CN109665524A - A kind of preparation method and supercapacitor of small particle graphene composite stone oil coke matrix activated carbon - Google Patents
A kind of preparation method and supercapacitor of small particle graphene composite stone oil coke matrix activated carbon Download PDFInfo
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- CN109665524A CN109665524A CN201710958262.2A CN201710958262A CN109665524A CN 109665524 A CN109665524 A CN 109665524A CN 201710958262 A CN201710958262 A CN 201710958262A CN 109665524 A CN109665524 A CN 109665524A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 333
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 134
- 239000002245 particle Substances 0.000 title claims abstract description 66
- 239000011159 matrix material Substances 0.000 title claims abstract description 55
- 239000000571 coke Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000004575 stone Substances 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002006 petroleum coke Substances 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 239000012190 activator Substances 0.000 claims abstract description 26
- 230000004913 activation Effects 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000004939 coking Methods 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 239000011265 semifinished product Substances 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000036961 partial effect Effects 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 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 8
- 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 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000011331 needle coke Substances 0.000 claims description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- -1 graphene modified activated carbon Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 18
- 239000003990 capacitor Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention provides a kind of preparation methods of graphene composite stone oil coke matrix activated carbon, include the following steps, petroleum coke particles and activator are carried out coking and activation under conditions of first gas first, then active carbon dispersion liquid is obtained after washing；Then after active carbon dispersion liquid, small particle graphene oxide solution and reducing agent Hybrid Heating above-mentioned steps obtained carries out electronation, semi-finished product are obtained；Finally under conditions of second gas, after the semi-finished product that above-mentioned steps are obtained are heat-treated, graphene composite stone oil coke matrix activated carbon is obtained.The petroleum coke matrix activated carbon that the present invention uses alkali chemical activation to cross, match small particle graphene oxide, graphene is realized in petroleum coke matrix activated carbon coated with uniform by in-situ reducing, stabilize the specific surface area of graphene modified activated carbon, improve dispersing uniformity, so that the structure of graphene is restored during high temperature reduction, substantially increase the conductivity of active carbon, reduces the impedance of supercapacitor.
Description
Technical field
The invention belongs to absorbent charcoal material technical field, it is related to the preparation method of a kind of modified petroleum coke matrix activated carbon and super
Grade capacitor more particularly to a kind of preparation method and supercapacitor of small particle graphene composite stone oil coke matrix activated carbon.
Background technique
Supercapacitor is a kind of new type of energy storage device that can provide powerful pulse power.Supercapacitor is due to energy storage original
Reason is that physical charge is adsorbed, and has good high-power charge-discharge performance, when charging, the electrode surface charge in polarized state
Attract the counter ions in electrolyte solution, so that these ions is invested electrode surface and form electric double layer capacitance, thus in positive and negative anodes
Between generate stable potential difference.Supercapacitor has charge/discharge speed fast, and power density is high, and has up to million times
Cycle life, adapt to adverse circumstances, it is substantially non-maintaining the features such as, at communication, military affairs, new-energy automobile, national grid, port
The multiple fields such as mouth machinery are successfully applied, and gradually start to substitute the secondary cells such as lithium battery in many fields.
The charge storage ability of supercapacitor depend primarily on electrode material can be used for storage specific surface area and charge it is intensive
Degree.In theory, electrode surface area is bigger, and charge is more intensive, and capacity is bigger.Currently used super capacitor electrode
Material be mainly with carbon-based material it is leading, especially active carbon has that cheap, good moldability, electrochemical stability be high, ratio
The features such as surface area is big is the current most widely used material in supercapacitor field.The specific surface area of active carbon, aperture point
The indices such as cloth, conductivity, surface functional group, bulk density can all influence the performance of supercapacitor.The preparation of active carbon
Generally by the preparation of physically activated and chemical activation, in the corruption of the material surfaces such as active carbon precursor such as coconut husk, petroleum coke, carbide resin
A certain size aperture out is lost, to form porous active carbon.However the specific surface area of active carbon, pore-size distribution, conductivity,
Surface functional group, the indices such as bulk density can all influence the performance of supercapacitor, thus prepare high-energy density and height
The electrode material of power density is always the key problem in supercapacitor field, and this electrode material needs stable ratio table
Area, reasonable pore-size distribution and good conductivity.
To the method for the modification of active carbon, mainly pass through potassium hydroxide reacts system with active carbon precursor at high temperature at present
It is standby.But the Properties of Activated Carbon of method preparation used still has very big deficiency, and be in particular in: the active carbon of preparation is mainly with micro-
Based on hole, pore-size distribution is unreasonable；Alkali ratio used in preparation process is higher；The Properties of Activated Carbon of preparation is still unable to satisfy
To the requirement in terms of capacity；The active carbon internal resistance of preparation is larger etc..And there is part using graphene modified activated carbon
Patent, but to active carbon source selectivity not strong, the research being lack of pertinence, and common compound path have it is following several:
One, graphene and active carbon physical mixed；Two, graphene or graphene oxide and active carbon precursor are blended, then co-activating.And
The poor dispersion of graphene causes conductivity undesirable, it is difficult to realize industrialized production, it is difficult to meet application demand.
