CN106115694A - The preparation method of a kind of composite type pitch matrix activated carbon and ultracapacitor - Google Patents
The preparation method of a kind of composite type pitch matrix activated carbon and ultracapacitor Download PDFInfo
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- CN106115694A CN106115694A CN201610451977.4A CN201610451977A CN106115694A CN 106115694 A CN106115694 A CN 106115694A CN 201610451977 A CN201610451977 A CN 201610451977A CN 106115694 A CN106115694 A CN 106115694A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000011159 matrix material Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- 230000004913 activation Effects 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 29
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 43
- 238000002156 mixing Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 238000004939 coking Methods 0.000 claims description 22
- 239000010426 asphalt Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000002010 green coke Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052756 noble gas Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011280 coal tar Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000011265 semifinished product Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 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
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000013021 overheating Methods 0.000 claims description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 239000006253 pitch coke Substances 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 5
- -1 based on micropore Chemical compound 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 30
- 238000001994 activation Methods 0.000 description 25
- 239000000843 powder Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 12
- 239000003610 charcoal Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000006148 magnetic separator Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 241000720974 Protium Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000006557 surface reaction Methods 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
- H01G11/32—Carbon-based
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides the preparation method of a kind of composite type pitch matrix activated carbon, graphene oxide and pitch coke are reduced and activation by the present invention jointly through high-temperature-coked, and graphene oxide is internally formed uniform network at pitch coke；Simultaneously through high-temperature activation and high temperature reduction, graphene oxide removing major part oxygen forms Graphene, so that activated carbon is internally formed good conductive network, reduces activated carbon internal resistance.The preparation method that the present invention provides effectively solves existing activated carbon mainly based on micropore, and pore-size distribution is unreasonable, and alkali ratio used in preparation process is higher, and Properties of Activated Carbon still cannot meet the problem bigger to the requirement in terms of capacity and internal resistance.Composite type pitch matrix activated carbon prepared by the present invention has reasonable pore-size distribution, bigger serface, low internal resistance, high power capacity, low impurity and the advantage of low oxygen-containing functional group, it is possible to as Supercapacitor carbon, obtains the more preferable ultracapacitor of performance.
Description
Technical field
The invention belongs to absorbent charcoal material technical field, particularly relate to the preparation method of a kind of composite type pitch matrix activated carbon
And ultracapacitor.
Background technology
Activated carbon, also known as activated carbon black, is black powder or bulk, graininess, cellular amorphous carbon, also has row
Arrange regular crystal carbon.In activated carbon outside de-carbon element, also comprise a small amount of protium and oxygen element, a part of source of these elements
Remain in activated carbon in the incomplete carbonization of activated carbon precursor, another part derive from activating reagent such as water or sodium hydroxide with
Activated carbon surface reaction forms the groups such as hydroxyl, carboxyl, carbonyl.In addition activated carbon there is also a part of ash, mainly by remaining
Inorganic salt composition in activated carbon, such as iron salt, sodium salt, potassium salt etc..
Activated carbon divide from raw material can be divided into wooden, ature of coal, petroleum coke and resin activity charcoal；Come from manufacture method
Point, it is divided into chemical method, Physical and physical chemistry combination method activated carbon.These activated carbon precursors in activation furnace in high temperature,
Activated carbon is formed with activator by pyrolysis, high temperature carbonization and priming reaction under certain pressure.In this activation process, huge
Big surface area and complicated pore structure gradually form.Activated carbon contains a large amount of micropore, has huge incomparable surface area, energy
Effectively removing colourity, stink, in removable secondary effluent, most organic pollutants and some inorganic matter, comprise some poisonous
Heavy metal.And according to activated carbon graphitization complexity, it is divided into again hard carbon and soft carbon, with lignin, resin it is as a rule
Raw material prepare for hard charcoal, with petroleum coke for raw material prepare as soft charcoal.
Along with world's attention to new energy technology, ultracapacitor is more and more applied.Compared with lithium battery,
Ultracapacitor has the features such as charge/discharge rates is fast, power density is high, life-span length, non-maintaining, environmental protection, although energy density
Still much lower than lithium battery, but the short slab of lithium battery can be made up in terms of power density, become lithium battery and other secondary
The strong of battery supplements, and has obtained successfully in multiple fields such as communication, military affairs, new-energy automobile, national grid, harbour machineries
Application.
