CN105575679A - Method for preparing graphene membrane electrode - Google Patents
Method for preparing graphene membrane electrode Download PDFInfo
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- CN105575679A CN105575679A CN201510960028.4A CN201510960028A CN105575679A CN 105575679 A CN105575679 A CN 105575679A CN 201510960028 A CN201510960028 A CN 201510960028A CN 105575679 A CN105575679 A CN 105575679A
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- graphene
- graphene oxide
- filter membrane
- oxide
- membrane
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 415
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 415
- 239000012528 membrane Substances 0.000 title claims abstract description 199
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 66
- 239000006185 dispersion Substances 0.000 claims abstract description 53
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 53
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 56
- 239000007787 solid Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000011435 rock Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 6
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 3
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940067157 phenylhydrazine Drugs 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229960005196 titanium dioxide Drugs 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000012466 permeate Substances 0.000 abstract 1
- 230000001603 reducing effect Effects 0.000 abstract 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 11
- 238000004146 energy storage Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 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
- H01G11/84—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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- 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)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to the technical field of graphene membranes, particularly to a method for preparing a graphene membrane electrode. Before a garphene membrane layer is adhered to a filter membrane, first part of a graphene oxide dispersion liquid is taken on the filter membrane to obtain a graphene oxide membrane layer through suction filtration, then a reducing agent is utilized to reduce the residual graphene oxide dispersion liquid, and a graphene membrane layer is composited on the graphene oxide membrane layer through vacuum filtration to form a graphene/graphene oxide composite film. When the additionally arranged graphene oxide membrane layer can permeate is infiltrated by a hydroiodic acid water solution, through reducing action of hydroiodic acid permeating to between the graphene oxide membrane layer and the filter membrane, the graphene/graphene oxide composite membrane is rapidly and completely stripped from the filter membrane, thereby solving the problem that when a traditional vacuum filtration method is utilized to prepare a graphene membrane, the graphene membrane is directly adhered to the filter membrane and is not easy to strip from the filter membrane; and after the graphene oxide membrane layer is reduced, the graphene membrane layer can be perfected, and the graphene oxide membrane layer and the graphene membrane layer form a unified whole, thereby improving the performance of a graphene membrane electrode.
Description
Technical field
The present invention relates to graphene film technical field, especially relate to a kind of preparation method of graphene film electrode.
Background technology
Since two professor AndreGeim and KonstantinNovoselov of Univ Manchester UK in 2010, because of successfully obtaining stable Graphene first, since obtaining Nobel Prize in physics, Graphene obtains broad scale research and application as a kind of special material.Theoretic perfect Graphene (Graphene) is a kind of monolayer two dimensional crystal, there is the highest intensity of known materials (Science, 2008,321,385-388) and the conductivity of excellence and thermal conductivity, in electricity, optics, magnetics, mechanics, chemistry, biology etc., the potentiality attracted people's attention are had.In energy storage, Graphene also obtains the research and development energetically of scientific research personnel in recent years.Two-dimensional films material a kind of form of practical function also can obtain industry and studies energetically as Graphene, and the toughness of high conductivity, high strength and excellence that nowadays the closelypacked graphene film of LBL self-assembly shows also is that industry is very paid close attention to.But, closelypacked Graphene rete can not allow electrolyte be fully utilized, thus Graphene is significantly limited in energy storage, and extensive preparation also can be the practical great difficult problem faced of current Graphene energy storage device for the graphene film of stored energy application.