Therefore, the absorbent charcoal material preparation method for how obtaining a kind of high-specific surface area that electric conductivity is more stable, makes it
It is more suitable for electrode material for super capacitor, and more conducively industrialization large-scale production, there is important practical usage, also become
One of the focus of perspective study personnel extensive concern in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of small particle graphene composite stone oil coke base work
Property charcoal and preparation method thereof, supercapacitor, the modified graphene composite stone oil coke base of small particle graphene provided by the invention
Active carbon has the features such as better conductivity, the high-specific surface area of stable uniform, favorable reproducibility and low internal resistance, Neng Gouzuo
For Supercapacitor carbon, the better supercapacitor of processability.
The present invention provides a kind of preparation methods of graphene composite stone oil coke matrix activated carbon, comprising the following steps:
A) petroleum coke particles and activator are subjected to coking and activation under conditions of first gas, then are lived after washing
Property charcoal dispersion liquid；
B active carbon dispersion liquid, small particle graphene oxide solution and the reducing agent Hybrid Heating for) obtaining above-mentioned steps into
After row electronation, semi-finished product are obtained；
C) under conditions of second gas, after the semi-finished product that above-mentioned steps are obtained are heat-treated, it is multiple to obtain graphene
Close petroleum coke matrix activated carbon.
Preferably, the mass concentration of the small particle graphene oxide solution is 0.1%~1%；
In the small particle graphene oxide solution, the average grain diameter of small particle graphene oxide is 2~5 μm.
Preferably, the petroleum coke includes one of coke beehive, sponge coke, shot coke and needle coke or a variety of；
The partial size of the petroleum coke particles is 10~14 μm；
The activator includes potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide one or more of them.
Preferably, the mass ratio of the petroleum coke particles and activator is 1:(2~4)；
The activator is graininess activator, and the partial size of the graininess activator is 10~15 μm；
The first gas includes one of air, oxygen, hydrogen, nitrogen, inert gas, carbon dioxide and vapor
Or it is a variety of.
Preferably, the temperature of the coking is 500~600 DEG C, and the time of the coking is 0.5~1 hour；
The temperature of the activation is 700~900 DEG C, and the time of the activation is 2~3 hours；
The washing includes pickling and/or washing.
Preferably, the concentration of the active carbon dispersion liquid is 0.01~0.1g/mL；
The mass ratio that the small particle graphene oxide accounts for the active carbon is 0.5%~10%；
The volume mass ratio of the reducing agent and the small particle graphene oxide is (1~3) mL:1g.
Preferably, the temperature of the heating is 70~90 DEG C, and the time of the electronation is 5~8 hours；
The reducing agent includes one of hydrazine hydrate, sodium borohydride, sodium sulfite and vitamin C or a variety of；
The second gas includes the mixed gas or reducibility gas of reducibility gas and protective gas.
Preferably, the reducibility gas includes hydrogen and/or ammonia；
The protective gas includes nitrogen and/or inert gas；
The temperature of the heat treatment is 700~900 DEG C, and the time of the heat treatment is 0.5~2 hour.
It preferably, further include being crushed, screening and one of magnetic separation step or a variety of after the heat treatment；
The partial size of the graphene composite stone oil coke matrix activated carbon is 10~15 μm.
The present invention provides a kind of supercapacitors, compound comprising graphene prepared by above-mentioned technical proposal any one
Petroleum coke matrix activated carbon.
