CN104934238A - Method for preparing porous graphene electrode material by air bubble template process and application of method - Google Patents
Method for preparing porous graphene electrode material by air bubble template process and application of method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000007772 electrode material Substances 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 abstract 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 8
- 238000010408 sweeping Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000002848 electrochemical method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect 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
- H01G11/84—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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a porous graphene electrode material by an air bubble template process and application of the method to a super-capacitor. The method comprises: preparing a graphene oxide solution by adopting an Hummers method, respectively adding sodium dodecyl benzene sulfonate and concentrated sulfuric acid into the graphene oxide solution to uniformly mix, thereby obtaining a mixed solution; and by taking the mixed solution as electrolyte and adopting a constant-potential petrochemical method, enabling the electrode surface to generate air bubbles in a reaction process and enabling the graphene oxide solution to generate reduction reaction, and assembling on the electrode surface by taking air bubbles as a template, thereby obtaining a porous graphene oxide electrode by virtue of co-action of electrochemical reduction deposition and the air bubble template. The preparation method is simple, gentle and cheap, so that the porous graphene electrode based on a large-area conductive substrate can be produced on a large scale; and the obtained graphene electrodes are inter-communicated porous structures with pores vertical to the conductive substrate; and the prepared porous graphene electrode material has the advantages of good conductivity, a large specific surface area and the like, and can be used as an electrode material of the supercapacitor.
Description
Technical field
The present invention relates to the method adopting constant potential, with graphene oxide mixed solution for electrolyte, conductive substrate produces bubble and the template deposited in this, as graphene oxide reduction; Also relate to simultaneously and this porous graphene electrode material is applied in ultracapacitor.
Background technology
Graphene is the two dimensional crystal with monoatomic layer thickness be made up of carbon, in known materials, there is the highest hardness and intensity, plane exists large-area delocalized pi-bond, pi-electron can move freely in the plane, and thus Graphene has good electronic transmission performance
1, the room-temperature conductivity of Graphene is about 5 × 10
3w m
-1g
-1, higher than diamond, carbon nano-tube, exceed 10 times than the thermal conductivity of copper.Graphene theoretical specific surface area is up to 2630m
2g
-1.In addition, Graphene also has the special performances such as room temperature Hall effect, bipolar electrolytic field effect, excellent light transmission
2.The two-dimensional structure of Graphene uniqueness and the physics of various excellence, chemical property make Graphene at electronic device
3, composite material
4, detect
5and energy storage
6huge application prospect is had in field.But graphene film interlayer has the effect such as hydrogen bond, Van der Waals force, make to attract each other between lamella, be easy to pile up thus be difficult to peel off dispersion, limiting its application.And graphene oxide is because its surface is with the functional group such as hydroxyl, carboxyl, can be dissolved in solution very well, take therefore graphene oxide as precursor power grapheme material, is a kind of very important method.Wherein, graphene oxide can be prepared by chemical oxidation native graphite, then through reduction means such as electronation, hot assisted Reduction, light assisted Reduction and electrochemical reductions, thus obtain the Graphene of the chemical conversion of conducting electricity.Wherein electrochemical reduction oxidation Graphene is as the effective method of reducing of one, and simple to operate, process control is widely used in preparing Graphene.But many researchers generally adopt the mode of dripping painting that graphene oxide is dropped in electrode surface
7, then the Graphene that reduces is obtained through electrochemical reduction, this method complicated operation, is unfavorable for preparation in enormous quantities, in addition the redox graphene build stack prepared of the method, poorly conductive, thus limits its application
