CN108996501B - Modified activated carbon material, preparation method and application - Google Patents
Modified activated carbon material, preparation method and application Download PDFInfo
- Publication number
- CN108996501B CN108996501B CN201710418281.6A CN201710418281A CN108996501B CN 108996501 B CN108996501 B CN 108996501B CN 201710418281 A CN201710418281 A CN 201710418281A CN 108996501 B CN108996501 B CN 108996501B
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- carbon material
- modified
- modified activated
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 442
- 239000000463 material Substances 0.000 title claims abstract description 162
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 112
- 239000002245 particle Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000006722 reduction reaction Methods 0.000 claims description 32
- 125000000524 functional group Chemical group 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011163 secondary particle Substances 0.000 claims description 19
- 230000003213 activating effect Effects 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- -1 aliphatic diamine Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000010612 desalination reaction Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 244000302661 Phyllostachys pubescens Species 0.000 claims description 6
- 235000003570 Phyllostachys pubescens Nutrition 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002006 petroleum coke Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 4
- 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 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- 239000002211 L-ascorbic acid Substances 0.000 claims description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 2
- 240000007817 Olea europaea Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 244000018633 Prunus armeniaca Species 0.000 claims description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 150000004662 dithiols Chemical class 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004299 exfoliation Methods 0.000 claims description 2
- 239000007849 furan resin Substances 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical group O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 239000003415 peat Substances 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims description 2
- 239000013520 petroleum-based product Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 238000001311 chemical methods and process Methods 0.000 claims 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 claims 1
- 235000014571 nuts Nutrition 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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)
Abstract
The invention provides a modified activated carbon material which is characterized by comprising activated carbon particles and a graphene sheet layer adsorbed on the activated carbon particles. According to the invention, the graphene material is adopted to modify the activated carbon, and at least part of the graphene material and the activated carbon are crosslinked together through a covalent bond, so that the graphene material is firmly combined on the activated carbon, and the effects of enhancing the specific surface area and the adsorption capacity of the activated carbon are achieved; from the aspect of dispersibility, the graphene material is firmly and effectively combined with the activated carbon, so that the dispersibility of the graphene material is reduced, and the uniformity of the modified activated carbon material in the using process is improved; for the reduced graphene oxide modified activated carbon material, the conductivity is enhanced, the specific surface area is increased, and the dispersibility is good.
Description
Technical Field
The invention belongs to the field of modified functional materials, and particularly relates to a modified activated carbon material, a preparation method and application thereof.
Background
The activated carbon material is amorphous carbon obtained by processing treatment, has a large specific surface area, and has good adsorption capacity on gases, inorganic or organic substances in solution, colloidal particles and the like. The Activated Carbon material mainly includes Activated Carbon (AC), Activated Carbon Fibers (ACF), and the like. The activated carbon material is used as an adsorbent with excellent performance, which is mainly determined by the unique adsorption surface structure characteristic and surface chemical property. The activated carbon material has stable chemical properties, high mechanical strength, acid resistance, alkali resistance and heat resistance, is insoluble in water and organic solvents, can be recycled, and is widely applied to various fields of chemical industry, environmental protection, food processing, metallurgy, medicine refining, military chemical protection and the like.
In the prior art, a method for modifying activated carbon by graphene is mostly a method of mixing graphene and activated carbon at a high temperature, and the method can combine materials of graphene and activated carbon, but has poor dispersion uniformity, poor mixing effect of graphene and activated carbon, improved performance of activated carbon materials and limited effect.
The graphene material modified activated carbon material needs to be developed in the field, and the graphene material and the activated carbon material can be firmly combined, so that good dispersibility, specific surface area, electrical properties and the like are obtained.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention relates to a modified activated carbon material which comprises activated carbon particles and graphene sheet layers adsorbed on the activated carbon particles.
The adsorption of the invention comprises physical adsorption and chemical adsorption, wherein the physical adsorption is also called Van der Waals adsorption, and the particles are adsorbed by intermolecular force; the chemisorption is the adsorption in which transfer, exchange, or sharing of electrons occurs between particles, forming an adsorption chemical bond. The term adsorption in the context of the present invention includes both physical adsorption and chemisorption, which is understood to mean both physical adsorption and chemisorption, or chemisorption.
Preferably, in the modified activated carbon material, at least part of the graphene sheet layers are adsorbed on the activated carbon particles through chemical bonds.
The graphene material and the activated carbon matrix are crosslinked through chemical bonds, the chemical bond crosslinking is firmer compared with Van der Waals force, and the graphene material firmly combined with the activated carbon material endows the activated carbon material with higher specific surface area and more excellent electrical properties.
Preferably, the modified activated carbon material comprises secondary particles of the modified activated carbon material, and the secondary particles of the modified activated carbon material comprise at least 2 activated carbon particles crosslinked by graphene sheets.
The secondary particles described in the present invention may be understood as particles obtained by agglomeration of monomer particles (e.g., activated carbon particles, graphene lamellar particles, particles of activated carbon adsorbing graphene, etc.). In the secondary particles of the modified activated carbon material of the present invention, there are secondary particles composed of at least 2 activated carbon particles (monomer particles) crosslinked by graphene sheets.
In any secondary particle of the modified activated carbon material, the kind and number of the monomer particles are not particularly limited, and for example, 2 (3, 4, 5, etc.) activated carbon particles may be agglomerated with 1 (2, 3, 4, 5, etc.) graphene sheet layer by chemisorption or physisorption.