The present invention provides a kind of preparation methods of graphene composite stone oil coke matrix activated carbon, include the following steps, first
Petroleum coke particles and activator are subjected to coking and activation under conditions of first gas, then obtain active carbon dispersion after washing
Liquid；Then active carbon dispersion liquid, small particle graphene oxide solution and reducing agent Hybrid Heating above-mentioned steps obtained carries out
After electronation, semi-finished product are obtained；Finally under conditions of second gas, the semi-finished product that above-mentioned steps are obtained are heat-treated
Afterwards, graphene composite stone oil coke matrix activated carbon is obtained.Compared with prior art, the present invention is for existing active carbon mainly with micro-
Based on hole, pore-size distribution is unreasonable, and the Properties of Activated Carbon of preparation is still unable to satisfy to the requirement etc. in terms of capacity and internal resistance
Problem.The patent of graphene modified activated carbon before being more directed to, but it is not strong to active carbon source selectivity, it is lack of pertinence
Research, although and can also obtain the active carbon of high specific area, specific surface area simultaneously unstable, poor reproducibility, and graphite
The dispersibility of alkene is still weak, and leads to the defect that conductivity is undesirable.The present invention especially uses petroleum coke matrix activated carbon conduct
Object is improved, optimizes and integrates from the entire step for starting charing, it is living using the petroleum coke base crossed by alkali chemical activation
Property charcoal be raw material, especially match small particle graphene oxide.Under the action of reducing agent, small particle graphene oxide is in aqueous solution
In restored, during reduction, what small particle graphene can be more uniform is coated to activated carbon surface, then passes through
The method of in-situ reducing realizes that graphene in the uniform cladding on petroleum coke matrix activated carbon surface, stabilizes graphene modified activated carbon
Specific surface area, improve dispersing uniformity, so that the structure of graphene is restored during subsequent high temperature reduction, thus
The conductivity for greatly improving active carbon thereby reduces the impedance of supercapacitor, and modified stone prepared by the present invention
Oil coke matrix activated carbon specific surface area is stablized, and performance is uniform, and reproduction performance is good, is more advantageous to large-scale industrial production and application.
The experimental results showed that graphene composite stone oil coke matrix activated carbon specific surface area prepared by the present invention be 1800~
2000m2/ g, mesoporous are 60~70%, and conductivity > 200S/m, button condensance is 2~4 Ω.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 1；
Fig. 2 is the AC impedance figure of supercapacitor prepared by the embodiment of the present invention 1~4 and common supercapacitor.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or capacitor area
The conventional purity used.
The present invention provides a kind of preparation methods of graphene composite stone oil coke matrix activated carbon, comprising the following steps:
A) petroleum coke particles and activator are subjected to coking and activation under conditions of first gas, then are lived after washing
Property charcoal dispersion liquid；
B active carbon dispersion liquid, small particle graphene oxide solution and the reducing agent Hybrid Heating for) obtaining above-mentioned steps into
After row electronation, semi-finished product are obtained；
C) under conditions of second gas, after the semi-finished product that above-mentioned steps are obtained are heat-treated, it is multiple to obtain graphene
Close petroleum coke matrix activated carbon.
Petroleum coke particles and activator are carried out coking and activation first by the present invention under conditions of first gas, then are washed
After obtain active carbon dispersion liquid.
The specific choice of the petroleum coke is not particularly limited in the present invention, with petroleum coke well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright petroleum coke preferably includes one of coke beehive, sponge coke, shot coke and needle coke or a variety of, more preferably honeycomb
Burnt, shot coke or needle coke, most preferably needle coke.
The quality of the petroleum coke is not particularly limited in the present invention, with petroleum coke quality well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright petroleum coke is preferably that phosphorus content is more than or equal to 90%, and sulfur content is preferably smaller than equal to 0.5% petroleum coke, and ash content is preferred
Less than or equal to 0.15%.
The partial size of the petroleum coke particles is not particularly limited in the present invention, and those skilled in the art can be according to practical life
Produce situation, product requirement and quality requirement are selected and are adjusted, the partial size of petroleum coke particles of the present invention is preferably 10~
14 μm, more preferably 10.5~13.5 μm, more preferably 11~13 μm.
The activator is not particularly limited in the present invention, is activated with petroleum coke well known to those skilled in the art with activation
Agent, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
It invents the activator and preferably includes potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide one or more of them, it is more excellent
It is selected as potassium hydroxide, sodium hydroxide, lithium hydroxide or calcium hydroxide, more preferably potassium hydroxide, sodium hydroxide or calcium hydroxide,
Most preferably potassium hydroxide.
The present invention especially limits the activator without other, is activated and is used with petroleum coke well known to those skilled in the art
Activator, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the present invention is for convenience of mixing, and the activator is preferably graininess activator, and the partial size of the graininess activator is preferably
10~15 μm, more preferably 11~14 μm, more preferably 12~13 μm.
The dosage of the activator is not particularly limited in the present invention, with petroleum coke well known to those skilled in the art activation
With the conventional amount used of activator, those skilled in the art can be according to practical condition, product requirement and quality requirement
Selected and adjusted, the mass ratio of pre- carbonization petroleum coke and activator of the present invention is preferably 1:(2~4), more preferably
1:(2.2~3.8), more preferably 1:(2.5~3.5), most preferably 1:2.5.
The first gas is not particularly limited in the present invention, is with protective gas well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The first gas preferably includes one of air, oxygen, hydrogen, nitrogen, inert gas, carbon dioxide and vapor or more
Kind, more preferably air, oxygen, hydrogen, nitrogen, inert gas, carbon dioxide or vapor.The present invention is to the inert gas
Be not particularly limited, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the present invention are particularly preferred as argon gas.