Although there is the graphene film that bibliographical information has hydrazine hydrate reduction graphene oxide vacuum filtration can obtain for energy storage, but this method needs to use expensive anodised aluminium filter membrane, and obtain graphene film and also cannot overcome the spontaneous stack effect of graphene nanometer sheet, cause, as the energy storage device of electrode material assembling, recycling the decline of performance.The graphene film prepared often is made to be difficult to complete stripping down from filter membrane if adopt organic filter membrane to take out film, destroy the integrality of film, peel off even if careful because not high being also easy to of graphene film intensity is broken, cannot use as electrode material as a whole, lose the meaning of graphene film itself.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of cost low, recycle good stability, easily peel off with filter membrane, there is high conductivity, high-specific surface area, and the preparation method of electrolyte contacts resistance is little, pliability is good graphene film electrode.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for graphene film electrode, it comprises the following steps:
1) take graphene oxide solid stirring and dissolving in water, adopt ultrasonic wave dispersion treatment, obtain the graphene oxide dispersion that concentration is 1-2mg/ml;
2) 5-20% getting graphene oxide dispersion is placed in Vacuum filtration device, by filter membrane vacuum filtration, obtains the graphene oxide rete be attached on filter membrane;
3) in remaining graphene oxide dispersion, add promoter regulates the pH value of graphene oxide dispersion to be after 9-11, then adds reducing agent, is under the condition of 80-95 DEG C in temperature, stirs reduction reaction 1-6 hour; Then use pure water, suction filtration is neutral, removes unnecessary reducing agent and promoter, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, adopt ultrasonic wave dispersion treatment, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into proppant, adopt ultrasonic wave dispersion treatment, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) filter membrane being attached with graphene/graphene oxide composite membrane is taken out in Vacuum filtration device, be immersed under normal temperature in hydriodic acid aqueous solution, rock gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, graphene/graphene oxide composite membrane continues to be immersed in hydriodic acid aqueous solution, is to leave standstill under the condition of 80-95 DEG C in temperature, reaction 0.5-3 hour, obtains moistening graphene film;
8) take out moistening graphene film, after soaking with cleaning agent the hydroiodic acid removing attachment, place under normal temperature and dry, obtained graphene film electrode.
Step 1) described in graphene oxide solid be standby by Brodie method, Staudenmaier method or Hummers legal system and obtain.
Step 2) described in filter membrane be PVDF filter membrane or CN-CA cellulose mixture filter membrane.
Step 2) described in graphene oxide thicknesses of layers be 20-50 μm.
Step 3) described in reducing agent be one in hydrazine hydrate, sodium borohydride aqueous solution, the phenylhydrazine aqueous solution, phenol solution, the Tea Polyphenols aqueous solution, aqueous solution of urea, potassium hydroxide aqueous solution, D/W, hydrobromic acid aqueous solution, aqueous acetic acid, sodium thiosulfate solution, sodium hydrate aqueous solution or the vitamin C aqueous solution.
Step 4) described in proppant be metal oxide powder or conductive black, described proppant addition is the 0.5-15% of graphene oxide solid masses.
Described metal oxide powder is the one in tin oxide, cobaltosic oxide, iron oxide, mangano-manganic oxide, manganous oxide, tri-iron tetroxide, molybdenum trioxide, nickel oxide, titanium dioxide, cupric oxide, cuprous oxide, LiFePO4, cerium oxide or vanadic oxide.
Step 1), step 3) and step 4) described in ultrasonic wave dispersion treatment be and be 10-30KHz at ultrasonic power, under temperature is the condition of 20-35 DEG C, carry out ultrasonic wave process 0.5-1.5 hour.
Step 3) described in promoter to be mass fraction be 28% ammoniacal liquor or mass fraction be the aqueous sodium carbonate of 5%; Step 6) described in the mass fraction of hydriodic acid aqueous solution be 40-47%.
Step 8) described in cleaning agent be made up of more than one in pure water, ethanol or acetone.
The present invention adopts above technical scheme, before filter membrane adheres to Graphene rete, the 5-20% first getting graphene oxide dispersion total amount first adheres to one deck graphene oxide rete by vacuum filtration on the organic filter membrane dissolving in hydroiodic acid, residue graphene oxide dispersion is reduced into graphene dispersing solution by recycling reducing agent, and in graphene dispersing solution, add proppant in case occur from stacking, then vacuum filtration is continued, on graphene oxide rete, composite graphite alkene rete forms graphene/graphene oxide composite membrane, described graphene/graphene oxide composite membrane comprises graphene oxide rete and Graphene rete, finally adopt hydriodic acid aqueous solution to carry out immersion to be separated and reduction, make the graphene oxide rete of graphene/graphene oxide composite membrane when being infiltrated by hydriodic acid aqueous solution, the reduction between graphene oxide rete and filter membrane is infiltrated into by hydroiodic acid, make graphene/graphene oxide composite membrane quick, intactly strip down from filter membrane, when solving tradition employing vacuum filtration legal system dexterously for graphene film, graphene film is attached directly on filter membrane and makes its problem not easily peeled off with filter membrane, simultaneously, graphene oxide rete follow-up reduced by hydriodic acid aqueous solution after, Graphene rete can not only be improved, and define unified entirety with Graphene rete, thus improve conductivity and the specific area of obtained graphene film electrode, it is made to be suitable for use as ultracapacitor, the energy storage electrode materials such as lithium battery.With tradition adopt hydroiodic acid/alcohol vapour at high temperature Reduced separating or adopt ultrasonic stripping method compared with, as long as the graphene/graphene oxide composite membrane be attached on filter membrane is immersed in hydriodic acid aqueous solution by the present invention under normal temperature, then rock gently and filter membrane just can be made to be separated completely with graphene/graphene oxide composite membrane, simple to operate, can not to break the integrality of graphene film, thus, the present invention can adopt the common organic filter membrane dissolving in hydroiodic acid and the anodised aluminium filter membrane of alternative traditional price costliness when vacuum filtration, greatly reduce production cost.