Preferably, the secondary particle of the modified activated carbon material has a particle size larger than that of the activated carbon particle.
In the modified activated carbon material of the present invention, a majority (which may be understood to be greater than 70%, or greater than 80% or greater than 90%) of the particles are present as secondary particles.
Preferably, the secondary particles of the modified activated carbon material have a particle size of 20 μm or less, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, or the like, preferably 12 μm or less, and more preferably 5 μm or less.
Since the particle size of the monomer particles (mainly activated carbon particles) is greatly different (for example, the particle size of common activated carbon particles is more than 1 μm, and the particle size of bamboo charcoal is mostly less than 1 μm), the size of the obtained secondary particles is also greatly different.
Optionally, the secondary particle of the modified activated carbon material has a particle size of 3 to 7 μm, such as 4 μm, 5 μm, 6 μm, and the like, preferably 4 to 6 μm.
Alternatively, the particle size of the modified activated carbon particles is 1 μm or less, for example, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, etc., preferably 0.5 to 0.8 μm.
Preferably, the specific surface area of the modified activated carbon material is 1000-3000 m2(iv)/g, preferably 2200 to 3000m2The amount of the modified activated carbon material is 0.7-10 nm has a continuously distributed pore structure, the average pore diameter is 2-10 nm, and the mesopore proportion is 10-50%.
The second purpose of the invention is to provide a preparation method of the modified activated carbon material, which is characterized by comprising the following steps:
(1) activating the activated carbon to obtain activated carbon modified with oxygen-containing functional groups;
(2) mixing the activated carbon modified with the oxygen-containing functional group with the graphene material containing the functional group, adding a cross-linking agent, and carrying out cross-linking polymerization to obtain the modified activated carbon material.
The graphene oxide modified activated carbon has more oxygen-containing functional groups, excellent specific surface area, stable chemical properties and excellent effect in the adsorption field. In the graphene oxide modified activated carbon, a large number of functional groups (such as various electronegative oxygen-containing functional groups such as epoxy groups, hydroxyl groups, carboxyl groups, carbonyl groups and the like) are distributed on the basal plane and the edge of the graphene oxide containing functional groups, cations can be effectively adsorbed through electrostatic adsorption, and the adsorption capacity of the graphene oxide modified activated carbon on cationic dyes and heavy metal ions is far higher than that of the traditional carbon adsorption material and exchange resin ions; a great amount of oxygen-containing functional groups endow the modified activated carbon with excellent hydrophilicity, and simultaneously, due to the fact that the graphene oxide with excellent hydrophilicity is difficult to separate after adsorption in practical application, adsorption active sites can be increased and recovery and separation are facilitated by crosslinking other groups on the surface of the graphene oxide.
Optionally, step (2) is followed by step (3): the reduction operation is carried out after the crosslinking polymerization.
The graphene oxide modified activated carbon material is reduced to obtain the reduced graphene oxide modified activated carbon material, and the reduced graphene oxide modified activated carbon material has large specific surface area and strong mechanical property and thermal conductivity. Compared with the graphene oxide modified activated carbon material, in the reduced graphene oxide modified activated carbon material, the oxygen-containing functional groups are reduced, the charge mobility is increased, the pore structure is orderly and reasonable, and the modified activated carbon material can be used for a supercapacitor electrode material, the functional groups and the number of the functional groups on the surface of the modified activated carbon have direct influence on the leakage characteristic, the specific capacitance, the voltage resistance and the service life, and the parameters are visual indicators for judging the quality of the capacitor, for example, the higher the hydroxyl concentration in an aqueous medium is, the higher the electrode leakage current is, the poorer the storage property is, the higher the carboxyl concentration is, the higher the static potential of the material is, the higher the possibility of oxygen precipitation reaction is, and the more unstable the electrode is; the increase of the charge mobility is beneficial to the electrode material to exert more conductive capability and realize the rapid transfer of charges; the ordered and reasonable pore structure is beneficial to the adsorption and transfer of electrolyte ions in different systems, thereby further playing a better capacitance characteristic.
The particle size of the activated carbon in step (1) is preferably 10 μm or less, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, etc., preferably 5 μm or less, and more preferably 3 μm or less.
Optionally, the particle size of the activated carbon is 3-7 μm, preferably 4-6 μm.
Optionally, the particle size of the activated carbon is below 1 μm, preferably 0.5-0.8 μm.
The source of the activated carbon is not particularly limited in the present invention, and any activated carbon available to those skilled in the art can be used in the present invention, and can be obtained commercially or prepared by any known method.
Preferably, the carbon source for preparing the activated carbon comprises any 1 or at least 2 of nutshell, bamboo material, coal, petroleum product, agricultural byproduct and macromolecule, preferably any 1 or at least 2 of coconut shell, petroleum coke, phenolic resin and moso bamboo.
Preferably, the nutshell core comprises any 1 or a combination of at least 2 of coconut shell, olive shell, walnut shell and apricot core.
Preferably, the bamboo material comprises moso bamboo and/or phyllostachys pubescens.
Preferably, the coal quality comprises any 1 or a combination of at least 2 of peat, lignite, bituminous coal.
Preferably, the petroleum based product comprises any 1 or a combination of at least 2 of bitumen, petroleum coke.
Preferably, the agricultural by-product comprises any 1 or a combination of at least 2 of rice hulls, straw, furfural residue.