The actual conditions of the coking are not particularly limited in the present invention, and those skilled in the art can be according to actual production
Situation, product requirement and quality requirement are selected and are adjusted, and the time of coking of the present invention is preferably 0.5~1 hour, more
Preferably 0.6~0.9 hour, more preferably 0.7~0.8 hour.The temperature of coking of the present invention is preferably 500~600 DEG C,
More preferably 520~580 DEG C, more preferably 540~560 DEG C, most preferably 550 DEG C.The present invention does not have the equipment of the coking
There is special limitation, with the equipment of petroleum coke coking well known to those skilled in the art, those skilled in the art can basis
Practical condition, product requirement and quality requirement are selected and are adjusted, and the equipment of coking of the present invention is preferably coking
Furnace.
The condition of the activation is not particularly limited in the present invention, with petroleum coke well known to those skilled in the art activation
Condition, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The temperature of activation of the present invention is preferably 700~900 DEG C, more preferably 725~875 DEG C, more preferably 750~850 DEG C, more
Preferably 775~825 DEG C, most preferably 800 DEG C；The time of the activation is preferably 2~3 hours, more preferably 2.2~2.8
Hour, more preferably 2.4~2.6 hours.
The equipment of the activation is not particularly limited in the present invention, with petroleum coke well known to those skilled in the art activation
Equipment, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement,
The equipment of activation of the present invention is preferably crucible.
The step of washing is not particularly limited in the present invention, after petroleum coke well known to those skilled in the art activation
Washing step, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the specific steps of washing of the present invention are more specific excellent preferably successively including Temperature fall, washing, pickling and washing
It is selected as Temperature fall, is washed to neutrality, pickling, then be washed to neutrality.
Spent pickling acid of the present invention is preferably one of hydrochloric acid, nitric acid and phosphoric acid or a variety of；The temperature of the washing
Preferably 20~100 DEG C, more preferably 40~80 DEG C, most preferably 50~100 DEG C.The present invention does not have the mode of the washing
Especially limitation, with the mode of washing after petroleum coke well known to those skilled in the art activation, those skilled in the art can be with
It is selected and is adjusted according to practical condition, product requirement and quality requirement, the mode of washing of the present invention is preferably wrapped
Include agitator treating and/or ultrasonic wave added washing, more preferably stirring and ultrasonic wave added washing.The mode filtered after the washing is excellent
It is selected as filters pressing or centrifugation.
Then the present invention mixes active carbon dispersion liquid, small particle graphene oxide solution and reducing agent that above-mentioned steps obtain
After closing heating progress electronation, semi-finished product are obtained.
The concentration of the active carbon dispersion liquid is not particularly limited in the present invention, and those skilled in the art can be according to reality
The condition of production, product requirement and quality requirement are selected and are adjusted, and the solid content of active carbon dispersion liquid of the present invention is preferred
For 0.01~0.1g/mL, more preferably 0.02~0.09g/mL, more preferably 0.03~0.08g/mL, most preferably 0.05~
0.06g/mL。
Active carbon dispersion liquid, small particle graphene oxide solution and the reducing agent mixing that the present invention again obtains above-mentioned steps
After carrying out electronation, semi-finished product are obtained.
The average grain diameter of the small particle graphene oxide is not particularly limited in the present invention, ripe with those skilled in the art
The partial size for the small particle graphene oxide known, those skilled in the art can according to practical condition, product requirement and
Quality requirement is selected and is adjusted, and the average grain diameter of graphene oxide of the present invention is preferably 2~5 μm, more preferably 2~
4 μm, more preferably 2~3 μm, most preferably 2 μm.
The concentration of the small particle graphene oxide solution is not particularly limited in the present invention, ripe with those skilled in the art
The concentration for the graphene oxide solution known, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the mass concentration of small particle graphene oxide solution of the present invention is preferably 0.1%~
1%, more preferably 0.3%~0.8%.More preferably 0.5%~0.6%.
Small particle graphene oxide of the present invention is not particularly limited, and is with routine GO well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The small particle graphene oxide is preferably single-layer graphene oxide or the less multilayer graphene oxide of the number of plies, more preferably singly
Layer graphene, the single layer rate are preferably higher than equal to 95%, and the number of plies of the multilayer graphene oxide is preferably 2~10 layers, more
Preferably 3~9 layers, more preferably 4~8 layers.
The source of the small particle graphene oxide is not particularly limited in the present invention, with well known to those skilled in the art
The source of graphene oxide, commercially available buy can also prepare according to the conventional preparation method, the present invention be guarantee and
The performance of later period modified activated carbon, optimization and complete process flow are improved, the small particle graphene oxide is preferably by Hummers
It is polished to obtain after method preparation.