The charge storage ability of ultracapacitor depend primarily on electrode material can be used for storage electricity specific surface area and electric charge intensive
Degree.In theory, electrode surface area is the biggest, and electric charge is the most intensive, and its capacity is the biggest.Owing to porous carbon has chemically stable
The features such as property, high-specific surface area, are the most widely used materials in current ultracapacitor field, and activated carbon are the most frequently used
Electrode material for super capacitor.
But the specific surface area of activated carbon, pore-size distribution, electrical conductivity, surface functional group, the indices such as bulk density is all
The performance of ultracapacitor can be affected, thus the electrode material preparing high-energy-density and high power density is always super capacitor
The key problem in device field, this electrode material needs high specific surface area, rational pore-size distribution and good conductance
Rate.
But the Supercapacitor carbon of business is still based on micropore at present, and mesopore content is relatively low；Internal resistance is higher, and preparation is super
Level capacitor need to add 5～10% conductive black for forming conductive network；In addition specific capacity is the most relatively low, energy density
Still differ farther out compared with lithium battery.
Therefore, a kind of absorbent charcoal material how is obtained so that it is be more suitable for electrode material for super capacitor, super for promoting
The development of level capacitor and the actual application of absorbent charcoal material are significant, and in also becoming field, perspective study personnel are wide
One of general focus of attention.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the composite type pitch matrix activated carbon of a kind of modification
Preparation method and ultracapacitor, the composite type pitch matrix activated carbon that the Graphene that the present invention provides is modified, have greatly than table
Area, low internal resistance, high power capacity, the feature such as low impurity and low oxygen-containing functional group, it is possible to as Supercapacitor carbon, obtain performance more preferable
Ultracapacitor.
The invention provides the preparation method of a kind of composite type pitch matrix activated carbon, comprise the following steps:
A), after being mixed with graphene oxide by the matrix pitch after fusing, mixture is obtained；
B) under conditions of noble gas and/or nitrogen, after mixture above-mentioned steps obtained carries out coking reduction,
To mixing green coke；
C) after the mixing green coke that above-mentioned steps obtained mixes again with alkali after pulverizing, at noble gas and/or nitrogen
Under the conditions of carry out pre-activate and activation, obtain semi-finished product；
D) semi-finished product above-mentioned steps obtained are through washing and dried, under conditions of protective gas, through overheated
After process, obtain composite type pitch matrix activated carbon.
Preferably, described matrix pitch includes coal tar asphalt and/or asphalt；
It is 0.1%～1% that the quality of described graphene oxide accounts for the ratio of described matrix pitch quality；
The temperature of described mixing is 100～180 DEG C.
Preferably, the concretely comprising the following steps of described mixing:
Under conditions of 150～180 DEG C, be stirred the matrix pitch after fusing with graphene oxide mixing 10～
30min, then shear-mixed 60～90min；It is cooled to 100～120 DEG C again and places 30～60min, the most again shearing mixed
Close 60～90min, obtain mixture.
Preferably, the temperature of described coking reduction is 450～500 DEG C；The time of described coking reduction is 6～12h.
Preferably, the particle diameter after described mixing green coke is pulverized is 50～100 μm；
Described alkali is graininess alkali, and the particle diameter of described graininess alkali is 10～300 μm.
Preferably, described alkali includes potassium hydroxide, sodium hydroxide, Lithium hydrate and calcium hydroxide one or more of which；
Described mixing green coke is 1:(0.5～5 with the mass ratio of alkali).
Preferably, described preactivated temperature is 350～500 DEG C；The described preactivated time is 1～4 hour；
The temperature of described activation is 700～950 DEG C, and the time of described activation is 0.5～4 hour.
Preferably, one or more during described protective gas includes hydrogen, ammonia, nitrogen and noble gas；
The temperature of described heat treatment is 700～900 DEG C, and the time of described heat treatment is 1～4 hour；
Preferably, also include after described heat treatment crushing, screening and magnetic separation step；
Described broken after particle diameter be 6～10 μm.
Present invention also offers a kind of ultracapacitor, comprise the compound drip prepared by technique scheme any one
Blue or green matrix activated carbon.
The invention provides the preparation method of a kind of composite type pitch matrix activated carbon, comprise the following steps, first will fusing
After matrix pitch mix with graphene oxide after, obtain mixture；Then under conditions of noble gas and/or nitrogen, will
After the mixture that above-mentioned steps obtains carries out coking reduction, obtain mixing green coke；The mixing coking powder again above-mentioned steps obtained
After again mixing with alkali after broken, under conditions of noble gas and/or nitrogen, carry out pre-activate and activation, obtain semi-finished product；?