8.Based on this, adopt the method for electrochemical reduction the graphene oxide of two dimension to be built into senior orderly Macro-Functions material, provide not only the means of its structure of multiple regulation and control and pattern, and the function and application of Graphene can be expanded.The physical and chemical performance excellent because of Graphene itself and loose structure make the electroactive material of electrode surface load be easy in electrode surface dispersion and transmit, three-dimensional structure provides large specific area, add electron transport rate, therefore electrochemical field is widely used in, as energy storage and conversion equipment (lithium ion battery, ultracapacitor and fuel solar cell etc.), therefore preparing three-dimensional porous Graphene electrodes material is the emphasis that people study.Template prepares the important method of three-dimensional porous material, and comprise hard template method and soft mode version method, hard template method adopts nickel foam usually
9, SiO
2ball
10deng as template, there is the advantage such as regular appearance, structure-controllable, but it is to sacrifice template for cost, has that preparation process complexity, experiment condition are harsh, expensive, the shortcoming such as to lose time.Relative to hard template method, soft template is usually with emulsion
11, bubble
12deng as template, have preparation process simple, the advantage such as cheap, wherein hydrogen bubble template is as a kind of method of soft template, has been widely used in and has prepared three-dimensional material
13.Hydrogen template utilizes hydrogen gas bubbles as Template preparation porous material, and it has, and cheap, preparation process is simple, structure-controllable and without the need to advantages such as reprocessings, is a kind of method effectively preparing three-dimensional porous material.The wherein generation of bubble, bubble are all that a step completes as the removal of Template preparation other materials and bubble template.In recent years, researchers' many three-dimensional porous metal materials that adopted hydrogen bubble template to prepare are as copper etc.
14, and it is rarely found to be applied to prepare material with carbon element.The present invention, both based on electrochemical reduction deposited oxide Graphene, utilizes the three-D pore structure of bubble template to regulate Graphene simultaneously in electrochemical deposition process.The preparation method of traditional Graphene super capacitor material first carries out the electronation of graphene oxide, mix a certain proportion of adhesive (as Nafion material) with the powder of redox graphene to be afterwards dissolved into pasty state and to drip and be coated in conductive substrates, thus preparation can be used for the Graphene electrodes of ultracapacitor.And compared with above-mentioned conventional method, the method that this patent proposes, by taking conductive substrates as work electrode electrochemical reduction oxidation Graphene, thus prepare the large-area graphene modified electrode with three-dimensional porous structure, this method is applicable in multiple conductive substrates as titanium sheet, copper sheet, platinized platinum, nickel sheet, carbon paper etc. carry out the deposition of graphene oxide; Simultaneously with the bubble produced in electro-reduction process for template, the three-D pore structure of regulation and control Graphene, makes this electrode material have senior orderly microstructure and excellent performance.And the method that this patent proposes, can be deposited directly to conductive substrates as the electrode in ultracapacitor, a step completes, cheap and can realize large-scale production using electrode material, be a kind of simple effectively economic method.
List of references:
1.K.S.Novoselov,A.K.Geim,S.V.Morozov,D.Jiang,Y Zhang,S.V.Dubonos,I.V.Grigorieva,A.A.Firsov,Scinece,2004,306,666-669.
2.(a)R.R.Nair,P.Blake,A.N.Grigorenko,K.S.Novoselov,T.J.Booth,T.Stauber,N.M.R.Peres,A.K.Geim,Science,2008,320,1308.(b)M.Polini,F.Guinea,M.Lewenstein,H.C.Manoharan and V.Pellegrini,Naturenanotechnology,2013,8,625-633.
3.G.A.Snook,P.Kao and A.S.Best,Journal of Power Sources,2011,196,1-12.
4.H.Zhou,G.Han,Y.Xiao,Y.Chang and H.-J.Zhai,Journal of Power Sources,2014,263,259-267.
5.X.Feng,Y.Zhang,J.Zhou,Y.Li,S.Chen,L.Zhang,Y.Ma,L.Wang and X.Yan,Nanoscale,2015,7,2427-2432.
6.X.Huang,H.Yu,J.Chen,Z.Lu,R.Yazami and H.H.Hng,Advanced materials,2014,26,1296-1303.
7.H.L.Guo,X.F.Wang,Q.Y.Qian,F.B.Wang and X.H.Xia,ACS Nano.,2009,3,2653-2659
8.(a)Y.Shao,；J.Wang,；M.Engelhard,；C.Wang,；Y.Lin,,.J.Mater.Chem.2010,20(4),743-748；(b)Zhang,H.；Zhang,X.；Zhang,D.；Sun,X.；Lin,H.；Wang,C.；Ma,Y.,The journal of physical chemistry.B 2013,117(6),1616-27.