Preferably, the polymer comprises any 1 or a combination of at least 2 of phenolic resin and furan resin.
The graphene material of the present invention is any material having graphene sheets, which can be known to those skilled in the art, and includes graphene, graphene oxide, functionalized graphene, and the like. The preparation method of the graphene material is not particularly limited in the present invention, and may be a graphite exfoliation method, a graphite oxidation and reduction method, a chemical vapor deposition method, or the like.
Preferably, the graphene material is a material having a graphene sheet structure, and includes any 1 or a combination of at least 2 of graphene, graphene oxide, and a graphene derivative.
Preferably, the graphene comprises graphite prepared by a stripping method, the graphene oxide is prepared by reduction, the graphite is prepared by oxidation reduction, the carbon-containing gas is prepared by a CVD method, and the graphene is prepared by a high-temperature cracking method by taking biomass as a raw material.
Preferably, the mass ratio of the activated carbon modified with oxygen-containing functional groups in the step (2) to the graphene material containing functional groups is 100:0.1 to 20, for example, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14, 100:15, 100:16, 100:17, 100:18, 100:19, etc., preferably 100:0.8 to 8, and more preferably 100:2 to 5.
Preferably, the step of activating in step (1) is: the activated carbon is mixed with an activating agent.
After the modified activated carbon is mixed with an activating agent, an active group can be formed on the activated carbon, so that the graphene material can be combined.
Preferably, the activator comprises an oxidizing agent, preferably any 1 or a combination of at least 2 of nitric acid, sulfuric acid, phosphoric acid, sodium hypochlorite, hydrogen peroxide.
Preferably, the addition amount of the activating agent is 0.1 to 10 times of the weight of the activated carbon, for example, 0.5 times, 0.7 times, 1.3 times, 1.8 times, 2.3 times, 2.8 times, 3.3 times, 3.8 times, 4.3 times, 4.8 times, 5.3 times, 5.8 times, 6.3 times, 6.8 times, 7.3 times, 7.8 times, 8.3 times, 8.8 times, 9.3 times, 9.8 times, and the like.
Preferably, the temperature of the activation is 35-85 ℃, such as 36 ℃, 42 ℃, 48 ℃, 52 ℃, 58 ℃, 62 ℃, 68 ℃, 72 ℃, 78 ℃, 82 ℃ and the like, and the activation time is 0.5-10 h, such as 0.6h, 1.2h, 1.7h, 2.2h, 2.7h, 3.2h, 3.7h, 4.2h, 4.7h, 5.2h, 5.7h, 6.2h, 6.7h, 7.2h, 7.7h, 8.2h, 8.7h, 9.2h, 9.7h and the like.
Preferably, the functionalized graphene material in step (2) comprises graphene oxide and/or aminated graphene.
Preferably, the cross-linking agent comprises any 1 or a combination of at least 2 of ethylene glycol, polyethylene glycol, ethanolamine, ethylenediamine, aliphatic diamine, melamine, dithiol, mercaptoethanol.
Preferably, the addition amount of the cross-linking agent is 0.1 to 10 times of the weight of the graphene material, for example, 0.5 times, 0.7 times, 1.3 times, 1.8 times, 2.3 times, 2.8 times, 3.3 times, 3.8 times, 4.3 times, 4.8 times, 5.3 times, 5.8 times, 6.3 times, 6.8 times, 7.3 times, 7.8 times, 8.3 times, 8.8 times, 9.3 times, 9.8 times, and the like.
Preferably, the pH value of the cross-linking polymerization is 4-8, such as 5, 6, 7, etc., the temperature of the cross-linking polymerization is 30-90 ℃, such as 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, etc., and the time is 0.5-5 h, such as 0.6h, 1.2h, 1.7h, 2.2h, 2.7h, 3.2h, 3.7h, 4.2h, 4.7h, etc.
Preferably, the reduction comprises a chemical reduction method, a carbonization reduction method or a microwave reduction method.
Preferably, the chemical method is contacting the modified activated carbon material with a chemical reducing agent comprising any 1 or a combination of at least 2 of hydrazine hydrate, L-ascorbic acid, sodium borohydride, sodium citrate, sodium hydroxide.
Preferably, the carbonization-reduction method is to carry out carbonization in a non-oxidizing atmosphere, wherein the carbonization temperature is 500-1000 ℃, and the carbonization time is 0.5-6 h.
Preferably, the microwave reduction method is to perform microwave reduction in a non-oxidizing atmosphere, wherein the microwave power is 1.5-0.8 kW, and the microwave time is 1-15 min.
Preferably, after the modified activated carbon material is reduced in the step (3), the modified activated carbon material is washed until the conductivity is constant, and then dried.
Preferably, the drying temperature is 40-120 ℃.
The invention also aims to provide the application of the modified activated carbon material, which is used in the fields of super capacitors, water treatment, seawater desalination and water desalination.
Preferably, the modified activated carbon material is used as an adsorption material for water treatment, a seawater desalination adsorption material and a water desalination adsorption material.
Preferably, the reduction product of the modified activated carbon material subjected to the reduction operation is used as an electrode material of a supercapacitor.