After semi-finished product that above-mentioned steps is obtained through washing and dried, under conditions of protective gas, after Overheating Treatment,
To composite type pitch matrix activated carbon.Compared with prior art, the present invention by graphene oxide and pitch coke jointly through high-temperature coke
Changing reduction and activation, graphene oxide is internally formed uniform network at pitch coke；Simultaneously through high-temperature activation and high temperature reduction,
Graphene oxide removing major part oxygen forms Graphene, so that activated carbon is internally formed good conductive network, reduces work
Property charcoal internal resistance, and from mechanism derive understand, the asphalt based active carbon obtained after graphene oxide doped prepared by the present invention
Mesopore is more, and this is often as graphene oxide lamella and uniformly inserts pitch coke and be internally formed similar sandwich structure, and alkali
Can be blocked by the most complete lamellar structure when caustic corrosion to graphene oxide lamella in activation composite material, alkali activates
Tend to crosswise development, thus improve mesoporous.The preparation method that the present invention provides effectively solves existing activated carbon master
Will be based on micropore, pore-size distribution is unreasonable, and alkali ratio used in preparation process is higher, and Properties of Activated Carbon still cannot
Meet the problem bigger to the requirement in terms of capacity and internal resistance.Test result indicate that, composite type pitch base prepared by the present invention
Activated carbon has reasonable pore-size distribution, bigger serface, low internal resistance, high power capacity, low impurity and the advantage of low oxygen-containing functional group, energy
Enough as Supercapacitor carbon, obtain the more preferable ultracapacitor of performance.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph of composite type pitch matrix activated carbon prepared by the present invention；
Fig. 2 is the electromicroscopic photograph of the composite type pitch matrix activated carbon of the embodiment of the present invention 1 preparation；
Fig. 3 is the graph of pore diameter distribution of the composite type pitch matrix activated carbon of the embodiment of the present invention 1 preparation.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
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
Limit.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or according to people in the art
Prepared by the conventional method known to Yuan.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytical pure or capacitor area
The conventional purity used.
The invention provides the preparation method of a kind of composite type pitch matrix activated carbon, comprise the following steps:
A), after being mixed with graphene oxide by the matrix pitch after fusing, mixture is obtained；
B) under conditions of noble gas and/or nitrogen, after mixture above-mentioned steps obtained carries out coking reduction,
To mixing green coke；
C) after the mixing green coke that above-mentioned steps obtained mixes again with alkali after pulverizing, at noble gas and/or nitrogen
Under the conditions of carry out pre-activate and activation, obtain semi-finished product；
D) semi-finished product above-mentioned steps obtained are through washing and dried, under conditions of protective gas, through overheated
After process, obtain composite type pitch matrix activated carbon.
After first matrix pitch after fusing is mixed by the present invention with graphene oxide, obtain mixture.
Described matrix pitch is not particularly limited by the present invention, with well known to those skilled in the art for preparing pitch coke
The matrix pitch of matrix activated carbon, those skilled in the art can be according to practical condition, product requirement and prescription
Selecting and adjust, the preferred Colophonium of matrix pitch of the present invention includes coal tar asphalt and/or asphalt, more preferably
Coal tar asphalt and/or asphalt, the most preferably phosphorus content are more than or equal to 90%, and sulfur content is less than or equal to 0.5%
Matrix pitch.
Graphene oxide of the present invention is preferably graphene oxide powder, more preferably single-layer graphene oxide powder；
Described monolayer rate is more preferably higher than equal to 95%.The sheet footpath of described graphene oxide is not particularly limited, with ability by the present invention
The sheet footpath of the graphene oxide known to field technique personnel, those skilled in the art can be according to practical condition, product
Requiring and prescription selects and adjusts, the average sheet footpath of graphene oxide of the present invention is preferably 1～50 μm, more excellent
Elect 5～45 μm, more preferably 10～40 μm, most preferably 20～30 μm as.Described single-layer graphene oxide is come by the present invention
Source is not particularly limited, and with the source of single-layer graphene oxide well known to those skilled in the art, commercially available buys also
Can prepare according to conventional preparation method.The addition of described graphene oxide is not particularly limited by the present invention, this area
Technical staff can select according to practical condition, product requirement and prescription and adjust, oxidation of the present invention
The quality of Graphene accounts for the ratio of described matrix pitch quality and is preferably 0.1%～1%, more preferably 0.2%～0.9%, more
It is preferably 0.3%～0.8%, most preferably 0.5%～0.6%.