The present invention carries out twice composite reduction by reducing agent and hydriodic acid aqueous solution, and add proppant, the graphene film electrode obtained is had, and conductance is high, graphene film interlayer has the features such as a large amount of hole, specific area are large, be conducive to electrolyte and enter electrode material inside, carry out Electrostatic Absorption at electrode surface, improve its charge storage ability.The present invention adds proppant in graphene dispersing solution, the graphene nanometer sheet interlayer overcoming conventional graphite alkene film produces from stacking phenomenon and then shortcoming that to cause that cyclical stability is poor, charge storage ability is decayed fast due to the stacking effect of π-π, the graphene film electrode that the present invention obtains is through experimental test, its cycle-index reaches 10,000 times, ratio capacitance decay is less than 7%, especially adopt hydrazine hydrate as reducing agent can also original place be more thorough, obtained graphene film electrode conductivity is high, specific area is large, generally can reach 800m
2/ g, under the current density of 1A/g, ratio capacitance can reach 160F/g; In addition, adopt the graphene film electrode that hydrazine hydrate reduction is obtained, due to doped with nitrogen-atoms, the contact resistance of itself and electrolyte is very little, to be conducive under high current density discharge and recharge, improve cycle charge discharge electrical stability.
The present invention is when vacuum filtration, by increasing one deck 20-50 μm of thick graphene oxide rete between filter membrane and Graphene rete in advance, graphene oxide rete can be allowed when being infiltrated by hydriodic acid aqueous solution, the reduction between graphene oxide rete and filter membrane is infiltrated into by hydroiodic acid, allow graphene/graphene oxide composite membrane easily strip down from filter membrane fast, and do not destroy the integrality of graphene/graphene oxide composite membrane.In addition, this graphene oxide rete set up is reduced into Graphene in subsequent operation, and defines unified entirety with the Graphene rete on upper strata, thus can not reduce the performance of graphene film electrode; Adopt the design of this double-layered compound film, can solve the graphene film that traditional vacuum suction method obtains very is dexterously be attached directly on filter membrane thus cause graphene film not easily from the problem that filter membrane is peeled off.Preparation method's processing ease of the present invention, the graphene film electrode of preparation has very high conductivity, excellent specific area, excellent pore volume and good pliability, and easy and filter membrane is peeled off, little with electrolyte contacts resistance, have can prevent from stacking, recycle the advantages such as good stability, the energy storage fields such as solar cell, ultracapacitor, lithium ion battery can be widely used in as electrode material.