The mode of the grinding is not particularly limited in the present invention, is with lapping mode well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The grinding is preferably ball milling.
The time of the grinding is not particularly limited in the present invention, is with milling time well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The time of the grinding is preferably 2~5h, more preferably 3~4h.
The additional amount of the small particle graphene oxide is not particularly limited in the present invention, and those skilled in the art can root
It is selected and is adjusted according to practical condition, product requirement and quality requirement, small particle graphene oxide of the present invention is molten
In liquid the quality of small particle graphene oxide account for the ratio of quality of activated carbon in the active carbon dispersion liquid be preferably 0.5%~
10%, more preferably 1%~9%, more preferably 3%~7%, more preferably 4%~6%.
The selection of the reducing agent is not particularly limited in the present invention, with well known to those skilled in the art conventionally used for also
The reducing agent of former GO, those skilled in the art can select according to practical condition, product requirement and quality requirement
Select and adjust, reducing agent of the present invention preferably include one of hydrazine hydrate, sodium borohydride, sodium sulfite and vitamin C or
It is a variety of, more preferably hydrazine hydrate, sodium borohydride, sodium sulfite or vitamin C.
The present invention is to further increase reduction effect, it is preferred to use the combination of ammonium hydroxide and reducing agent is first adjusted with ammonium hydroxide
PH value is alkalinity, is restored again.The pH value is preferably 10~11.
The additional amount of the reducing agent is not particularly limited in the present invention, is routinely added to well known to those skilled in the art
Amount, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The volume mass ratio for inventing the reducing agent and the graphene oxide is preferably (1~3) mL:1g, more preferably (1.2~
2.8) mL:1g, more preferably (1.5~2.5) mL:1g, more preferably (1.7~2.3) mL:1g, most preferably 2mL:1g.
The mixed mode is not particularly limited in the present invention, is with hybrid mode well known to those skilled in the art
Can, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, the present invention
The mixing is preferably ultrasonic mixing and/or is stirred, more preferably ultrasonic agitation mixing.The power of the ultrasound is preferably
600~2000W, more preferably 1000~1600W, more preferably 1200~1400W.The revolving speed of the stirring is preferably 200~
500rpm, more preferably 300~400rpm.
The present invention is not particularly limited to the temperature of the heating, with graphene oxide well known to those skilled in the art
The temperature of electronation, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, the temperature of heating of the present invention is preferably 70~90 DEG C, more preferably 72~88 DEG C, more preferably 75~85
DEG C, more preferably 77~83 DEG C, most preferably 80 DEG C.
The electronation is not particularly limited in the present invention, with graphite oxide alkylene well known to those skilled in the art
The condition of reduction is learned, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the temperature of electronation of the present invention is the temperature heated.The time of the electronation is preferably 5~8 small
When, more preferably 5.5~7.5 hours, more preferably 6~7 hours, most preferably 6 hours.
Under the action of reducing agent, small particle graphene oxide is restored the present invention in aqueous solution, in reduction
In the process, small particle graphene can be coated to activated carbon surface, exist to realize graphene by the method for in-situ reducing
The uniform cladding on petroleum coke matrix activated carbon surface.
The present invention finally under conditions of second gas, after the semi-finished product that above-mentioned steps are obtained are heat-treated, obtains
Graphene composite stone oil coke matrix activated carbon obtains graphene composite stone oil coke matrix activated carbon.
The second gas is not particularly limited in the present invention, contains reducibility gas with well known to those skilled in the art
Protective gas, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, second gas of the present invention preferably includes the mixed gas or reproducibility gas of reducibility gas and protective gas
The mixed gas of body, more preferably reducibility gas and protective gas, the reducibility gas preferably include hydrogen and/or ammonia
Gas, more preferably hydrogen or ammonia.The protective gas preferably includes nitrogen and/or inert gas, more preferably nitrogen or
Argon gas.
The condition of the heat treatment is not particularly limited in the present invention, with petroleum coke well known to those skilled in the art preparation
The heat treatment step of active carbon, those skilled in the art can be according to practical condition, product requirement and quality requirements
It is selected and is adjusted, the temperature of heat treatment of the present invention is preferably 700~900 DEG C, more preferably 720~880 DEG C, more excellent
It is selected as 750~850 DEG C, more preferably 770~830 DEG C, most preferably 800 DEG C；The time of the heat treatment is preferably 0.5~2
Hour, more preferably 0.8~1.8 hour, more preferably 1~1.5 hour, most preferably 1 hour.