The fourth purpose of the invention is to provide a super capacitor, and the electrode material of the super capacitor comprises the modified activated carbon material.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the graphene material is adopted to modify the activated carbon, and at least part of the graphene material and the activated carbon are crosslinked together through a covalent bond, so that the graphene material is firmly combined on the activated carbon, and the effects of enhancing the specific surface area and the adsorption capacity of the activated carbon are achieved;
(2) from the aspect of dispersibility, the graphene material is firmly and effectively combined with the activated carbon, so that the dispersibility of the graphene material is reduced, and the uniformity of the modified activated carbon material in the using process is improved;
(3) for the reduced graphene oxide modified activated carbon material, the conductivity is enhanced, the specific surface area is increased, and the dispersibility is good.
Drawings
FIG. 1 is a 5000-fold magnified electron micrograph of the modified activated carbon material obtained in example 4;
FIG. 2 is an electron micrograph of the modified activated carbon material obtained in example 4, magnified 20000 times;
FIG. 3 is an electron micrograph at 3000 times magnification of a modified activated carbon material obtained in example 7;
FIG. 4 is an electron micrograph at 30000 magnification of a modified activated carbon material obtained in example 7;
fig. 5 is a constant current charge/discharge diagram in a water system.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A modified activated carbon material is prepared by the following steps:
(1) uniformly dispersing 10g of activated carbon (1-10 mu M) to be modified in 500mL of 0.1M sulfuric acid solution, stirring at 80 ℃ for 1h, and then cleaning the precipitate until the pH value is close to 7 to obtain activated carbon;
(2) dispersing activated carbon in 100mL of 1 wt% ethylene glycol aqueous solution, then dripping 150mL of 0.5 wt% graphene oxide aqueous solution under the reflux condition at 80 ℃, and continuously stirring for 12h to obtain graphene oxide modified activated carbon material dispersion liquid;
(3) and filtering the graphene oxide modified activated carbon material dispersion liquid, cleaning the precipitate with clear water, and then drying and grinding the precipitate to obtain the graphene oxide modified activated carbon material.
Example 2
The difference from example 1 is that step (3) is: adding 5mL of 20 wt% hydrazine hydrate into the graphene oxide modified activated carbon material dispersion liquid at room temperature, then washing the precipitate with deionized water until the conductivity of the washing liquid is constant, and finally drying and grinding the filter cake at 80 ℃ to obtain the graphene modified activated carbon.
Example 3
A modified activated carbon material is prepared by the following steps:
(1) uniformly dispersing 5g of activated carbon (1-10 mu M) in 500mL of 0.1M sulfuric acid solution, stirring for 5h at 40 ℃, and then cleaning the precipitate until the pH value is close to 7 to obtain activated carbon;
(2) dispersing activated carbon in 100mL of 10 wt% ethylene glycol aqueous solution, then dripping 150mL of 0.5 wt% graphene oxide aqueous solution under the reflux condition at 80 ℃, and continuously stirring for 12h to obtain graphene oxide modified activated carbon material dispersion liquid;
(3) and drying the graphene oxide modified activated carbon material dispersion liquid at a constant temperature of 60 ℃ to obtain the graphene oxide modified activated carbon material.
Example 4
The difference from example 3 is that step (3) is: drying the graphene oxide modified activated carbon material dispersion liquid at a constant temperature of 60 ℃, then placing the graphene oxide modified activated carbon material dispersion liquid in a nitrogen protection environment for microwave treatment at 1000 ℃ for 60min for reduction, then washing a microwave reduction product by using deionized water until the conductivity of filtrate is stable, and finally drying and grinding a filter cake at 80 ℃ to obtain the graphene modified activated carbon.
FIGS. 1 and 2 are electron micrographs at different magnification of the modified activated carbon material obtained in example 4.
As can be seen from fig. 1 and 2, the modified activated carbon material provided by the invention has a composite structure of a graphene thin layer and activated carbon particles, wherein the graphite sheet layer is crosslinked on the activated carbon particles through chemical bonds, the particle density of the activated carbon is microscopically improved, and the activated carbon is fixed on the graphene sheet layer through a crosslinking agent, so that pi-pi accumulation of graphene is effectively inhibited, and the microscopical feature of interconnection of carbon particles-GR thin layer-carbon particles is realized.
Example 5
The difference from the example 2 lies in: the step (3) is as follows: drying the graphene oxide modified activated carbon material dispersion liquid at a constant temperature of 60 ℃, then placing the graphene oxide modified activated carbon material dispersion liquid in a nitrogen protection environment for microwave treatment at 1000 ℃ for 60min for reduction, then washing a microwave reduction product by using deionized water until the conductivity of filtrate is stable, and finally drying and grinding a filter cake at 80 ℃ to obtain the graphene modified activated carbon.
Example 6
A modified activated carbon material is prepared by the following steps:
(1) uniformly dispersing 5g of activated carbon (1-10 mu M) in 500mL of 0.1M phosphoric acid solution, stirring for 5h at 40 ℃, and then cleaning the precipitate until the pH value is close to 7 to obtain activated carbon;
(2) dispersing activated carbon in 100mL of 10 wt% melamine aqueous solution, then dripping 150mL of 0.5 wt% graphene oxide aqueous solution under the reflux condition at 80 ℃, and continuously stirring for 12 hours to obtain graphene oxide modified activated carbon material dispersion liquid;
(3) and drying the graphene oxide modified activated carbon material dispersion liquid at a constant temperature of 60 ℃ to obtain the graphene oxide modified activated carbon material.