Accompanying drawing explanation
Now the present invention is further elaborated by reference to the accompanying drawings:
Fig. 1 is the photo of graphene film electrode of the present invention;
Fig. 2 is the cyclic voltammetry curve figure of the graphene film electrode that the embodiment of the present invention 1 obtains;
Fig. 3 is the ultracapacitor constant current charge-discharge curve chart by graphene film electrode assembling of the present invention under current density is 1A/g;
Fig. 4 is the ratio capacitance situation map by ultracapacitor 10000 circulation constant current charge-discharges of graphene film electrode assembling of the present invention under current density is 1A/g.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation:
A preparation method for graphene film electrode, it comprises the following steps:
1) take graphene oxide solid stirring and dissolving in water, adopt ultrasonic wave dispersion treatment, obtain the graphene oxide dispersion that concentration is 1-2mg/ml;
2) 5-20% getting graphene oxide dispersion is placed in Vacuum filtration device, by filter membrane vacuum filtration, obtains the graphene oxide rete be attached on filter membrane;
3) in remaining graphene oxide dispersion, add promoter regulates the pH value of graphene oxide dispersion to be after 9-11, then adds reducing agent, is under the condition of 80-95 DEG C in temperature, stirs reduction reaction 1-6 hour; Then use pure water, suction filtration is neutral, removes unnecessary reducing agent and promoter, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, adopt ultrasonic wave dispersion treatment, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into proppant, adopt ultrasonic wave dispersion treatment, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) filter membrane being attached with graphene/graphene oxide composite membrane is taken out in Vacuum filtration device, be immersed under normal temperature in hydriodic acid aqueous solution, rock gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, graphene/graphene oxide composite membrane continues to be immersed in hydriodic acid aqueous solution, is to leave standstill under the condition of 80-95 DEG C in temperature, reaction 0.5-3 hour, obtains moistening graphene film;
8) take out moistening graphene film, after soaking with cleaning agent the hydroiodic acid removing attachment, place under normal temperature and dry, obtained graphene film electrode.
Step 1) described in graphene oxide solid be standby by Brodie method, Staudenmaier method or Hummers legal system and obtain.
Step 2) described in filter membrane be PVDF filter membrane or CN-CA cellulose mixture filter membrane.
Step 2) described in graphene oxide thicknesses of layers be 20-50 μm.
Step 3) described in reducing agent be one in hydrazine hydrate, sodium borohydride aqueous solution, the phenylhydrazine aqueous solution, phenol solution, the Tea Polyphenols aqueous solution, aqueous solution of urea, potassium hydroxide aqueous solution, D/W, hydrobromic acid aqueous solution, aqueous acetic acid, sodium thiosulfate solution, sodium hydrate aqueous solution or the vitamin C aqueous solution.
Step 4) described in proppant be metal oxide powder or conductive black, described proppant addition is the 0.5-13% of graphene oxide solid masses.
Described metal oxide powder is the one in tin oxide, cobaltosic oxide, iron oxide, mangano-manganic oxide, manganous oxide, tri-iron tetroxide, molybdenum trioxide, nickel oxide, titanium dioxide, cupric oxide, cuprous oxide, LiFePO4, cerium oxide or vanadic oxide.
Step 1), step 3) and step 4) described in ultrasonic wave dispersion treatment be and be 10-30KHz at ultrasonic power, under temperature is the condition of 20-35 DEG C, carry out ultrasonic wave process 0.5-1.5 hour.
Step 3) described in promoter to be mass fraction be 28% ammoniacal liquor or mass fraction be the aqueous sodium carbonate of 5%; Step 6) described in the mass fraction of hydriodic acid aqueous solution be 40-47%.
Step 8) described in cleaning agent be made up of more than one in pure water, ethanol or acetone.
