CN107093525A - A kind of preparation method of the electrode material of oxidized graphene aqueous solution processing - Google Patents
A kind of preparation method of the electrode material of oxidized graphene aqueous solution processing Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 30
- 238000010129 solution processing Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 230000004913 activation Effects 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 12
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000003763 carbonization Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- PESZCXUNMKAYME-UHFFFAOYSA-N Citroflex A-4 Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)C(C(C)=O)C(=O)OCCCC PESZCXUNMKAYME-UHFFFAOYSA-N 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 13
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 13
- 229940071182 stannate Drugs 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000002845 discoloration Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 4
- -1 it is agitated Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention discloses a kind of preparation method of the electrode material of oxidized graphene aqueous solution processing, the technique after graphite oxidation by will obtain graphite oxide, again with the processing of graphene oxide water solution Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection, it is modified again, then it is placed in reactor and adds mixed solvent, polyvinylpyrrolidone and positive silicic acid propyl ester, intermediate is obtained through high-temperature process, then intermediate is subjected to the operation such as curing process, add other compositions, it is agitated, coating, drying, electrode slice is made in the steps such as roll-in.The electrode material for the oxidized graphene aqueous solution processing being prepared from, its specific capacity is big, good cycling stability, stable electrochemical property, energy density are high, with preferable application prospect.Application of the electrode material handled as oxidized graphene aqueous solution made from the preparation technology in ultracapacitor is prepared is also disclosed simultaneously.
Description
Technical field
The present invention relates to this technical field of capacitor material, a kind of oxidized graphene aqueous solution processing is related specifically to
Electrode material preparation method.
Background technology
The demand of world today's energy relies primarily on chemical fuel, but chemical fuel is increasingly in short supply.People are in the urgent need to height
Effect, cleaning, the novel energy of reusable edible.So novel renewable energy research is a focus.But regenerative resource,
Such as utilization of wind energy, solar energy regenerative resource is had a strong impact on by season, meteorological and regional condition, therefore develops new storage
Energy device, is effectively to utilize one of key issue of regenerative resource.Scientists have successively developed different types of electrochemistry
Energy storage device, such as lithium ion battery, fuel cell, ultracapacitor.
Ultracapacitor is new energy storage device, there is significant advantage：Energy density is high, and the discharge and recharge time is short, circulation
Long lifespan.For a capacitor, its core is electrode, and electrode material is the chemical property of determining electrode
Key.Different according to the principle that ultracapacitor stores energy, electrode material can probably be divided into three classes：Carbon material is (as lived
Property charcoal, graphene etc.), metal hydroxides or oxide (such as ruthenium-oxide, nickel hydroxide, cobalt hydroxide, nickel oxide, titanium dioxide
Manganese etc.) and conducting polymer (such as polyacetylene, polythiophene).In recent years, with super capacitor of the graphene as electrode material
Device also appears in the newspapers repeatly, is limited yet with the Ultrahigh of carbon material, the electricity of the ultracapacitor based on graphene nano material
Capacitive energy is simultaneously unsatisfactory, generally only 100~200F/g.On the other hand, although though conducting polymer materials polyaniline has
There is the specific capacitance value higher than carbon material, but the electrical conductivity of common polyaniline material is still relatively low, and cyclical stability is unsatisfactory,
This also just directly constrains its practical application.Therefore, finally given to evade the shortcoming of different materials with high specific capacitance
And stable ultracapacitor is, it is necessary to develop a kind of new composite electrode with preferable cooperative effect.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of system of the electrode material of oxidized graphene aqueous solution processing
Preparation Method, the technique is handled by will obtain graphite oxide after graphite oxidation, then with graphene oxide water solution Hybrid Heating,
Then high-temperature process obtains activation products under nitrogen protection, then is modified, and is then placed in reactor and adds deionized water
With the mixed solvent, polyvinylpyrrolidone and positive silicic acid propyl ester of absolute ethyl alcohol, intermediate is obtained after high-temperature process, is connect
Intermediate curing process, ball-milling treatment, carbonization treatment, finally add tributyl 2-acetylcitrate, lead zinc niobate,
Electrode slice is made in barium stannate, conductive agent, binding agent, the step such as agitated, coating, drying, roll-in.The oxidized stone being prepared from
The electrode material of black aqueous solution processing, its specific capacity is big, good cycling stability, stable electrochemical property, energy density are high, tool
There is preferable application prospect.The electrode material handled as oxidized graphene aqueous solution made from the preparation technology is also disclosed simultaneously
Expect the application in ultracapacitor is prepared.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of the electrode material of oxidized graphene aqueous solution processing, comprises the following steps：
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15-25 min are incubated, 15-20g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200
Rpm speed stirring reaction 80-90 min, question response terminates to add the dioxygen that 300 mL mass fractions are 2.5% in backward container
Water, mixed liquor is stirred to discoloration, filter while hot with 150 rpm speed, by the gained filter cake hydrochloric acid solution of mass concentration 3%
Washing 2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite is obtained
Oxide；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, mixed liquor be then placed in 85 DEG C of baking oven heating 30-40 min, thick slurry is obtained, then under nitrogen protection in
High-temperature process 1.5h at 1000-1200 DEG C, obtains high-temperature activation product, in being carried out with watery hydrochloric acid to high-temperature activation product tentatively
With, then high-temperature activation product is washed 3-5 times to pH with deionized water neutrality is fully achieved, it is placed in 70 DEG C of vacuum drying chambers and does
Dry 8h, obtains modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, stirring reaction 2-3 h,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
Machine ball milling 2-3 h, powder obtained by ball milling is placed in atmosphere tube type stove, and carbonization treatment, treatment temperature are carried out under argon gas protection
For 950 DEG C, processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, bonding
Agent according to（65-70）:（11-13）:（7-9）:（5-8）:（3-5）:（2-4）Ratio mixing, add appropriate amount of deionized water, stirring
It is uniform to be coated in thick on stainless (steel) wire, then it is dried into 8-24 h in 80-130 DEG C of vacuum drying chamber, through roll-in
After be cut into electrode slice, obtain finished product.