Example 7
The difference from example 6 is that step (3) is: drying the graphene oxide modified activated carbon material dispersion liquid at a constant temperature of 60 ℃, carbonizing the graphene oxide modified activated carbon material dispersion liquid at a temperature of 600 ℃ for 10 hours under the protection of nitrogen for reduction, cleaning a reduction product by using deionized water until the conductivity of filtrate is stable, and finally drying and grinding a filter cake at a temperature of 80 ℃ to obtain the graphene modified activated carbon.
FIGS. 3 and 4 are electron micrographs at different magnification of the modified activated carbon material obtained in example 7.
As can be seen from fig. 3 and 4, the modified activated carbon material provided by the invention has a composite structure of a graphene thin layer and activated carbon particles, wherein the graphite sheet layer is crosslinked on the activated carbon particles through chemical bonds, the particle density of the activated carbon is microscopically improved, and the activated carbon is fixed on the graphene sheet layer through a crosslinking agent, so that pi-pi accumulation of graphene is effectively inhibited, and the microscopical feature of interconnection of carbon particles-GR thin layer-carbon particles is realized.
Example 8
The difference from the example 3 is that the activating agent in the step (1) is sodium hypochlorite solution, the mass of the sodium hypochlorite in the sodium hypochlorite solution is 10g, the activating temperature is 35 ℃, and the time is 10 h.
Example 9
The difference from the example 4 is that the activating agent in the step (1) is sodium hypochlorite solution, the mass of the sodium hypochlorite in the sodium hypochlorite solution is 10g, the activating temperature is 35 ℃, and the time is 10 h.
Example 10
The difference from the example 3 is that the activating agent in the step (1) is nitric acid solution, the mass of nitric acid in the nitric acid solution is 50g, the activating temperature is 50 ℃, and the time is 1 h.
Example 11
The difference from example 4 is that the activating agent in step (1) is nitric acid solution, the mass of sulfuric acid in the nitric acid solution is 10g, the activating temperature is 50 ℃, and the time is 1 h.
Example 12
The difference from example 3 is that 100mL of 10 wt% aqueous ethylene glycol solution in step (2) was replaced with 100mL of 50 wt% aqueous ethylene glycol solution, and the crosslinking polymerization temperature was 30 ℃ and the time was 3 hours.
Example 13
The difference from example 4 is that 100mL of 10 wt% aqueous ethylene glycol solution in step (2) was replaced with 100mL of 50 wt% aqueous ethylene glycol solution, and the crosslinking polymerization temperature was 30 ℃ and the time was 3 hours.
Example 14
A modified activated carbon material is prepared by the following steps:
(1) uniformly dispersing 5g of activated carbon (1-10 mu M) in 500mL of 0.1M sulfuric acid solution, stirring for 5h at 40 ℃, and then cleaning the precipitate until the pH value is close to 7 to obtain activated carbon;
(2) dispersing activated carbon in 100mL of 10 wt% ethylene glycol aqueous solution, then dripping 100mL of 0.5 wt% stripped graphene aqueous solution under the reflux condition at 80 ℃, and continuously stirring for 12 hours to obtain graphene modified activated carbon material dispersion liquid;
(3) and drying the graphene modified activated carbon material dispersion liquid at a constant temperature of 60 ℃ to obtain the graphene modified activated carbon material.
Comparative example 1
The activated carbon material to be modified used in the examples was taken as comparative example 1.
Comparative example 2
In the embodiment, the activated carbon material to be modified is placed under the protection of nitrogen and carbonized at 600 ℃ for 10h for reduction, the reduction product is washed by deionized water until the conductivity of the filtrate is stable, and finally the filter cake is dried at 80 ℃ and then ground to obtain the high-temperature modified activated carbon.
Comparative example 3
5g of activated carbon (1-10 mu m) and 0.1g of graphene obtained by a stripping method are mixed and ground for 1 hour to obtain the graphene modified activated carbon material.
Performance testing
(1) Specific surface area: GB/T19587-2004 method for determining specific surface area of solid substance by using gas adsorption BET principle;
(2) resistivity: GB 242530-2009 method for measuring resistivity of carbon material
(3) Specific capacitance: the graphene modified activated carbon of example 7 and example 11 and the activated carbon to be modified of comparative example 1 were respectively used as electrode materials, the electrode materials were dispersed in 1.5mL of anhydrous ethanol, conductive carbon black and a polytetrafluoroethylene binder were sequentially added, the mass ratio of the electrode materials to the conductive carbon black to the binder was 8:1:1, the electrode materials were ultrasonically mixed and then applied dropwise to a foam nickel-based electrode, and the electrode was dried to obtain a working electrode, a mercury oxide electrode was used as a reference electrode, a platinum sheet was used as a counter electrode, and an electrolyte was 6M KOH.
(4) Preparing 1.mg/mL methylene blue solution, weighing 1g of adsorbent, placing the adsorbent in a centrifugal tube of 70mL of methylene blue solution, reacting for 360min in a constant temperature shaking table (25 ℃, 250r/min) in a dark place, performing centrifugal separation, measuring absorbance of supernate by using UV-Vis, and calculating the adsorption capacity according to the following formula:
qe＝(C0–Ce)·V/m
wherein, C0And CeInitial and equilibrium concentrations of methylene blue (mg/mL), respectively; m is the mass of the modified activated carbon material; v is the volume of methylene blue solution (mL); q. q.seAs an equilibrium adsorption amount (mg/g).