Embodiment 1
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Hummers legal system to obtain freeze drying, take 100mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 10KHz, under temperature is the condition of 20 DEG C, carry out ultrasonic wave process 1.5 hours, obtain the graphene oxide dispersion that concentration is 1mg/ml;
2) get 10ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the PVDF filter membrane of pore-size 0.2 μm;
3) add in remaining graphene oxide dispersion mass fraction be 28% ammoniacal liquor regulate the pH value of graphene oxide dispersion to be after 10, add the hydrazine hydrate that 0.5ml mass fraction is 85% again, be under the condition of 90 DEG C in temperature, stir reduction reaction 4 hours; Then use pure water, suction filtration is neutral, removes unnecessary hydrazine hydrate and ammoniacal liquor, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 20KHz at ultrasonic power, under temperature is the condition of 25 DEG C, carries out ultrasonic wave process 1 hour, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the conductive black of 5mg, be 10KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 0.5 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 20ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 47%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 47% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 95 DEG C in temperature, react 1 hour, obtain moistening graphene film;
8) take out moistening graphene film, after soaking with pure water the hydroiodic acid removing attachment, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
Embodiment 2
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Hummers legal system to obtain freeze drying, take 200mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 10KHz, under temperature is the condition of 30 DEG C, carry out ultrasonic wave process 1 hour, obtain the graphene oxide dispersion that concentration is 2mg/ml;
2) get 5ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the PVDF filter membrane of pore-size 0.2 μm;
3) add in remaining graphene oxide dispersion mass fraction be 28% ammoniacal liquor regulate the pH value of graphene oxide dispersion to be after 11, add the hydrazine hydrate that 0.5ml mass fraction is 85% again, be under the condition of 95 DEG C in temperature, stir reduction reaction 3 hours; Then use pure water, suction filtration is neutral, removes unnecessary hydrazine hydrate and ammoniacal liquor, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 20KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1 hour, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the conductive black of 10mg, be 20KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 30ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 47%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 47% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 95 DEG C in temperature, react 1.5 hours, obtain moistening graphene film;
8) take out moistening graphene film, after soaking with pure water the hydroiodic acid removing attachment, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
Embodiment 3
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Hummers legal system to obtain freeze drying, take 200mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 20KHz, under temperature is the condition of 25 DEG C, carry out ultrasonic wave process 1.5 hours, obtain the graphene oxide dispersion that concentration is 2mg/ml;
2) get 15ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the PVDF filter membrane of pore-size 0.2 μm;
3) add in remaining graphene oxide dispersion mass fraction be 5% aqueous sodium carbonate regulate the pH value of graphene oxide dispersion to be after 9, the sodium borohydride powder of 1000mg is first dissolved in the pure water of 20ml and forms sodium borohydride aqueous solution, again sodium borohydride aqueous solution gradation is joined in graphene oxide dispersion, be under the condition of 95 DEG C in temperature, stir reduction reaction 6 hours; Then use pure water, suction filtration is neutral, removes unnecessary sodium borohydride and sodium carbonate, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 30KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1.5 hours, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the conductive black of 5mg, be 20KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 30ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 45%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 45% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 85 DEG C in temperature, react 2 hours, obtain moistening graphene film;
8) take out moistening graphene film, be after the pure water of 5:1 and alcohol mixeding liquid soak the hydroiodic acid removing attachment by volume ratio, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
Embodiment 4
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Staudenmaier legal system to obtain freeze drying, take 200mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 30KHz, under temperature is the condition of 20 DEG C, carry out ultrasonic wave process 0.5 hour, obtain the graphene oxide dispersion that concentration is 2mg/ml;
2) get 15ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the CN-CA cellulose mixture filter membrane of pore-size 0.2 μm;
3) add in remaining graphene oxide dispersion mass fraction be 5% aqueous sodium carbonate regulate the pH value of graphene oxide dispersion to be after 10, the sodium borohydride powder of 1000mg is first dissolved in the pure water of 15ml and forms sodium borohydride aqueous solution, again sodium borohydride aqueous solution gradation is joined in graphene oxide dispersion, be under the condition of 95 DEG C in temperature, stir reduction reaction 4 hours; Then use pure water, suction filtration is neutral, removes unnecessary sodium borohydride and sodium carbonate, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 30KHz at ultrasonic power, under temperature is the condition of 20 DEG C, carries out ultrasonic wave process 1 hour, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the trimanganese tetroxide nano powder of 10mg, be 30KHz at ultrasonic power, under temperature is the condition of 20 DEG C, carries out ultrasonic wave process 0.5 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 25ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 40%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 40% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 80 DEG C in temperature, react 3 hours, obtain moistening graphene film;