9.Y.Ito,Y.Tanabe,H.J.Qiu,K.Sugawara,S.Heguri,N.H.Tu,K.K.Huynh,T.Fujita,T.Takahashi,K.Tanigaki and M.Chen,AngewandteChemie,2014,53,4822-4826.
10.H.W.Liang,X.Zhuang,S.Bruller,X.Feng and K.Mullen,Naturecommunications,2014,5,4973.
11.S.Gan,L.Zhong,T.Wu,D.Han,J.Zhang,J.Ulstrup,Q.Chi and L.Niu,Advanced materials,2012,24,3958-3964.
12.H.S.Ahn,J.W.Jang,M.Seol,J.M.Kim,D.J.Yun,C.Park,H.Kim,D.H.Youn,J.Y.Kim,G.Park,S.C.Park,J.M.Kim,D.I.Yu,K.Yong,M.H.Kimand J.S.Lee,Scientific reports,2013,3,1396.
13.J.l.Azevedo,C.Costa-Coquelard,P.Jegou,T.Yu and J.-J.Benattar,The Journalof Physical Chemistry C,2011,115,14678-14681.
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Summary of the invention
Technical problem: the object of this invention is to provide a kind of hydrogen bubble template and prepare porous graphene electrode material and the application in ultracapacitor thereof.Solve the cost that prior art exists high, the problems such as step is complicated, provide a kind of simple, cheap, gentle synthesizing porous Graphene electrodes material of method.The porous material of the present invention's synthesis has the advantages such as size is controlled, good conductivity, specific area are large.
Technical scheme: the method for the bubble Template preparation Graphene porous electrode material that the present invention announces comprises the following steps:
Adopt hydrogen bubble template to prepare the method for porous graphene electrode material, it is characterized in that comprising the following steps:
1) adopt Hummers legal system for graphene oxide solution, respectively through pickling, washing, and be placed in after bag filter dialyses and reach a neutrality in, freeze drying, obtains graphene oxide powder;
2) prepare graphite oxide solution, after ultrasonic 30min, add neopelex and the concentrated sulfuric acid, stir and make it mix, obtain mixed solution;
3) using this mixed solution as electrolyte, conductive substrate is as work electrode, and platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, connects electrochemical appliance, selects constant potential method
15, under certain electrochemical conditions, working electrode surface produces bubble hydrogen, and reduces in this, as graphene oxide the template be deposited on conductive substrate, obtains porous graphene electrode material.
4) gained Graphene porous electrode is placed in distilled water, soaks removing impurity.
5) using porous graphene electrode as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.
Step 1) described in employing Hummers legal system specifically comprise the following steps for the preparation process of graphene oxide solution:
Under ice-water bath and stirring condition, successively the concentrated sulfuric acid, graphite powder and sodium nitrate are joined in beaker; To be mixed evenly after, slowly add potassium permanganate, and continue to stir in ice bath; Then, reaction temperature is increased to 35 DEG C, and reacts at this temperature; Then, first add 150mL deionized water, then system temperature is increased to 90 DEG C, continue vigorous stirring; After question response completes, add deionized water under agitation successively and percent by volume is the hydrogen peroxide of 30%; Above-mentioned product is placed in centrifuge tube, uses volume ratio 1:10 diluted hydrochloric acid aqueous solution and deionized water centrifuge washing successively; After centrifugal completing, by solid by ultrasonic dissolution in deionized water, transfer to dialysis in bag filter subsequently and remove remaining metal ion and acid, until solution is neutral; Finally by the reactant after dialysis, centrifugal by 4000 turns/min, abandon the graphite of the non-complete oxidation of bottom, obtain GO colloid aqueous solution, by freeze drying process, obtain graphene oxide powder.