The test results are shown in table 1:
table 1 shows the results of the performance tests of the modified activated carbon materials of examples and comparative examples
The performance test result shows that the surface area of the modified activated carbon material is increased, certain oxygen-containing functional groups are introduced into the activated carbon material and the graphene oxide, and the adsorption capacity of methylene blue is remarkably increased; the resistivity of the graphene oxide modified activated carbon material is increased, the resistivity of the activated carbon material modified by reduction treatment or direct use of graphene is reduced, the modified electrode promotes the transfer of charges and electrolyte ions in a water system, the specific capacitance is increased, and products obtained by reduction methods, microwave reduction and high-temperature reduction have better resistivity and specific capacitance.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (47)
1. A modified activated carbon material is characterized by comprising activated carbon particles and graphene sheets adsorbed on the activated carbon particles; the modified activated carbon material comprises secondary particles of the modified activated carbon material, and the secondary particles comprise at least 2 activated carbon particles crosslinked through graphene sheets;
the modified activated carbon material is prepared by adopting the following method, and the method comprises the following steps:
(1) mixing activated carbon with an activating agent for activation to obtain activated carbon modified with oxygen-containing functional groups; the activating agent is selected from any 1 or combination of at least 2 of nitric acid, sulfuric acid, phosphoric acid, sodium hypochlorite or hydrogen peroxide; the activation temperature is 35-85 ℃, and the activation time is 0.5-10 h;
(2) mixing the activated carbon modified with the oxygen-containing functional group with the graphene material containing the functional group, adding a cross-linking agent, and carrying out cross-linking polymerization to obtain a modified activated carbon material; the mass ratio of the activated carbon modified with the oxygen-containing functional group to the graphene material containing the functional group is 100: 2-20.
2. The activated carbon material of claim 1, wherein at least a portion of the graphene sheets are adsorbed on the activated carbon particles by chemical bonds.
3. The modified activated carbon material of claim 1, wherein the secondary particles of the modified activated carbon material have a particle size greater than the particle size of the activated carbon particles.
4. The modified activated carbon material of claim 1, wherein the secondary particles of the modified activated carbon material have a particle size of 20 μm or less.
5. The modified activated carbon material of claim 4, wherein the secondary particles of the modified activated carbon material have a particle size of less than 12 μm.
6. The modified activated carbon material of claim 5, wherein the secondary particles of the modified activated carbon material have a particle size of less than 5 μm.
7. The modified activated carbon material of claim 1, wherein the secondary particles of the modified activated carbon material have a particle size of between 3 μm and 7 μm.
8. The modified activated carbon material of claim 7, wherein the secondary particles of the modified activated carbon material have a particle size of between 4 and 6 μm.
9. The modified activated carbon material of claim 1, wherein the modified activated carbon particles have a particle size of 1 μm or less.
10. The modified activated carbon material of claim 9, wherein the modified activated carbon particles have a particle size of 0.5 to 0.8 μm.
11. The modified activated carbon material of claim 1, wherein the modified activated carbon material has a specific surface area of 1000 to 3000m2The modified activated carbon material has a continuously distributed pore structure at 0.7-10 nm, the average pore diameter is 2-10 nm, and the proportion of mesopores is 10-50%.
12. The modified activated carbon material of claim 11, wherein the modified activated carbon material has a specific surface area of 2200 to 3000m2/g。
13. A method for preparing a modified activated carbon material according to any one of claims 1 to 12, comprising the steps of:
(1) mixing activated carbon with an activating agent for activation to obtain activated carbon modified with oxygen-containing functional groups; the activating agent comprises any 1 or combination of at least 2 of nitric acid, sulfuric acid, phosphoric acid, sodium hypochlorite and hydrogen peroxide; the activation temperature is 35-85 ℃, and the activation time is 0.5-10 h;
(2) mixing the activated carbon modified with the oxygen-containing functional group with the graphene material containing the functional group, adding a cross-linking agent, and carrying out cross-linking polymerization to obtain a modified activated carbon material; the mass ratio of the activated carbon modified with the oxygen-containing functional group to the graphene material containing the functional group is 100: 2-20.
14. The method according to claim 13, wherein step (2) is followed by step (3): the reduction operation is carried out after the crosslinking polymerization.
15. The method according to claim 13, wherein the particle size of the activated carbon in the step (1) is 10 μm or less.
16. The method according to claim 15, wherein the particle size of the activated carbon in the step (1) is 5 μm or less.
17. The method according to claim 16, wherein the particle size of the activated carbon in the step (1) is 3 μm or less.
18. The method according to claim 13, wherein the particle size of the activated carbon in the step (1) is 3 to 7 μm.
19. The method according to claim 18, wherein the activated carbon of the step (1) has a particle size of 4 to 6 μm.
20. The method according to claim 13, wherein the particle size of the activated carbon in the step (1) is 1 μm or less.
21. The method according to claim 20, wherein the particle size of the activated carbon in the step (1) is 0.5 to 0.8 μm.
22. The method of claim 13, wherein the carbon source for preparing activated carbon comprises any 1 or a combination of at least 2 of nutshell, bamboo, coal, petroleum products, agricultural by-products, and polymers.
23. The method of claim 22, wherein the carbon source for preparing activated carbon comprises any 1 or a combination of at least 2 of coconut shell, petroleum coke, phenolic resin, and moso bamboo.
24. The method of claim 22, wherein the nut shell comprises any 1 or a combination of at least 2 of coconut shells, olive shells, walnut shells, and apricot shells.
25. The method of claim 22, wherein the bamboo material comprises phyllostachys pubescens and/or phyllostachys pubescens.