The temperature of described mixing is not particularly limited by the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust, and the temperature of mixing of the present invention is preferably 100～180 DEG C, more excellent
Elect 110～170 DEG C as, more preferably 120～160 DEG C, most preferably 130～150 DEG C.The present invention concrete step to described mixing
Rapid and mode is not particularly limited, with blend step well known to those skilled in the art and mode, those skilled in the art
Can select according to practical condition, product requirement and prescription and adjust, the present invention is to be formed uniformly to be combined
Graphene oxide composite asphalt, improves the performance of final composite, and the concrete steps of described mixing are preferably:
Under conditions of 150～180 DEG C, be stirred the matrix pitch after fusing with graphene oxide mixing 10～
30min, then shear-mixed 60～90min；It is cooled to 100～120 DEG C again and places 30-60min, shear-mixed the most again
60～90min, obtain mixture, i.e. graphene oxide composite asphalt.
150～180 DEG C of the present invention, more preferably 155～175 DEG C, most preferably 160～170 DEG C；Described stirring mixes
The time closed is preferably 10～30min, more preferably 12～28min, more preferably 14～26min, most preferably 16～
24min.The time of shear-mixed of the present invention is preferably 60～90min, more preferably 65～85min, most preferably 70～
80min；Other conditions of described shear-mixed are not particularly limited by the present invention, and those skilled in the art can be raw according to reality
Product situation, product requirement and prescription select and adjust, the rotating speed of shear-mixed of the present invention be preferably 90～
240rmp, more preferably 110～220rmp, more preferably 130～200rmp, most preferably 150～180rmp；The present invention is to institute
The equipment stating shear-mixed is not particularly limited, and those skilled in the art can be according to practical condition, product requirement and matter
Amount requirement selects and adjusts, and the equipment of shear-mixed of the present invention is preferably cutter.The temperature of cooling of the present invention
Spend preferably 100～120 DEG C, more preferably 102～118 DEG C, more preferably 105～115 DEG C, most preferably 108～112 DEG C；Institute
Stating time of placement is preferably 30～60min, more preferably 35～55min, most preferably 40～50min.Of the present invention again
The time of secondary shear-mixed is preferably 60～90min, more preferably 65～85min, most preferably 70～80min；The present invention couple
Other conditions of described shear-mixed again are not particularly limited, and those skilled in the art can be according to practical condition, product
Product require and prescription selects and adjusts, and the rotating speed of shear-mixed again of the present invention is preferably 90～240rmp,
More preferably 110～220rmp, more preferably 130～200rmp, most preferably 150～180rmp.
The present invention is by by graphene oxide with Colophonium at a certain temperature, through special shear-mixed step, is formed
The most compound graphene oxide composite asphalt (mixture), improves the performance of composite type pitch matrix activated carbon, carries for the later stage
Supply favourable basis.
The present invention is then under conditions of noble gas and/or nitrogen, and mixture above-mentioned steps obtained carries out coking
After reduction, obtain mixing green coke.
Described noble gas is not particularly limited by the present invention, those skilled in the art can according to practical condition,
Product requirement and prescription select and adjust, and the present invention is particularly preferred as argon.Described coking is reduced by the present invention
Condition is not particularly limited, and with the condition of pitch coke coking well known to those skilled in the art, those skilled in the art can
To select according to practical condition, product requirement and prescription and to adjust, the temperature of coking of the present invention reduction
It is preferably 450～500 DEG C, more preferably 455～495 DEG C, more preferably 460～490 DEG C, most preferably 470～480 DEG C；Institute
The time stating coking reduction is preferably 6～12h, more preferably 7～11h, most preferably 8～10h.The present invention is to described coking also
Former equipment is not particularly limited, the equipment reduced with coking well known to those skilled in the art, coking of the present invention
The equipment of reduction is preferably coking furnace.
After mixing green coke that above-mentioned steps is obtained by the present invention again mixes again with alkali after pulverizing, at noble gas and/or
Carry out pre-activate and activation under conditions of nitrogen, obtain semi-finished product.