Step 2) in, the concentration of neopelex is 50mM-400mM; The concentration of graphene oxide solution is 1mg/mL-5mg/ml.
Step 2) in, neopelex is dispersed in graphene oxide solution, adds 50 μMs of concentrated sulfuric acids, stirs and makes it mix, obtain mixed solution.
Step 3) in, using mixed solution as electrolyte, adopt constant potential electrochemical techniques.
Step 3) in, fix electrochemical conditions deposition voltage respectively, select-0.8V ~-1.2V; Sedimentation time, selects 10s-120s.
Step 3) in, conductive substrate is gold plaque, platinized platinum, titanium sheet, copper wire, or the graphene film for conducting electricity.
Step 4) in, gained Graphene porous electrode is placed in distilled water, soaks 30min and remove impurity.
Step 5) in, detect the capacitor performance of Graphene porous material, adopt cyclic voltammetry, change and sweep speed from 50mV/s-5000mV/s.
Step 6) in, detect the capacitor performance of Graphene porous material, adopt chronoptentiometry, change current density from 0.5mA/cm
2-5mA/cm
2, the charge-discharge performance of Graphene porous material.
Beneficial effect: this preparation method is simple, gentle, cheap, can large-scale production based on the Graphene porous electrode of large area conductive substrates, the Graphene electrodes obtained is intercommunication loose structure, pore structure controllable, and hole is perpendicular to conductive substrates; In addition, this material has the advantages such as good conductivity, specific area be large, can be used as the electrode material of ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the SEM figure of Graphene porous electrode (gold plaque is as substrate) prepared by variable concentrations neopelex solution,
Fig. 2 is the SEM figure of the Graphene porous electrode (gold plaque is as substrate) under different sedimentation time,
The SEM figure of the Graphene porous material on the different conductive substrate of Fig. 3
Fig. 4 is the cyclic voltammetry figure that Graphene porous electrode is applied in ultracapacitor, sweeps speed from 50mV/s-5000mV/s.
Fig. 5 is the charging and discharging curve that Graphene porous electrode is applied in ultracapacitor, and current density is from 0.5mA/cm
2-5mA/cm
2.
Implement technical descriptioon:
Constant potential electrochemical techniques and constant potential electrochemical process is adopted in this patent, carry out redox graphene and be deposited in conductive substrates, wherein potentiostatic method is the current potential by controlling to measure electrode, reach and a constant current potential is applied to the electrode measured, impel a kind of method that it reacts under this current potential.The method is widely used in electrochemical reaction because of advantages such as condition are simple, easy to operate.
Cyclic voltammetry is adopted to study the fast charging and discharging performance of this porous graphene electrode material in this patent, wherein cyclic voltammetry is the shallow charge and discharge process by simulation electrode surface, the invertibity of electrode reaction is judged, a kind of effective method of the possibility of Electrode reaction mechanism, Interfacial Adsorption or New phase formation, the character of coupling reaction etc. by curve shape.Cyclic voltammetry curve can be used for the capacitive property of more various material, when its shape presents class rectangle, illustrate that electrode material has good charge-discharge performance, when capacitance is constant, along with the increase of sweep speed, electric current is the increase of ratio with it, and still can keep good rectangle, illustrate that this electrode material has fast charging and discharging ability, be applicable to big current work.The voltage range adopted in patent is-0.4V-0.8V, and sweeping speed is increased gradually by 50mV/s-5000mV/s.