Preferably, the step（4）Diameter of particle after middle ball milling is less than 2 μm.
Preferably, the step（5）Middle carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conduction
Agent, binding agent are according to 68:11:8:7:4:3 ratio mixing.
Preferably, the step（5）In conductive agent it is any one in acetylene black, CNT carbon black, activated carbon
Kind.
Preferably, the step（5）In binding agent in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol
Any one.
Exist present invention also offers the electrode material of the oxidized graphene aqueous solution obtained by above-mentioned preparation technology processing
Prepare the application in ultracapacitor.
Compared with prior art, its advantage is the present invention：
（1）The electrode material preparation technology of the oxidized graphene aqueous solution processing of the present invention after graphite oxidation by will obtain stone
Black oxide, then handled with graphene oxide water solution Hybrid Heating, then high-temperature process obtains activation production under nitrogen protection
Thing, then be modified, then it is placed in reactor and adds mixed solvent, the polyvinylpyrrolidone of deionized water and absolute ethyl alcohol
And positive silicic acid propyl ester, intermediate is obtained after high-temperature process, then by intermediate curing process, ball-milling treatment, carbon
Change is handled, and finally adds tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, binding agent, agitated, coating,
Electrode slice is made in the steps such as drying, roll-in.The electrode material for the oxidized graphene aqueous solution processing being prepared from, its specific capacity
Greatly, good cycling stability, stable electrochemical property, energy density are high, with preferable application prospect.
（2）The oxidized graphene aqueous solution processing of the present invention electrode material raw material is cheap, technique simple, suitable for big rule
Mould industrialization is used, practical.
Embodiment
The technical scheme of invention is described in detail with reference to specific embodiment.
Embodiment 1
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15 min are incubated, 15 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 80, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 30 min, thick slurry is obtained, then under nitrogen protection in 1000
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 3 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8h, is modified
Graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, acetylene black, carboxylic first
Base sodium cellulosate is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
8 h are dried in 80 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
Embodiment 2
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
20 min are incubated, 17 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 85, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 35 min, thick slurry is obtained, then under nitrogen protection in 1100
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 4 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8h, is modified
Graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2.5,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2.5, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, under argon gas protection
Carbonization treatment is carried out, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, CNT carbon
Black, hexafluoropropene is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
16 h are dried in 105 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
Embodiment 3
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
25 min are incubated, 20g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm speed
The min of rate stirring reaction 90, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 40 min, thick slurry is obtained, then under nitrogen protection in 1200
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 5 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8 h, is changed
Property graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 3 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 3, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, activated carbon, poly- second
Enol is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 24 h in 130 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
Comparative example 1
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15 min are incubated, 15 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 80, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 30 min, thick slurry is obtained, then under nitrogen protection in 1000
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 3 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8h, is modified
Graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, acetylene black, carboxylic first
Base sodium cellulosate is according to 80:9:12:15:2:6 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, coating
8 h are dried in 80 DEG C of vacuum drying chamber on stainless (steel) wire, then by it, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
Comparative example 2
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
20 min are incubated, 17 g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 85, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 35 min, thick slurry is obtained, then under nitrogen protection in 1100