8) take out moistening graphene film, be after the pure water of 1:1 and alcohol mixeding liquid soak the hydroiodic acid removing attachment by volume ratio, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
Embodiment 5
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Brodie legal system to obtain freeze drying, take 200mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 20KHz, under temperature is the condition of 30 DEG C, carry out ultrasonic wave process 0.5 hour, obtain the graphene oxide dispersion that concentration is 2mg/ml;
2) get 5ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the PVDF filter membrane of pore-size 0.2 μm;
3) concentration adding 10ml in remaining graphene oxide dispersion is the 5mg/ml vitamin C aqueous solution, under nitrogen protection, and 90 DEG C of stirring reactions 12 hours; Then use pure water, suction filtration is neutral, removes unnecessary vitamin C, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 20KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1 hour, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the conductive black of 5mg, be 15KHz at ultrasonic power, under temperature is the condition of 30 DEG C, carries out ultrasonic wave process 1 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 30ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 45%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 45% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 95 DEG C in temperature, react 2 hours, obtain moistening graphene film;
8) take out moistening graphene film, be after the pure water of 8:2 and alcohol mixeding liquid soak the hydroiodic acid removing attachment by volume ratio, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
Embodiment 6
A preparation method for graphene film electrode, it comprises the following steps:
1) the graphene oxide solid after adopting Brodie legal system to obtain freeze drying, take 200mg graphene oxide solid is dissolved in the water of 100ml after stirring, ultrasonic power be 30KHz, under temperature is the condition of 35 DEG C, carry out ultrasonic wave process 1 hour, obtain the graphene oxide dispersion that concentration is 2mg/ml;
2) get 5ml graphene oxide dispersion and be placed in Vacuum filtration device, by filter membrane vacuum filtration, obtain the graphene oxide rete be attached on filter membrane; Wherein, the filter membrane of employing is the CN-CA cellulose mixture filter membrane of pore-size 0.45 μm;
3) add in remaining graphene oxide dispersion mass fraction be 28% ammoniacal liquor regulate the pH value of graphene oxide dispersion to be after 10, add the hydrazine hydrate that 0.5ml mass fraction is 85% again, be under the condition of 95 DEG C in temperature, stir reduction reaction 3 hours; Then use pure water, suction filtration is neutral, removes unnecessary hydrazine hydrate and ammoniacal liquor, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, be 30KHz at ultrasonic power, under temperature is the condition of 35 DEG C, carries out ultrasonic wave process 1 hour, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into the conductive black of 5mg and the trimanganese tetroxide nano powder of 5mg, be 30KHz at ultrasonic power, under temperature is the condition of 35 DEG C, carries out ultrasonic wave process 1 hour, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) taken out in Vacuum filtration device by the filter membrane being attached with graphene/graphene oxide composite membrane, being immersed in 30ml mass fraction under normal temperature is in the hydriodic acid aqueous solution of 45%, rocks gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, it is in the hydriodic acid aqueous solution of 45% that graphene/graphene oxide composite membrane continues to be immersed in mass fraction, is to leave standstill under the condition of 95 DEG C in temperature, react 3 hours, obtain moistening graphene film;
8) take out moistening graphene film, be after the pure water of 3:2 and alcohol mixeding liquid soak the hydroiodic acid removing attachment by volume ratio, place under normal temperature and dry, obtained graphene film electrode.
The graphene film electrode performance parameter testing data that the present embodiment obtains are as shown in table 1.
As can be seen from the cyclic voltammetric song of graphene film electrode prepared by the embodiment of the present invention 1 shown in Fig. 2, under the sweep speed of cyclic voltammetric is the test condition of 100mV/s, the ready-made extraordinary symmetrical rectangular of curve table, electric double layer energy storage characteristic is well embodied.
From can be learnt by the ultracapacitor constant current charge-discharge curve chart of graphene film electrode assembling of the present invention current density is 1A/g shown in Fig. 3, its ratio capacitance value reaches 160F/g, curve does not almost demonstrate discharge voltage and falls, more common Graphene compact reactor integrated membrane (60-80F/g) improves a lot, shows excellent performance in energy storage.
From can be learnt by the ratio capacitance situation map of ultracapacitor 10000 circulation constant current charge-discharges of graphene film electrode assembling of the present invention current density is 1A/g shown in Fig. 4, it is through 10000 circulation constant current charge-discharges, ratio capacitance only decays 5%, good cycling stability, shows excellent performance in energy storage.