The present invention is by by petroleum coke active carbon and small particle graphene oxide be compound and in-situ reducing, so that active carbon table
Uniformly wrap up one layer of small particle graphene oxide, the creative graphene oxide using specific average grain diameter, so that oxidation in face
The more uniform dispersed encapsulated of graphene is in activated carbon surface, to further improve graphene modified petroleum coke active carbon
Performance, improve dispersing uniformity, restore the structure of graphene preferably, from
And the conductivity of active carbon is greatly improved, the impedance of supercapacitor is thereby reduced, while specific surface area is uniform, reappeared
Property is strong, and graphene dosage is few, is suitable for industrialized production.
The present invention is to improve the quality of final product, further preferably includes broken, screening and magnetic separation step after the heat treatment；
The detailed process and condition of the broken, screening and magnetic separation step is not particularly limited in the present invention, and those skilled in the art can
To be selected and be adjusted according to practical condition, product requirement and quality requirement, broken partial size of the present invention is excellent
It is selected as 10~15 μm, more preferably 11~14 μm, more preferably 12~10 μm.
The present invention also provides a kind of supercapacitors, multiple comprising graphene prepared by above-mentioned technical proposal any one
Close petroleum coke matrix activated carbon.The definition of the supercapacitor is not particularly limited in the present invention, ripe with those skilled in the art
The definition for the supercapacitor known.
Above-mentioned steps of the present invention provide the preparation method and super capacitor of a kind of graphene composite stone oil coke matrix activated carbon
Device, the present invention especially use petroleum coke matrix activated carbon as improve object, from start charing entire step optimize and
Integration uses the petroleum coke matrix activated carbon crossed by alkali chemical activation for raw material, matches the graphene oxide water of specific small particle
Solution.Under the action of the electronation especially selected, small particle graphene oxide is restored in aqueous solution, is being restored
During, small particle graphene can be coated to activated carbon surface, to realize that graphene exists by the method for in-situ reducing
The uniform cladding on petroleum coke matrix activated carbon surface.Keep the structure of small particle graphene extensive during subsequent high temperature reduction
It is multiple, the conductivity of active carbon is improved, to reduce the impedance of supercapacitor, and modified petroleum prepared by the present invention is burnt
Matrix activated carbon specific surface area is stablized, and performance is uniform, and reproduction performance is good, is more advantageous to large-scale industrial production and application.
The experimental results showed that graphene composite stone oil coke matrix activated carbon specific surface area prepared by the present invention be 1800~
2000m2/ g, mesoporous are 60~70%, and conductivity > 200S/m, button condensance is 2~4 Ω.
In order to further illustrate the present invention, with reference to embodiments to a kind of graphene composite stone oil coke provided by the invention
The preparation method and supercapacitor of matrix activated carbon are described in detail, but it is to be understood that these embodiments are with this hair
Implemented under premised on bright technical solution, the detailed implementation method and specific operation process are given, is only further
Illustrate the features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to
Following embodiments.
Embodiment 1
By 100g petroleum coke (10~14 μm, carbon content > 90%), 250g KOH is put into 2L nickel alloy crucible after mixing
In, sealing is placed in Muffle furnace, and reaction system is stirred to react 0.5h at 550 DEG C, then raises temperature to 800 DEG C, reacts 2h.Instead
After answering, mixture is washed and is filtered, remove the highly basic in mixture, then use dilute hydrochloric acid pickling, removed in mixture
Foreign ion obtains super-activated carbon.
Graphene oxide prepared by Hummers method grinds 6h, obtains the small particle graphene oxide that partial size is 2 μm, presses
After 1% ratio and the ultrasonic agitation dispersion of the super-activated carbon of preparation, the hydrazine hydrate (ml) of 2 times of addition graphene oxide quality (g)
Water-bath reduction, reduction temperature are 80 DEG C, recovery time 8h.It filters drying for 24 hours after reaction, small particle oxidation is prepared
Graphene is modified super-activated carbon, i.e. graphene composite stone oil coke matrix activated carbon.
The graphene composite stone oil coke matrix activated carbon prepared to the embodiment of the present invention 1 characterizes.
It is shone referring to the scanning electron microscope that Fig. 1, Fig. 1 are graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 1
Piece.
The graphene composite stone oil coke matrix activated carbon prepared to the embodiment of the present invention 1 detects, the results showed that, the present invention
The graphene coated petroleum coke matrix activated carbon specific surface area of preparation is 1800m2/ g, conductivity 200S/m.
Supercapacitor is prepared using graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 1, is briefly walked
It is rapid as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
Performance detection is carried out to supercapacitor prepared by the embodiment of the present invention 1.
Referring to fig. 2, Fig. 2 is that supercapacitor and common supercapacitor prepared by the embodiment of the present invention 1~4 exchanges resistance
Anti- figure.
As shown in Figure 2, button capacitor internal resistance is substantially reduced after graphene being added.