Particle diameter after described mixing green coke is pulverized by the present invention is not particularly limited, and those skilled in the art can be according to reality
The border condition of production, product requirement and prescription select and adjust, and the particle diameter after mixing green coke of the present invention is pulverized is excellent
Elect 50～100 μm, more preferably 60～90 μm, most preferably 70～80 μm as.Described alkali is not particularly limited by the present invention, with
Pitch coke activation alkali well known to those skilled in the art, those skilled in the art can be according to practical condition, product
Product require and prescription selects and adjusts, and alkali of the present invention preferably includes potassium hydroxide, sodium hydroxide, Lithium hydrate
With calcium hydroxide one or more of which, more preferably potassium hydroxide, sodium hydroxide, Lithium hydrate or calcium hydroxide, more preferably
For potassium hydroxide, sodium hydroxide or calcium hydroxide, most preferably potassium hydroxide.Described alkali is not had other to limit especially by the present invention
System, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, the present invention
For convenience of mixing, described alkali is preferably graininess alkali, and the particle diameter of described graininess alkali is preferably 10～300 μm, and more preferably 50
～250 μm, more preferably 100～200 μm, most preferably 130～170 μm.The consumption of described alkali is limited by the present invention the most especially
System, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, the present invention
The mass ratio of described mixing green coke and alkali is preferably 1:(0.5～5), more preferably 1:(1～4.5), more preferably 1:(1.5～
4), most preferably 1:(2～3.5).
Described noble gas is not particularly limited by the present invention, those skilled in the art can according to practical condition,
Product requirement and prescription select and adjust, and the present invention is particularly preferred as argon.The present invention is to described mixing again not
Having restriction especially, those skilled in the art can select according to practical condition, product requirement and prescription and adjust
Whole, the present invention is preferably batch mixer mixing.
Described preactivated condition is not particularly limited by the present invention, pre-with Colophonium green coke well known to those skilled in the art
The condition of activation, those skilled in the art can select according to practical condition, product requirement and prescription
And adjustment, preactivated temperature of the present invention is preferably 350～500 DEG C, more preferably 375～475 DEG C, and more preferably 400
～450 DEG C, most preferably 410～440 DEG C；The described preactivated time is preferably 1～4 hour, and more preferably 1.5～3.5 is little
Time, most preferably 2～3 hours.The condition of described activation is not particularly limited by the present invention, with well known to those skilled in the art
The condition of Colophonium green coke activation, those skilled in the art can be according to practical condition, product requirement and prescription
Selecting and adjust, the temperature of activation of the present invention is preferably 700～950 DEG C, more preferably 725～925 DEG C, more preferably
It is 750～900 DEG C, most preferably 800～850 DEG C；The time of described activation is preferably 0.5～4 hour, more preferably 1～3.5
Hour, more preferably 1.5～3 hours, most preferably 2～2.5 hours.The equipment of described pre-activate and activation is not had by the present invention
Limit especially, with Colophonium green coke pre-activate well known to those skilled in the art and the equipment of activation, those skilled in the art
Can select according to practical condition, product requirement and prescription and adjust, pre-activate of the present invention and activation
Equipment be preferably crucible.
The semi-finished product that above-mentioned steps is finally obtained by the present invention are through washing and dried, in the condition of protective gas
Under, after Overheating Treatment, obtain composite type pitch matrix activated carbon.
The step of described washing is not particularly limited by the present invention, activates with Colophonium green coke well known to those skilled in the art
After washing step, those skilled in the art can select according to practical condition, product requirement and prescription
Selecting and adjust, the concrete steps of washing of the present invention include Temperature fall, washing, pickling and washing the most successively, more specifically
It is preferably Temperature fall, is washed to neutrality, pickling, then is washed to neutrality.Spent pickling acid of the present invention is preferably hydrochloric acid, nitric acid
With one or more in phosphoric acid；The temperature of described washing is preferably 20～100 DEG C, more preferably 40～80 DEG C, most preferably
50～100 DEG C.Described dry step is not particularly limited by the present invention, and those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust.
Described protective gas is not particularly limited by the present invention, with protective gas well known to those skilled in the art i.e.
Can, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, the present invention
Described protective gas preferably includes one or more in hydrogen, ammonia, nitrogen and noble gas, more preferably hydrogen, ammonia
One or both in gas, nitrogen and argon.The condition of described heat treatment is not particularly limited by the present invention, with art technology
The heat treatment step of activated carbon prepared by pitch coke known to personnel, and those skilled in the art can be according to actual production feelings
Condition, product requirement and prescription select and adjust, and the temperature of heat treatment of the present invention is preferably 700～900 DEG C, more
It is preferably 720～880 DEG C, more preferably 750～850 DEG C, most preferably 770～830 DEG C；The time of described heat treatment is preferably
1～4 hour, more preferably 1.5～3.5 hours, most preferably 2～3 hours.