The performance test data of graphene film electrode under current density is 1A/g prepared by table 1 embodiment of the present invention 1-5
As can be seen here, graphene film electrode cycle stable charge/discharge prepared by the present invention is good, has the advantages such as conductivity is high, charge storage ability strong, ratio capacitance decay is little; Embodiments of the invention 2 are preferred versions.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for graphene film electrode, is characterized in that: it comprises the following steps:
1) take graphene oxide solid stirring and dissolving in water, adopt ultrasonic wave dispersion treatment, obtain the graphene oxide dispersion that concentration is 1-2mg/ml;
2) 5-20% getting graphene oxide dispersion is placed in Vacuum filtration device, by filter membrane vacuum filtration, obtains the graphene oxide rete be attached on filter membrane;
3) in remaining graphene oxide dispersion, add promoter regulates the pH value of graphene oxide dispersion to be after 9-11, then adds reducing agent, is under the condition of 80-95 DEG C in temperature, stirs reduction reaction 1-6 hour; Then use pure water, suction filtration is neutral, removes unnecessary reducing agent and promoter, dry, obtains Graphene solid; By Graphene dissolution of solid in the pure water of 100ml, adopt ultrasonic wave dispersion treatment, obtain graphene dispersing solution;
4) in graphene dispersing solution, be added into proppant, adopt ultrasonic wave dispersion treatment, obtain Graphene mixed liquor;
5) Graphene mixed liquor is poured into step 2) filter membrane is attached with in the Vacuum filtration device of graphene oxide rete, continue vacuum filtration, on graphene oxide rete, compound one deck Graphene rete forms graphene/graphene oxide composite membrane, obtains the graphene/graphene oxide composite membrane be attached on filter membrane;
6) filter membrane being attached with graphene/graphene oxide composite membrane is taken out in Vacuum filtration device, be immersed under normal temperature in hydriodic acid aqueous solution, rock gently and filter membrane is separated with graphene/graphene oxide composite membrane;
7) after filter membrane is separated with graphene/graphene oxide composite membrane, taken out by filter membrane, graphene/graphene oxide composite membrane continues to be immersed in hydriodic acid aqueous solution, is to leave standstill under the condition of 80-95 DEG C in temperature, reaction 0.5-3 hour, obtains moistening graphene film;
8) take out moistening graphene film, after soaking with cleaning agent the hydroiodic acid removing attachment, place under normal temperature and dry, obtained graphene film electrode.
2. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: the graphene oxide solid described in step 1) is standby by Brodie method, Staudenmaier method or Hummers legal system and obtain.
3. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: step 2) described in filter membrane be PVDF filter membrane or CN-CA cellulose mixture filter membrane.
4. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: step 2) described in graphene oxide thicknesses of layers be 20-50 μm.
5. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: the reducing agent described in step 3) is the one in hydrazine hydrate, sodium borohydride aqueous solution, the phenylhydrazine aqueous solution, phenol solution, the Tea Polyphenols aqueous solution, aqueous solution of urea, potassium hydroxide aqueous solution, D/W, hydrobromic acid aqueous solution, aqueous acetic acid, sodium thiosulfate solution, sodium hydrate aqueous solution or the vitamin C aqueous solution.
6. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: the proppant described in step 4) is metal oxide powder or conductive black, described proppant addition is the 0.5-15% of graphene oxide solid masses.
7. the preparation method of a kind of graphene film electrode according to claim 6, is characterized in that: described metal oxide powder is the one in tin oxide, cobaltosic oxide, iron oxide, mangano-manganic oxide, manganous oxide, tri-iron tetroxide, molybdenum trioxide, nickel oxide, titanium dioxide, cupric oxide, cuprous oxide, LiFePO4, cerium oxide or vanadic oxide.
8. the preparation method of a kind of graphene film electrode according to claim 1, it is characterized in that: the ultrasonic wave dispersion treatment described in step 1), step 3) and step 4) is and is 10-30KHz at ultrasonic power, under temperature is the condition of 20-35 DEG C, carries out ultrasonic wave process 0.5-1.5 hour.
9. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: the promoter described in step 3) to be mass fraction be 28% ammoniacal liquor or mass fraction be the aqueous sodium carbonate of 5%; The mass fraction of the hydriodic acid aqueous solution described in step 6) is 40-47%.
10. the preparation method of a kind of graphene film electrode according to claim 1, is characterized in that: the cleaning agent described in step 8) is made up of more than one in pure water, ethanol or acetone.
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| CN107857251A (en) * | 2017-10-13 | 2018-03-30 | 浙江大学 | A kind of nanometer grade thickness independent self-supporting expandable graphite alkene film and preparation method thereof |
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| CN112635732A (en) * | 2020-12-17 | 2021-04-09 | 中国电子科技集团公司第十八研究所 | Preparation method of graphene/lithium cobaltate composite positive electrode material |
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