Embodiment 2
By 100g petroleum coke (10~14 μm, carbon content > 90%), 250g KOH is put into 2L nickel alloy crucible after mixing
In, sealing is placed in Muffle furnace, and reaction system is stirred to react 0.5h at 550 DEG C, then raises temperature to 800 DEG C, reacts 2h.Instead
After answering, mixture is washed and is filtered, the highly basic in mixture of going out then uses dilute hydrochloric acid pickling, removes in mixture
Foreign ion obtains super-activated carbon.
Graphene oxide prepared by Hummers method grinds 6h, obtains the small particle graphene oxide that partial size is 2 μm, presses
After 3% ratio and the ultrasonic agitation dispersion of the super-activated carbon of preparation, the hydrazine hydrate (ml) of 2 times of addition graphene oxide quality (g)
Water-bath reduction, reduction temperature are 80 DEG C, recovery time 8h.It filters drying for 24 hours after reaction, small particle oxidation is prepared
Graphene is modified super-activated carbon, i.e. graphene composite stone oil coke matrix activated carbon.
The graphene composite stone oil coke matrix activated carbon prepared to the embodiment of the present invention 2 detects, the results showed that, the present invention
The graphene coated petroleum coke matrix activated carbon specific surface area of preparation is 1950m2/ g, conductivity 230S/m.
Supercapacitor is prepared using graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 2, is briefly walked
It is rapid as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
Performance detection is carried out to supercapacitor prepared by the embodiment of the present invention 2.
Referring to fig. 2, Fig. 2 is that supercapacitor and common supercapacitor prepared by the embodiment of the present invention 1~4 exchanges resistance
Anti- figure.
As shown in Figure 2, button capacitor internal resistance is substantially reduced after graphene being added.
Embodiment 3
By 100g petroleum coke (10~14 μm, carbon content > 90%), 250g KOH is put into 2L nickel alloy crucible after mixing
In, sealing is placed in Muffle furnace, and reaction system is stirred to react 0.5h at 550 DEG C, then raises temperature to 800 DEG C, reacts 2h.Instead
After answering, mixture is washed and is filtered, the highly basic in mixture of going out then uses dilute hydrochloric acid pickling, removes in mixture
Foreign ion obtains super-activated carbon.
Graphene oxide prepared by Hummers method grinds 6h, obtains the small particle graphene oxide that partial size is 2 μm, presses
After 6% ratio and the ultrasonic agitation dispersion of the super-activated carbon of preparation, the hydrazine hydrate (ml) of 2 times of addition graphene oxide quality (g)
Water-bath reduction, reduction temperature are 80 DEG C, recovery time 8h.It filters drying for 24 hours after reaction, small particle oxidation is prepared
Graphene is modified super-activated carbon, i.e. graphene composite stone oil coke matrix activated carbon.
The graphene composite stone oil coke matrix activated carbon prepared to the embodiment of the present invention 3 detects, the results showed that, the present invention
The graphene coated petroleum coke matrix activated carbon specific surface area of preparation is 1950m2/ g, conductivity 270S/m.
Supercapacitor is prepared using graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 3, is briefly walked
It is rapid as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
Performance detection is carried out to supercapacitor prepared by the embodiment of the present invention 3.
Referring to fig. 2, Fig. 2 is that supercapacitor and common supercapacitor prepared by the embodiment of the present invention 1~4 exchanges resistance
Anti- figure.
As shown in Figure 2, button capacitor internal resistance is substantially reduced after graphene being added.
Embodiment 4
By 100g petroleum coke (10~14 μm, carbon content > 90%), 250g KOH is put into 2L nickel alloy crucible after mixing
In, sealing is placed in Muffle furnace, and reaction system is stirred to react 0.5h at 550 DEG C, then raises temperature to 800 DEG C, reacts 2h.Instead
After answering, mixture is washed and is filtered, the highly basic in mixture of going out then uses dilute hydrochloric acid pickling, removes in mixture
Foreign ion obtains super-activated carbon.
Graphene oxide prepared by Hummers method grinds 6h, obtains the small particle graphene oxide that partial size is 2 μm, presses
After 9% ratio and the ultrasonic agitation dispersion of the super-activated carbon of preparation, the hydrazine hydrate (ml) of 2 times of addition graphene oxide quality (g)
Water-bath reduction, reduction temperature are 80 DEG C, recovery time 8h.It filters drying for 24 hours after reaction, small particle oxidation is prepared
Graphene is modified super-activated carbon, i.e. graphene composite stone oil coke matrix activated carbon.
The graphene composite stone oil coke matrix activated carbon prepared to the embodiment of the present invention 4 detects, the results showed that, the present invention
The graphene coated petroleum coke matrix activated carbon specific surface area of preparation is 1980m2/ g, conductivity 290S/m.