The present invention is to improve the quality of final product, further preferably includes crushing, screening and magnetic separation step after described heat treatment；
Described broken, screening and the detailed process of magnetic separation step and condition are not particularly limited by the present invention, and those skilled in the art can
To select according to practical condition, product requirement and prescription and to adjust, of the present invention broken after particle diameter excellent
Elect 6～10 μm, more preferably 7～9 μm as.
See the electromicroscopic photograph that Fig. 1, Fig. 1 are composite type pitch matrix activated carbon prepared by the present invention.
The present invention has prepared Graphene composite type pitch matrix activated carbon through above-mentioned steps, and the present invention will be by aoxidizing
Graphene with Colophonium at a certain temperature, through special shear-mixed step, defines the most compound graphene oxide multiple
Closing Colophonium (mixture), then graphene oxide and pitch coke are jointly reduced and activation through high-temperature-coked, graphene oxide exists
Pitch coke is internally formed uniform network；Simultaneously through high-temperature activation and high temperature reduction, graphene oxide removing major part oxygen shape
Become Graphene, so that activated carbon is internally formed good conductive network, reduce activated carbon internal resistance.The preparation that the present invention provides
Method effectively solves existing activated carbon mainly based on micropore, and pore-size distribution is unreasonable, alkali ratio used in preparation process
Example is higher, and Properties of Activated Carbon still cannot meet the problem bigger to the requirement in terms of capacity and internal resistance.Stone will be aoxidized
Ink alkene adds in Colophonium and common coking reduction, and graphene oxide is internally formed uniform network at pitch coke.Prepared by the present invention
Composite type pitch matrix activated carbon there is reasonable pore-size distribution, bigger serface, low internal resistance, high power capacity, low impurity and low oxygen-containing
The advantage of functional group, it is possible to as Supercapacitor carbon, obtains the more preferable ultracapacitor of performance.Test result indicate that, the present invention
The composite type pitch matrix activated carbon specific surface area of preparation is 2300～3200m2/ g, mesoporous is 35%～50%, mean diameter
Being 6～10 μm, nitrogen content is 1%～3%, metal impurities < 100ppm, low resistance, organic system quality than electric capacity be up to 160～
210F/g, good cycling stability.
Present invention also offers a kind of ultracapacitor, comprise the compound drip prepared by technique scheme any one
Blue or green matrix activated carbon.The definition of described ultracapacitor is not particularly limited by the present invention, with well known to those skilled in the art super
The definition of level capacitor.
In order to further illustrate the present invention, a kind of composite type pitch base activity present invention provided below in conjunction with embodiment
Preparation method and the ultracapacitor of charcoal are described in detail, but it is to be understood that these embodiments are with skill of the present invention
Implement under premised on art scheme, give detailed embodiment and concrete operating process, simply for further illustrating
The features and advantages of the present invention rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following
Embodiment.
Embodiment 1
Taking 500g coal tar asphalt, heating is allowed to melt, and keeps temperature 150 DEG C；Weigh 5g graphene oxide powder to add
Coal tar asphalt, stirs 20min, then uses cutter stirring 90min, shear rate 150rmp；It is cooled to 120 DEG C and places
60min, shears 90min the most again, obtains the coal tar asphalt that graphene oxide is fully dispersed；
Under nitrogen protection, this Colophonium being heated in coking furnace 450 DEG C and keep 8h, natural cooling, then in pulverizer
It is ground into the powder of 50～100 μm；Add the KOH of 1500g powder and uniformly mix.This mixture is added metallic nickel earthenware
Crucible, is warming up to 450 DEG C with the speed of 10～20 DEG C/min under nitrogen atmosphere and keeps 3h；Then with the speed of 10～20 DEG C/min
Degree is warming up to 750 DEG C of activation 2h, is naturally down to room temperature.Product is soluble in water, and cyclic washing, to neutral, is subsequently adding the salt of 6M
Acid backflow 2h, filters, deionized water wash to neutrality, vacuum drying.Gained pressed powder is added in rotary furnace, at 10% hydrogen
Being warming up to 800 DEG C under gas-nitrogen mixture and keep 2h, cooling, secondary ball milling is ground into the powder of 6～9 μm, through magnetic separator
Remove unnecessary metal ion, obtain composite type pitch matrix activated carbon (asphaltic base Supercapacitor carbon).