26. The method of claim 22, wherein the coal comprises any 1 or a combination of at least 2 of peat, lignite, bituminous coal.
27. The method of claim 22, wherein the petroleum-based product comprises any 1 or a combination of at least 2 of asphalt, petroleum coke.
28. The method of claim 22, wherein the agricultural by-product comprises any 1 or a combination of at least 2 of rice hulls, straw, furfural residue.
29. The method of claim 22, wherein the polymer comprises any 1 or a combination of at least 2 of phenolic resin and furan resin.
30. The method of claim 22, wherein the graphene material comprises any 1 or a combination of at least 2 of graphene, graphene oxide, and graphene derivatives.
31. The method according to claim 30, wherein the graphene comprises graphite prepared by a exfoliation method, graphene oxide is prepared by reduction, graphite is prepared by oxidation-reduction, carbon-containing gas is prepared by a CVD method, and biomass is used as a raw material and is prepared by a high-temperature pyrolysis method.
32. The preparation method of claim 13, wherein the mass ratio of the activated carbon modified with the oxygen-containing functional group in the step (2) to the graphene material containing the functional group is 100: 2-8.
33. The preparation method of claim 32, wherein the mass ratio of the activated carbon modified with the oxygen-containing functional group in the step (2) to the graphene material containing the functional group is 100: 2-5.
34. The preparation method of claim 13, wherein the addition amount of the activating agent is 0.1 to 10 times the weight of the activated carbon.
35. The method of claim 13, wherein the cross-linking agent of step (2) comprises any 1 or a combination of at least 2 of ethylene glycol, polyethylene glycol, propylene glycol, polypropyleneglycol, butylene glycol, cyclopentanediol, cyclohexanediol, ethanolamine, ethylenediamine, aliphatic diamine, melamine, dithiol, mercaptoethanol.
36. The preparation method according to claim 13, wherein the addition amount of the cross-linking agent is 0.1 to 10 times the weight of the graphene material.
37. The method according to claim 13, wherein the pH of the cross-linking polymerization is 4 to 8, the temperature of the cross-linking polymerization is 30 to 90 ℃, and the time is 0.5 to 12 hours.
38. The method of claim 13, wherein the reducing comprises chemical reduction, charring reduction, or microwave reduction.
39. The method of claim 38, wherein the chemical process is contacting the modified activated carbon material with a chemical reducing agent comprising any 1 or a combination of at least 2 of hydrazine hydrate, L-ascorbic acid, sodium borohydride, sodium citrate, and sodium hydroxide.
40. The preparation method according to claim 38, wherein the carbonization-reduction method comprises carbonization in a non-oxidizing atmosphere, wherein the carbonization temperature is 500-1000 ℃ and the carbonization time is 0.5-6 h.
41. The method according to claim 38, wherein the microwave reduction is carried out in a non-oxidizing atmosphere, the microwave power is 5.1-0.7 kW, the microwave time is 1-15 min, and the microwave reduction temperature is 800-1200 ℃.
42. The method according to claim 14, wherein the modified activated carbon material is reduced in the step (3), washed until the conductivity is constant, and dried.
43. The method of claim 42, wherein the drying temperature is 40 to 120 ℃.
44. Use of the modified activated carbon material according to any one of claims 1 to 12, wherein the modified activated carbon material is used in the fields of supercapacitors, water treatment, seawater desalination and water desalination.
45. The use of claim 44, wherein the modified activated carbon material is used as an adsorbent material for water treatment, desalination of sea water, desalination of water.
46. The use according to claim 44, wherein the reduced modified activated carbon material is used as an electrode material for a supercapacitor.
47. A supercapacitor, wherein an electrode material of the supercapacitor comprises the modified activated carbon material according to any one of claims 1 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418281.6A CN108996501B (en) | 2017-06-06 | 2017-06-06 | Modified activated carbon material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710418281.6A CN108996501B (en) | 2017-06-06 | 2017-06-06 | Modified activated carbon material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108996501A CN108996501A (en) | 2018-12-14 |
| CN108996501B true CN108996501B (en) | 2021-02-26 |
Family
ID=64572819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710418281.6A Active CN108996501B (en) | 2017-06-06 | 2017-06-06 | Modified activated carbon material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108996501B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160512B (en) * | 2018-10-22 | 2021-11-30 | 中国林业科学研究院林产化学工业研究所 | Biomass gasification residue formed activated carbon and preparation method thereof |
| CN109573960A (en) * | 2018-12-17 | 2019-04-05 | 江苏诺斯特拉环保科技有限公司 | Waste Sulfuric Acid recycles method of disposal |
| CN111659346A (en) * | 2019-03-08 | 2020-09-15 | 天津大学 | Haze collecting, absorbing and converting system based on primary battery principle |
| CN109894078A (en) * | 2019-03-13 | 2019-06-18 | 湖北第二师范学院 | A kind of cocoanut active charcoal adsorbent material and manufacture craft based on water process |
| CN110371974B (en) * | 2019-08-21 | 2021-03-05 | 福建省鑫森炭业股份有限公司 | Active carbon for removing hydrogen sulfide and preparation method thereof |
| CN110510610A (en) * | 2019-09-20 | 2019-11-29 | 安徽大学 | A kind of method of hydrogen peroxide and the combined modified active carbon electrode material of phosphoric acid |