Supercapacitor is prepared using graphene composite stone oil coke matrix activated carbon prepared by the embodiment of the present invention 4, is briefly walked
It is rapid as follows:
This active carbon is mixed into homogenate with CMC with binder SBR, is uniformly coated on aluminium foil, through drying, is rolled, punching
After be assembled into button capacitor (organic system, 2.7V).
Performance detection is carried out to supercapacitor prepared by the embodiment of the present invention 4.
Referring to fig. 2, Fig. 2 is that supercapacitor and common supercapacitor prepared by the embodiment of the present invention 1~4 exchanges resistance
Anti- figure.
As shown in Figure 2, button capacitor internal resistance is substantially reduced after graphene being added.
Above the preparation method to a kind of small particle graphene oxide modified petroleum coke matrix activated carbon provided by the invention and
Supercapacitor is described in detail, and specific case used herein carries out the principle of the present invention and embodiment
It illustrates, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including best mode, and
And but also any person skilled in the art can practice the present invention, including any device or system of manufacture and use, and
Implement the method for any combination.It should be pointed out that for those skilled in the art, not departing from original of the invention
, can be with several improvements and modifications are made to the present invention under the premise of reason, these improvement and modification also fall into right of the present invention and want
In the protection scope asked.The range of the invention patent protection is defined by the claims, and may include those skilled in the art
It is conceivable that other embodiments.If there is these other embodiments the structure for being not different from claim character express to want
Element, or if they include the equivalent structural elements with the character express of claim without essence difference, these other
Embodiment should also be included in the scope of the claims.
Claims (10)
1. a kind of preparation method of graphene composite stone oil coke matrix activated carbon, which comprises the following steps:
A) petroleum coke particles and activator are subjected to coking and activation under conditions of first gas, then obtain active carbon after washing
Dispersion liquid；
B active carbon dispersion liquid, small particle graphene oxide solution and the reducing agent Hybrid Heating for) obtaining above-mentioned steps
After learning reduction, semi-finished product are obtained；
C) under conditions of second gas, after the semi-finished product that above-mentioned steps are obtained are heat-treated, graphene composite stone is obtained
Oil coke matrix activated carbon.
2. preparation method according to claim 1, which is characterized in that the quality of the small particle graphene oxide solution is dense
Degree is 0.1%~1%；
In the small particle graphene oxide solution, the average grain diameter of small particle graphene oxide is 2~5 μm.
3. preparation method according to claim 1, which is characterized in that the petroleum coke includes coke beehive, sponge coke, bullet
One of burnt and needle coke is a variety of；
The partial size of the petroleum coke particles is 10~14 μm；
The activator includes potassium hydroxide, sodium hydroxide, lithium hydroxide and calcium hydroxide one or more of them.
4. preparation method according to claim 1, which is characterized in that the mass ratio of the petroleum coke particles and activator is
1:(2~4)；
The activator is graininess activator, and the partial size of the graininess activator is 10~15 μm；
The first gas includes one of air, oxygen, hydrogen, nitrogen, inert gas, carbon dioxide and vapor or more
Kind.
5. preparation method according to claim 1, which is characterized in that the temperature of the coking is 500~600 DEG C, described
The time of coking is 0.5~1 hour；
The temperature of the activation is 700~900 DEG C, and the time of the activation is 2~3 hours；
The washing includes pickling and/or washing.
6. preparation method according to claim 1, which is characterized in that the concentration of the active carbon dispersion liquid be 0.01~
0.1g/mL；
The mass ratio that the small particle graphene oxide accounts for the active carbon is 0.5%~10%；
The volume mass ratio of the reducing agent and the small particle graphene oxide is (1~3) mL:1g.
7. preparation method according to claim 1, which is characterized in that the temperature of the heating is 70~90 DEG C, describedization
The time for learning reduction is 5~8 hours；
The reducing agent includes one of hydrazine hydrate, sodium borohydride, sodium sulfite and vitamin C or a variety of；
The second gas includes the mixed gas or reducibility gas of reducibility gas and protective gas.
8. preparation method according to claim 7, which is characterized in that the reducibility gas includes hydrogen and/or ammonia；
The protective gas includes nitrogen and/or inert gas；
The temperature of the heat treatment is 700~900 DEG C, and the time of the heat treatment is 0.5~2 hour.
9. preparation method according to claim 1, which is characterized in that further include being crushed, screening and magnetic after the heat treatment
Select one of step or a variety of；
The partial size of the graphene composite stone oil coke matrix activated carbon is 10~15 μm.
10. a kind of supercapacitor, which is characterized in that include graphene composite stone prepared by claim 1~9 any one
Oil coke matrix activated carbon.
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| CN114832777A (en) * | 2022-05-11 | 2022-08-02 | 浙江大学 | Modification method for removing perfluorocarboxylic acid in water by using enhanced activated carbon and prepared modified activated carbon |
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