See the electromicroscopic photograph of the composite type pitch matrix activated carbon that Fig. 2, Fig. 2 are the embodiment of the present invention 1 preparation.
See the graph of pore diameter distribution of the composite type pitch matrix activated carbon that Fig. 3, Fig. 3 are the embodiment of the present invention 1 preparation.
Detecting the composite type pitch matrix activated carbon of above-described embodiment 1 preparation, the specific surface area of activated carbon is
3200m2/ g, mesoporous is 65%, and mean diameter is 7.4 μm, and nitrogen content is 1.5%, metal impurities < 100ppm.
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V), when electric current density is 2A/g, quality is 210F/g than electric capacity.
Embodiment 2
Taking 200g coal tar asphalt, heating is allowed to melt, and keeps temperature 180 DEG C；Weigh 1g graphene oxide powder to add
Coal tar asphalt, stirs 20min, then uses cutter stirring 90min, shear rate 150rmp；It is cooled to 120 DEG C and places
60min, shears 90min the most again, obtains the coal tar asphalt that graphene oxide is fully dispersed；
Under nitrogen protection, this Colophonium being heated in coking furnace 500 DEG C and keep 6h, natural cooling, then in pulverizer
It is ground into the powder of 50～100 μm；Add the KOH of 500g powder and uniformly mix.This mixture is added metallic nickel crucible,
Under nitrogen atmosphere, it is warming up to 450 DEG C with the speed of 10～20 DEG C/min and keeps 3h；Then with the speed of 10～20 DEG C/min
It is warming up to 750 DEG C of activation 1.5h, is naturally down to room temperature.Product is soluble in water, and cyclic washing, to neutral, is subsequently adding the salt of 6M
Acid backflow 2h, filters, deionized water wash to neutrality, vacuum drying.Gained pressed powder is added in rotary furnace, under ammonia
Being warming up to 800 DEG C and keep 2h, cooling, secondary ball milling is ground into the powder of 6～9 μm, removes unnecessary metal through magnetic separator
Ion, obtains asphaltic base Supercapacitor carbon.
Detecting the composite type pitch matrix activated carbon of above-described embodiment 2 preparation, the specific surface area of activated carbon is
2500m2/ g, mesoporous is 68%, and mean diameter is 6.9 μm, and nitrogen content is 1.6%, metal impurities < 100ppm.
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V), when electric current density is 2A/g, quality is 190F/g than electric capacity.
Embodiment 3
Taking 200g asphalt, heating is allowed to melt, and keeps temperature 160 DEG C；Weigh 0.5g graphene oxide powder to add
Asphalt, stirs 20min, then uses cutter stirring 90min, shear rate 150rmp；It is cooled to 100～120 DEG C also
Place 60min, the most again shear 90min, obtain the asphalt that graphene oxide is fully dispersed；
Under nitrogen protection, this Colophonium being heated in coking furnace 500 DEG C and keep 6h, natural cooling, then in pulverizer
It is ground into the powder of 50～100 μm；Add the KOH of 200g powder and uniformly mix.This mixture is added metallic nickel crucible,
Under nitrogen atmosphere, it is warming up to 500 DEG C with the speed of 10～20 DEG C/min and keeps 3h；Then with the speed of 10～20 DEG C/min
It is warming up to 800 DEG C of activation 2h, is naturally down to room temperature.Product is soluble in water, and cyclic washing, to neutral, is subsequently adding the hydrochloric acid of 6M
Backflow 2h, filters, and deionized water wash, to neutral, is vacuum dried.Gained pressed powder is added in rotary furnace, rises under hydrogen
Temperature to 800 DEG C and keep 2h, cooling, secondary ball milling is ground into the powder of 6～9 μm, through magnetic separator remove unnecessary metal from
Son, obtains asphaltic base Supercapacitor carbon.
Detecting the composite type pitch matrix activated carbon of above-described embodiment 3 preparation, the specific surface area of activated carbon is
2300m2/ g, mesoporous is 58%, and mean diameter is 7.5 μm, and nitrogen content is 1.6%, metal impurities < 100ppm.
This activated carbon is mixed homogenate with binding agent SBR with CMC, is uniformly coated on aluminium foil, drying, roll, punching
After be assembled into ultracapacitor (organic system, 2.7V), when electric current density is 2A/g, quality is 160F/g than electric capacity.