Chronoptentiometry is adopted to study the discharge and recharge time of this porous graphene electrode material in this patent, ideally, the charging and discharging curve of ultracapacitor is isosceles triangle, but due to the existence of electrode material internal resistance, and the capacitance of electrode can have certain change along with electrode potential, thus charging and discharging curve to have in various degree bending.The voltage range adopted in patent is-0.4V-0.8V, and current density is from 0.5mA/cm
2-5mA/cm
2.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the Graphene porous electrode prepared under different surfaces surfactant concentration.As can be seen from Figure 1, the porous graphene electrode prepared by the present invention has the three-dimensional porous structure of intercommunication, regular appearance, and pore size is relevant with the concentration of surfactant.When surfactant concentration is 50mM, have adjusted the interfacial tension between hydrogen gas bubbles and solution, that impels that bubble can be more uniform and stable exists in solution, and its redox graphene pore size distribution prepared as dynamic masterplate is comparatively even, and hole dimension is about 50 μm.But when the concentration of surfactant increases to 100mM, when 200mM, 300mM, from figure b, c, d, the hole dimension of macropore Graphene electrodes presents uneven, the phenomenon that distribution is wider, but its pattern is not obviously distinguished.This illustrates, at identical conditions, the concentration of neopelex affects the interfacial tension between bubble hydrogen and solution, thus controls the structure of three-dimensional macropore grapheme material.It can thus be appreciated that the pattern of three-dimensional macropore Graphene electrodes and the size concentration depending on surfactant tightly, this phenomenon is also very identical with bibliographical information.
Fig. 2 is the SEM figure of the Graphene porous electrode under different sedimentation time.As can be seen from Figure 2, porous graphene material prepared by the present invention is along with the growth (a, 10s b, 30s c, 60s d, 90s) of sedimentation time, and it is using bubble as template, and place's deposition around bubble, hole height and thickness all become large.
Fig. 3 is the SEM figure of the Graphene porous material on different conductive substrate, there is figure known, grapheme material can successfully be deposited on different conductive substrates as Ti, Pt, graphene film, Cu silk, and present three-dimensional porous structure, regular appearance, illustrate that hydrogen bubble template is prepared porous graphene electrode material and had very wide range of application, be applicable to the preparation of the porous graphene material on different conductive substrate.
Fig. 4 is the porous graphene electrode prepared of the present invention different cyclic voltammetry figure swept under speed in 1M KCl
16.As can be seen from Figure 4, the cyclic voltammetry curve of this three-dimensional porous Graphene electrodes material presents good rectangle, describe this electrode material and can carry out ion diffuse fast, there is desirable electric double layer capacitance performance, and its peak area increases along with the increase of sweeping speed, under the height of 5000mV/s sweeps speed, cyclic voltammetry curve is not still out of shape for rectangle, illustrates that this material has fast charging and discharging ability.
Fig. 5 is the charging and discharging curve figure of porous graphene electrode in 1MKCl solution
16.As can be seen from Figure 5, the charging and discharging curve of porous graphene presents symmetrical triangle, describes the character that it has electric double layer capacitance.Along with the increase of current density, its discharge and recharge time decreased.When current density is 0.5mA/cm
2time, its electric capacity is 11.25mF/cm
2,
Embodiment
The concrete grammar of Graphene porous electrode material prepared by the present invention is further illustrated as instantiations such as work electrodes below by changing preparation condition such as the concentration of the concentration of graphene solution, electrochemical deposition voltage and time, surfactant and different conductive substrates.
Embodiment 1
(1) preparation of graphene oxide solution
Under ice-water bath and stirring condition, successively the concentrated sulfuric acid, graphite powder and sodium nitrate are joined in beaker.To be mixed evenly after, slowly add potassium permanganate, and continue to stir in ice bath.Then, reaction temperature is increased to 35 DEG C, and reacts at this temperature.Then, first add 150mL ionized water, then system temperature is increased to 90 DEG C of continuation vigorous stirring.After question response completes, add deionized water and hydrogen peroxide (30%) under agitation successively.Above-mentioned product is placed in centrifuge tube, use watery hydrochloric acid (1:10) aqueous solution and deionized water centrifuge washing successively.After centrifugal completing, by solid by ultrasonic dissolution in deionized water, transfer to dialysis in bag filter subsequently and remove remaining metal ion and acid, until solution is neutral.Finally by the reactant after dialysis, centrifugal by 4000 turns/min (rpm), abandon the graphite of the non-complete oxidation of bottom, obtain GO colloid aqueous solution.By freeze drying process, obtain graphene oxide powder.
