out
Electrochemical property test, test result is as shown in Figure 6.According to Fig. 6, the symmetry of assembling
Formula ultracapacitor charging and discharging curve is close to straight line, and presents the character shape of isosceles triangle,
Illustrate that discharge and recharge rapidly and does not has obvious pressure drop, show assembled symmetrical expression super capacitor
Device internal resistance is less, affects when high current charge-discharge and substantially can ignore；According to calculating at 1A/g
Electric current density under the quality of capacitor be up to 251F/g than electric capacity.
Embodiment 3:
In the present embodiment, concrete operations order and method are essentially identical with embodiment 1, difference
Place is:
In step (4): the graphene oxide solid prepared in step (2) is distributed to distillation
Water is configured to the graphene oxide dispersion of 50mg/mL；Nickel foam in step (3) is coated with
After smearing, the nickel foam scribbling graphene oxide dispersion is put in baking oven dry under the conditions of 60 DEG C
Dry 5 hours, prepare the equally distributed graphene oxide of graphene oxide/nickel foam composite；
In step (5): by the graphene oxide/nickel foam composite wood of preparation in step (4)
Material is placed on flame upper 60 second of the alcohol burner lighted, and eye-observation is fast to brown color composite
Speed is expanded and after becoming atrous, and knock down the flame prepares redox graphene/nickel foam and is combined
Material, is Graphene/nickel foam composite electrode；
In step (6): the redox graphene/nickel foam that will prepare in step (5)
Composite depresses to thin slice at the pressure of 10MPa, using as electrode slice, then with hydroxide
Sodium water solution and glass fiber filter paper cooperation are assembled into symmetrical expression ultracapacitor.
The present embodiment utilize electrochemical workstation (Shanghai occasion China CHI 760D type) not
With under the conditions of charging or discharging current density (1-32A/g), the symmetrical expression ultracapacitor assembled is carried out
Electrochemical property test, test result is as shown in Figure 7.According to Fig. 7, electric current density
Increasing makes the ratio electric capacity of symmetrical expression ultracapacitor decline, and the 236F/g when 1A/g is always
Drop to 153F/g during 32A/g, illustrate that this symmetrical expression ultracapacitor has good high speed
Charge-discharge performance.
The foregoing is only the better embodiment of the present invention, protection scope of the present invention not with
Above-mentioned embodiment is limited, as long as what those skilled in the art were made according to content of the present invention
Equivalence change, all should include in the protection domain described in claims.
Claims (1)
1. the fast preparation method of Graphene/nickel foam composite electrode, it is characterised in that specifically include
Following processing step:
(1) oxidizing process of flaky graphite: first native graphite is placed in P2O5With 80 DEG C under the conditions of dense
The mixed liquor of sulphuric acid pre-oxidizes 6 hours, pre-oxidation graphite is filtered, wash, use potassium permanganate after drying
Continue oxidation 3 hours, be subsequently adding deionized water and make solution stir 2 hours under 35 DEG C of constant temperatures,
It is eventually adding the hydrogen peroxide solution that mass fraction is 30% and is neutralized reaction, directly with unreacted potassium permanganate
Color to whole mixed liquor becomes bright orange；
(2) graphene oxide washing and be dried: the glassy yellow liquid obtained in step (1) is existed
It is centrifuged 10-30 minute under the rotating speed of 3000-5000 rev/min, by gained precipitate mass fraction is
Remove settled solution after the aqueous hydrochloric acid solution dispensing laundry of 0.8%-1.5%, centrifugal treating, repeat above-mentioned dispersion and wash
Wash, centrifugal treating three times；Then gained precipitate it is distributed in the methanol that mass fraction is 99.9% and is centrifuged
Process, repeat above-mentioned dispersion, centrifugal treating three times, finally gained is centrifuged product in vacuum drying oven in
It is vacuum dried 24 hours under the conditions of 30-60 DEG C, obtains being dried graphene oxide solid；
(3) pretreatment of nickel foam: the nickel foam that thickness is 0.5-5mm is immersed in molar concentration is
Supersound process 15 minutes in the diluted hydrochloric acid aqueous solution of 0.5mol/L, then with the acetone punching of mass fraction 99.9%
Wash 5 times, then by supersound process after deionized water washing by soaking more than 15 minutes, be then placed in vacuum drying oven
In under the conditions of 50 DEG C drying for standby；
(4) preparation of graphene oxide/nickel foam composite: the graphite oxide that will prepare in step (2)
Alkene solid is distributed in distilled water be configured to the graphene oxide dispersion that mass concentration is 10-50mg/mL, so
After by graphene oxide dispersion uniform application pretreated nickel foam surface in step (3), scrape many
Put into after remaining graphene oxide dispersion in baking oven and be dried 5 hours under the conditions of 30-60 DEG C, prepare oxidation stone
Ink alkene/nickel foam composite；
(5) preparation of Graphene/nickel foam composite electrode: by the graphite oxide of preparation in step (4)
Alkene/nickel foam composite is placed in the 1-600 second on the flame of the alcohol burner lighted, until the oxidation stone of brown color
Ink alkene/nickel foam composite is the most expanded and become atrous, prepare after knock down the flame redox graphene/
Nickel foam composite is Graphene/nickel foam composite electrode；
(6) preparation of ultracapacitor and test: the redox graphene/bubble that will prepare in step (5)
Foam nickel composite material is pressed into thin slice under 1-10Mpa pressure, using as electrode slice, then with molar concentration
Sodium hydrate aqueous solution for 6mol/L is electrolyte, with glass fiber filter paper for barrier film group in a conventional manner
Dress up symmetrical expression ultracapacitor.
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| CN109473288A (en) * | 2018-10-22 | 2019-03-15 | 江苏大学 | A method of three-dimensional grapheme/foam nickel composite material is prepared by raw material of luffa |
| CN110078043A (en) * | 2019-04-01 | 2019-08-02 | 暨南大学 | A kind of three-dimensional carbon or three-dimensional carbon/grapheme foam and its preparation method and application |
| CN111249765A (en) * | 2020-02-25 | 2020-06-09 | 中国科学院化学研究所 | Pressurized fluid extraction system and method for removing metal ions from carbon material |
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