Preparation method and ultracapacitor to a kind of composite type pitch matrix activated carbon that the present invention provides are carried out above
Detailed introduction, principle and the embodiment of the present invention are set forth by specific case used herein, above enforcement
The explanation of example is only intended to help to understand method and the core concept thereof of the present invention, including best mode, and also makes ability
Any technical staff in territory can put into practice the present invention, including manufacturing and using any device or system, and implements any combination
Method.It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention,
The present invention can also be carried out some improvement and modification, these improve and modify the protection domain also falling into the claims in the present invention
In.The scope of patent protection of the present invention is defined by the claims, and those skilled in the art can be included it is conceivable that its
His embodiment.If these other embodiments have the structural element being not different from claim character express, if or
They include the equivalent structural elements without essence difference of the character express with claim, then these other embodiments also should be wrapped
Containing within the scope of the claims.
Claims (10)
1. the preparation method of a composite type pitch matrix activated carbon, it is characterised in that comprise the following steps:
A), after being mixed with graphene oxide by the matrix pitch after fusing, mixture is obtained；
B) under conditions of noble gas and/or nitrogen, after mixture above-mentioned steps obtained carries out coking reduction, mixed
Symphysis is burnt；
C) after mixing green coke above-mentioned steps obtained mixes again with alkali after pulverizing, in noble gas and/or the condition of nitrogen
Under carry out pre-activate and activation, obtain semi-finished product；
D) semi-finished product above-mentioned steps obtained are through washing and dried, under conditions of protective gas, through Overheating Treatment
After, obtain composite type pitch matrix activated carbon.
Preparation method the most according to claim 1, it is characterised in that described matrix pitch include coal tar asphalt and/or
Asphalt；
It is 0.1%～1% that the quality of described graphene oxide accounts for the ratio of described matrix pitch quality；
The temperature of described mixing is 100～180 DEG C.
Preparation method the most according to claim 2, it is characterised in that concretely comprising the following steps of described mixing:
Under conditions of 150～180 DEG C, it is stirred mixing 10～30min with graphene oxide by the matrix pitch after fusing,
Then shear-mixed 60～90min；Be cooled to 100～120 DEG C again and place 30～60min, the most again shear-mixed 60～
90min, obtains mixture.
Preparation method the most according to claim 1, it is characterised in that the temperature of described coking reduction is 450～500 DEG C；
The time of described coking reduction is 6～12h.
Preparation method the most according to claim 1, it is characterised in that described mixing green coke pulverize after particle diameter be 50～
100μm；
Described alkali is graininess alkali, and the particle diameter of described graininess alkali is 10～300 μm.
Preparation method the most according to claim 1, it is characterised in that described alkali includes potassium hydroxide, sodium hydroxide, hydrogen-oxygen
Change lithium and calcium hydroxide one or more of which；
Described mixing green coke is 1:(0.5～5 with the mass ratio of alkali).
Preparation method the most according to claim 1, it is characterised in that described preactivated temperature is 350～500 DEG C；Institute
Stating the preactivated time is 1～4 hour；
The temperature of described activation is 700～950 DEG C, and the time of described activation is 0.5～4 hour.
Preparation method the most according to claim 1, it is characterised in that described protective gas includes hydrogen, ammonia, nitrogen
With one or more in noble gas；
The temperature of described heat treatment is 700～900 DEG C, and the time of described heat treatment is 1～4 hour.
Preparation method the most according to claim 1, it is characterised in that also include after described heat treatment crushing, screening and magnetic
Select step；
Described broken after particle diameter be 6～10 μm.
10. a ultracapacitor, it is characterised in that comprise the composite type pitch base prepared by claim 1～9 any one
Activated carbon.
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| CN109665523A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of graphene composite stone oil coke matrix activated carbon |
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| CN109659149A (en) * | 2018-12-27 | 2019-04-19 | 广东聚石化学股份有限公司 | A kind of graphene absorbent charcoal composite material and its preparation method and application |
| CN109659149B (en) * | 2018-12-27 | 2021-04-06 | 广东聚石化学股份有限公司 | Graphene activated carbon composite material and preparation method and application thereof |
| CN114843111A (en) * | 2022-05-17 | 2022-08-02 | 清华大学 | Multilevel-structure carbon nanocomposite and preparation method and application thereof |
| CN114843111B (en) * | 2022-05-17 | 2024-01-30 | 清华大学 | Multi-level structure carbon nano composite material and preparation method and application thereof |
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