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 4 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8h, is modified
Graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 2.5,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 2.5, gained diameter of particle is less than 2 μm；
（5）By step（4）Obtained powder, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, CNT carbon black, hexafluoro
Propylene is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 16 h in 105 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
Comparative example 3
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 70% is added in reaction vessel jointly, under 45 DEG C of water-bath
25 min are incubated, 30 g potassium permanganate is added, temperature 90 DEG C are risen to rapidly after maintaining 10 min, with 200 rpm's
The min of speed stirring reaction 90, question response terminates to add the hydrogen peroxide that 300 mL mass fractions are 2.5% in backward container, with 150
Rpm speed stirs mixed liquor to discoloration, filters while hot, and gained filter cake is washed 2 times with the hydrochloric acid solution of mass concentration 3%, then
It is washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite oxide is obtained；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 4 mg/mL graphene oxide water solution
Close, then mixed liquor is placed in 85 DEG C of baking oven and heats 40 min, thick slurry is obtained, then under nitrogen protection in 1500
High-temperature process 1.5h at DEG C, obtains high-temperature activation product, and high-temperature activation product is tentatively neutralized with watery hydrochloric acid, then spend from
High-temperature activation product is washed 5 times and neutrality is fully achieved to pH by sub- water, is placed in 70 DEG C of vacuum drying chambers and is dried 8 h, is changed
Property graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 2, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, the h of stirring reaction 3 will
Obtained product is centrifuged according to 3000 rpm rotating speed, and gained sediment is washed with deionized water, is placed in 90 DEG C very
6 h are dried in empty drying box, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
The h of machine ball milling 3, gained diameter of particle is less than 2 μm, and powder obtained by ball milling is placed in atmosphere tube type stove, enters under argon gas protection
Row carbonization treatment, treatment temperature is 950 DEG C, and processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, activated carbon, poly- second
Enol is according to 68:11:8:7:4:3 ratio mixing, adds appropriate amount of deionized water, is evenly stirred until thick, be coated in stainless
On steel mesh, then it is dried into 24 h in 130 DEG C of vacuum drying chamber, electrode slice is cut into after roll-in, finished product is obtained.
The performance test results of the electrode material of obtained oxidized graphene aqueous solution processing are as shown in table 1.
The electrode material of oxidized graphene aqueous solution processing made from embodiment 1-3 and comparative example 1-3 is entered respectively
Row specific capacity, capacity retention rate, energy density, this several performance tests of current density coefficient of stabilization.
Table 1
| Specific capacitance（F/g, 1A/g） | Capacity retention rate（%, 1000 cyclic voltammetries） | Energy density（Wh/kg） | Current density coefficient of stabilization（%, 12h, compared with original value） | |
| Embodiment 1 | 399 | 98.6 | 10.08 | 93.5 |
| Embodiment 2 | 397 | 99.1 | 10.03 | 94.4 |
| Embodiment 3 | 394 | 98.2 | 10.07 | 92.3 |
| Comparative example 1 | 257 | 79.3 | 7.03 | 72.9 |
| Comparative example 2 | 251 | 78.7 | 7.21 | 69.0 |
| Comparative example 3 | 287 | 82.7 | 7.51 | 75.7 |
The electrode material preparation technology of the oxidized graphene aqueous solution processing of the present invention after graphite oxidation by will obtain graphite
Oxide, then handled with graphene oxide water solution Hybrid Heating, then high-temperature process obtains activation products under nitrogen protection,
Be modified again, be then placed in reactor the mixed solvent for adding deionized water and absolute ethyl alcohol, polyvinylpyrrolidone and
Positive silicic acid propyl ester, obtains intermediate after high-temperature process, then by intermediate curing process, ball-milling treatment, carbonization
Processing, finally adds agitated tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, binding agent, coating, dries
Electrode slice is made in the steps such as dry, roll-in.The electrode material for the oxidized graphene aqueous solution processing being prepared from, its specific capacity
Greatly, good cycling stability, stable electrochemical property, energy density are high, with preferable application prospect.The oxidized stone of the present invention
The electrode material raw material of black aqueous solution processing is cheap, technique is simple, is used suitable for heavy industrialization, practical.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright description is made, or directly or indirectly it is used in other related technology necks
Domain, is included within the scope of the present invention.