(2) formula of electrolyte
Preparation 1mg/mL, 3mg/mL, 5mg/mL graphene oxide solution, by its ultrasonic 30min, after add 50 μMs of concentrated sulfuric acids, 50mM neopelex, is stirred.
(3) electrochemical deposition porous graphene electrode
The mixed solution of preparation is placed in electrolytic cell, adopt constant potential electrochemical method, gold plaque electrode is as work electrode, platinum plate electrode is as to electrode, saturated calomel electrode is as the three-electrode system of reference electrode, under-1.2V voltage conditions, deposit 120s, be placed in distilled water water and soak 30min, freeze drying obtains Graphene porous electrode.
(4) using the porous graphene electrode of preparation as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.Cyclic voltammetry, sweeping speed is: 50mV/s-5000mV/s; Charge-discharge test, current density is: 0.5mA/cm
2-5mA/cm
2.
Embodiment 2
(1) graphene oxide solution is prepared with reference to the method for embodiment 1
(2) formula of electrolyte
Preparation 3mg/mL graphene oxide solution, by its ultrasonic 30min, after add 50 μMs of concentrated sulfuric acids, 50mM neopelex, is stirred.
(3) electrochemical deposition porous graphene electrode
The mixed solution of preparation is placed in electrolytic cell, adopt constant potential electrochemical method, gold plaque electrode is as work electrode, platinum plate electrode is as to electrode, saturated calomel electrode is as the three-electrode system of reference electrode, under-1.2V voltage conditions, deposit different time 10s-120s, be placed in distilled water and soak 30min, freeze drying obtains Graphene porous electrode.
(4) using porous graphene electrode as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.Cyclic voltammetry, sweeping speed is: 50mV/s-5000mV/s; Charge-discharge test, current density is: 0.5mA/cm
2-5mA/cm
2.
Embodiment 3
(1) graphene oxide solution is prepared with reference to the method for embodiment 1
(2) formula of electrolyte
Preparation 3mg/mL graphene oxide solution, by its ultrasonic 30min, after add 50 μMs of concentrated sulfuric acids, 50mM neopelex, is stirred.
(3) electrochemical deposition porous graphene electrode
The mixed solution of preparation is placed in electrolytic cell, adopt constant potential electrochemical method, gold plaque electrode is as work electrode, platinum plate electrode as to electrode, saturated calomel electrode as the three-electrode system of reference electrode ,-0.8V under different voltage conditions,-1.0V,-1.2V deposits different time 120s, is placed in distilled water and soaks 30min, and freeze drying obtains Graphene porous electrode.
(4) using porous graphene electrode as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.Cyclic voltammetry, sweeping speed is: 50mV/s-5000mV/s; Charge-discharge test, current density is: 0.5mA/cm
2-5mA/cm
2.
Embodiment 4
(1) graphene oxide is prepared with reference to the method for embodiment 1
(2) formula of electrolyte
Preparation 3mg/mL graphene oxide solution, by its ultrasonic 30min, after add 50 μMs of concentrated sulfuric acids, 50mM, 100mM, 200mM, 300mM, 400mM neopelex, is stirred.
(3) electrochemical deposition porous graphene electrode
The mixed solution of preparation is placed in electrolytic cell, adopt constant potential electrochemical method, gold plaque electrode is as work electrode, platinum plate electrode is as to electrode, saturated calomel electrode is as the three-electrode system of reference electrode, under-1.2V voltage conditions, deposit 120s, be placed in distilled water and soak 30min, freeze drying obtains Graphene porous electrode.
(4) using porous graphene electrode as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.Cyclic voltammetry, sweeping speed is: 50mV/s-5000mV/s; Charge-discharge test, current density is: 0.5mA/cm
2-5mA/cm
2.
Embodiment 5
(1) graphene oxide solution is prepared with reference to the method for embodiment 1
(2) formula of electrolyte
Preparation 3mg/mL graphene oxide solution, by its ultrasonic 30min, after add 50 μMs of concentrated sulfuric acids, 50mM neopelex, is stirred.