Claims (6)
1. a kind of preparation method of the electrode material of oxidized graphene aqueous solution processing, it is characterised in that comprise the following steps：
（1）The sulfuric acid of 50 g graphite and 120 mL mass concentrations 85% is added in reaction vessel jointly, under 45 DEG C of water-bath
15-25 min are incubated, 15-20g potassium permanganate is added, temperature 70 DEG C are risen to rapidly after maintaining 10 min, with 200
Rpm speed stirring reaction 80-90 min, question response terminates to add the dioxygen that 300 mL mass fractions are 2.5% in backward container
Water, mixed liquor is stirred to discoloration, filter while hot with 150 rpm speed, by the gained filter cake hydrochloric acid solution of mass concentration 3%
Washing 2 times, then be washed with deionized 2 times, the filter cake after cleaning is placed in drying box at 75 DEG C and dries 8h, graphite is obtained
Oxide；
（2）By step（1）Obtained graphite oxide and 300 mL mass concentrations are mixed for 5 mg/mL graphene oxide water solution
Close, mixed liquor be then placed in 85 DEG C of baking oven heating 30-40 min, thick slurry is obtained, then under nitrogen protection in
High-temperature process 1.5h at 1000-1200 DEG C, obtains high-temperature activation product, in being carried out with watery hydrochloric acid to high-temperature activation product tentatively
With, then high-temperature activation product is washed 3-5 times to pH with deionized water neutrality is fully achieved, it is placed in 70 DEG C of vacuum drying chambers and does
Dry 8h, obtains modified graphite oxide；
（3）By step（2）Obtained modified graphite oxide is as the deionized water that in reactor, adds 300 mL and anhydrous
The volume ratio of alcohol mixed solvent, deionized water and absolute ethyl alcohol is 1.5, and 15 are stirred at 200 DEG C with 1200 rpm speed
Min, then adds 10 g polyvinylpyrrolidones and 5 g positive silicic acid propyl esters, then heats to 250 DEG C, stirring reaction 2-3 h,
Obtained product is centrifuged according to 3000 rpm rotating speed, gained sediment is washed with deionized water, be placed in 90 DEG C
6 h are dried in vacuum drying chamber, intermediate is obtained；
（4）By step（3）Gained intermediate is put into the h of curing process 15 in 220 DEG C of drying box, is then used ball milling
Machine ball milling 2-3 h, powder obtained by ball milling is placed in atmosphere tube type stove, and carbonization treatment, treatment temperature are carried out under argon gas protection
For 950 DEG C, processing time is 5 h, obtains carbonization compound；
（5）By step（4）Obtained carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, bonding
Agent according to（65-70）:（11-13）:（7-9）:（5-8）:（3-5）:（2-4）Ratio mixing, add appropriate amount of deionized water, stirring
It is uniform to be coated in thick on stainless (steel) wire, then it is dried into 8-24 h in 80-130 DEG C of vacuum drying chamber, through roll-in
After be cut into electrode slice, obtain finished product.
2. the preparation method of the electrode material of oxidized graphene aqueous solution processing according to claim 1, its feature exists
In the step（4）Diameter of particle after middle ball milling is less than 2 μm.
3. the preparation method of the electrode material of oxidized graphene aqueous solution processing according to claim 1, its feature exists
In the step（5）It is middle carbonization compound, tributyl 2-acetylcitrate, lead zinc niobate, barium stannate, conductive agent, binding agent according to
68:11:8:7:4:3 ratio mixing.
4. the preparation method of the electrode material of oxidized graphene aqueous solution processing according to claim 1, its feature exists
In the step（5）In any one in acetylene black, CNT carbon black, activated carbon of conductive agent.
5. the preparation method of the electrode material of oxidized graphene aqueous solution processing according to claim 1, its feature exists
In the step（5）In any one in sodium carboxymethylcellulose, hexafluoropropene, polyvinyl alcohol of binding agent.
6. the electrode material that the oxidized graphene aqueous solution obtained according to any one of the claim 1-5 preparation technologies is handled
Application in ultracapacitor is prepared.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110165321A1 (en) * | 2010-01-07 | 2011-07-07 | Aruna Zhamu | Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103198931A (en) * | 2013-03-22 | 2013-07-10 | 哈尔滨工业大学深圳研究生院 | Preparation method of graphene nano-fiber and super-capacitor application thereof |
| CN103253658A (en) * | 2013-05-13 | 2013-08-21 | 常州第六元素材料科技股份有限公司 | Graphene with high volumetric specific capacitance and preparation method thereof |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN105321726A (en) * | 2014-07-21 | 2016-02-10 | 中国科学院大连化学物理研究所 | High-magnification active carbon and active graphene composite electrode material and preparation method thereof |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110165321A1 (en) * | 2010-01-07 | 2011-07-07 | Aruna Zhamu | Continuous process for producing spacer-modified nano Graphene electrodes for supercapacitors |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
| CN103198931A (en) * | 2013-03-22 | 2013-07-10 | 哈尔滨工业大学深圳研究生院 | Preparation method of graphene nano-fiber and super-capacitor application thereof |
| CN103253658A (en) * | 2013-05-13 | 2013-08-21 | 常州第六元素材料科技股份有限公司 | Graphene with high volumetric specific capacitance and preparation method thereof |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN105321726A (en) * | 2014-07-21 | 2016-02-10 | 中国科学院大连化学物理研究所 | High-magnification active carbon and active graphene composite electrode material and preparation method thereof |
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