(3) electrochemical deposition porous graphene electrode
The mixed solution of preparation is placed in electrolytic cell, adopt the electrochemical method of constant potential, the different conductive substrate of titanium sheet, platinized platinum, graphene film, four kinds, copper wire is as work electrode, platinum plate electrode is as to electrode, saturated calomel electrode is as the three-electrode system of reference electrode, under-1.2V voltage conditions, deposit 120s, be placed in distilled water and soak 30min, freeze drying obtains Graphene porous electrode.
(4) using porous graphene electrode as work electrode, platinized platinum is as to electrode, and saturated calomel electrode, as reference electrode, in 1MKCl solution, detects its capacitive property.Cyclic voltammetry, sweeping speed is: 50mV/s-5000mV/s; Charge-discharge test, current density is: 0.5mA/cm
2-5mA/cm
2.
Claims (8)
1. hydrogen bubble template prepares a method for porous graphene electrode material, it is characterized in that comprising the following steps:
1) adopt Hummers legal system for graphene oxide solution, respectively through pickling, washing, this solution is placed in bag filter dialysis one week, after reaching neutrality, freeze drying process, obtains graphene oxide powder;
2) graphene oxide solution is prepared, it is ultrasonic, and add neopelex and the concentrated sulfuric acid, stir and make it mix, obtain mixed solution;
3) using this mixed solution as electrolyte, connect electrochemical appliance, select constant potential electrochemical techniques, adopt three-electrode system, using conductive substrate as work electrode, platinum plate electrode is as to electrode, saturated calomel electrode, as reference electrode, control voltage and time, makes electrode surface produce bubble, and reduce in this, as graphene oxide the template be deposited on conductive substrate, thus obtain porous graphene electrode material;
4) gained Graphene porous electrode is placed in distilled water, soaks removing impurity and ' through freeze drying, obtain dry Graphene porous electrode.
2. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 1) described in Hummers legal system specifically comprise the following steps for graphene oxide solution:
Under ice-water bath and stirring condition, successively the concentrated sulfuric acid, graphite powder and sodium nitrate are joined in beaker; To be mixed evenly after, slowly add potassium permanganate, and continue to stir in ice bath; Then, reaction temperature is increased to 35oC, and reacts at this temperature; Then, first add 150mL deionized water, then system temperature is increased to 90oC, continue vigorous stirring; After question response completes, add deionized water under agitation successively and percent by volume is the hydrogen peroxide of 30%; Above-mentioned product is placed in centrifuge tube, uses volume ratio 1:10 diluted hydrochloric acid aqueous solution and deionized water centrifuge washing successively; After centrifugal completing, by solid by ultrasonic dissolution in deionized water, transfer to dialysis in bag filter subsequently and remove remaining metal ion and acid, until solution is neutral; Finally by the reactant after dialysis, centrifugal by 4000 turns/min, abandon the graphite of the non-complete oxidation of bottom, obtain GO colloid aqueous solution, by freeze drying process, obtain graphene oxide powder.
3. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 2) in, the concentration of graphene oxide is 1-5mg/mL.
4. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 2) in, the concentration of neopelex is 50mM-400mM.
5. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 2) in, add 50 μMs of concentrated sulfuric acids
The method of bubble Template preparation porous graphene electrode, is characterized in that: step 3 as claimed in claim 1) in, the voltage of electrochemical deposition is-0.8V ~-1.2V.
6. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 3) in, the time of electrochemical deposition is 10s-90s.
7. the method for bubble Template preparation porous graphene electrode as claimed in claim 1, is characterized in that: step 3) in, conductive substrate is gold plaque, platinized platinum, titanium sheet, copper wire, the graphene film of conduction or conduction carbon paper.
8. the porous graphene electrode prepared of hydrogen bubble template, in the application of ultracapacitor, is characterized in that change sweeps speed from 50mV/s-5000mV/s, changes current density from 0.5mA/cm as claimed in claim 1
2-5mA/cm
2, detect the capacitive property of Graphene porous material.
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