| CN111203182A (en) * | 2020-01-17 | 2020-05-29 | 中国科学院宁波材料技术与工程研究所 | Modified activated carbon for adsorbing phenol and preparation method and application thereof |
| CN112125691A (en) * | 2020-09-19 | 2020-12-25 | 山东天久高科新材料有限公司 | Preparation method of modified carbon-carbon composite material |
| CN113368815B (en) * | 2021-05-06 | 2023-07-18 | 广东工业大学 | Modification auxiliary agent, modified activated carbon slurry and preparation method and application of modified auxiliary agent and modified activated carbon slurry |
| EP4108647A1 (en) * | 2021-06-21 | 2022-12-28 | eeplasma GmbH | Method for the preparation of core particles which can be coated with liquid fertilisers |
| CN113651323A (en) * | 2021-08-04 | 2021-11-16 | 桂东县湘浙活性炭有限公司 | Production process of wood activated carbon |
| CN114632493A (en) * | 2022-03-18 | 2022-06-17 | 华侨大学 | Graphene composite modified activated carbon material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253658A (en) * | 2013-05-13 | 2013-08-21 | 常州第六元素材料科技股份有限公司 | Graphene with high volumetric specific capacitance and preparation method thereof |
| CN103523776A (en) * | 2013-09-30 | 2014-01-22 | 山东聊城鲁西化工集团有限责任公司 | Preparation method for activated carbon for super capacitor |
| CN103723721A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of graphene-modified activated carbon for supercapacitor |
| CN105923632A (en) * | 2016-04-18 | 2016-09-07 | 方大炭素新材料科技股份有限公司 | Preparation method of active carbon for super capacitor based on graphene composite modification |
| WO2016171239A1 (en) * | 2015-04-22 | 2016-10-27 | ステラケミファ株式会社 | Cross-linked structure of carbon material and method for producing same |
| CN106082210A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound active fruit shell carbon and preparation method thereof, application |
-
2017
- 2017-06-06 CN CN201710418281.6A patent/CN108996501B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253658A (en) * | 2013-05-13 | 2013-08-21 | 常州第六元素材料科技股份有限公司 | Graphene with high volumetric specific capacitance and preparation method thereof |
| CN103523776A (en) * | 2013-09-30 | 2014-01-22 | 山东聊城鲁西化工集团有限责任公司 | Preparation method for activated carbon for super capacitor |
| CN103723721A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of graphene-modified activated carbon for supercapacitor |
| WO2016171239A1 (en) * | 2015-04-22 | 2016-10-27 | ステラケミファ株式会社 | Cross-linked structure of carbon material and method for producing same |
| CN105923632A (en) * | 2016-04-18 | 2016-09-07 | 方大炭素新材料科技股份有限公司 | Preparation method of active carbon for super capacitor based on graphene composite modification |
| CN106082210A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound active fruit shell carbon and preparation method thereof, application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108996501A (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108996501B (en) | Modified activated carbon material, preparation method and application | |
| Fan et al. | Ti3C2-MXene composite films functionalized with polypyrrole and ionic liquid-based microemulsion particles for supercapacitor applications | |
| Bandyopadhyay et al. | Facile synthesis of novel sulfonated polyaniline functionalized graphene using m-aminobenzene sulfonic acid for asymmetric supercapacitor application | |
| Shi et al. | Nickel–cobalt bimetallic tungstate decorated 3D hierarchical porous carbon derived from lignin for high-performance supercapacitor applications | |
| Han et al. | Preparation and electrochemical performances of graphene/polypyrrole nanocomposite with anthraquinone-graphene oxide as active oxidant | |
| Senthilkumar et al. | Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte | |
| Su et al. | Nitrogen-containing microporous carbon nanospheres with improved capacitive properties | |
| An et al. | Non-covalently functionalizing a graphene framework by anthraquinone for high-rate electrochemical energy storage | |
| Alabadi et al. | Nitrogen-doped activated carbons derived from a co-polymer for high supercapacitor performance | |
| Peng et al. | A novel fabrication of nitrogen-containing carbon nanospheres with high rate capability as electrode materials for supercapacitors | |
| Zhu et al. | High‐performance supercapacitor electrode materials from chitosan via hydrothermal carbonization and potassium hydroxide activation | |
| WO2011053668A1 (en) | High surface area and low structure carbon blacks for energy storage applications | |
| Zhong et al. | Supermolecule-regulated synthesis strategy of general biomass-derived highly nitrogen-doped carbons toward potassium-ion hybrid capacitors with enhanced performances | |
| Wang et al. | Boosting Supercapacitor Performance of Graphene by Coupling with Nitrogen‐Doped Hollow Carbon Frameworks | |
| Zhang et al. | Robust production of ultrahigh surface area carbon sheets for energy storage | |
| Zhang et al. | Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application | |
| Zhang et al. | Interconnected nanoporous carbon structure delivering enhanced mass transport and conductivity toward exceptional performance in supercapacitor | |
| Wang et al. | Highly hydrophilic carbon dots' decoration on NiCo2O4 nanowires for greatly increased electric conductivity, supercapacitance, and energy density | |
| Delaporte et al. | Multi-carbonyl molecules immobilized on high surface area carbon by diazonium chemistry for energy storage applications | |
| Bhakare et al. | Eco-friendly biowaste-derived graphitic carbon as black pigment for conductive paint | |
| Soni et al. | Synthesis of Ultrathin PEDOT on Carbon Nanotubes and Shear Thinning Xanthan Gum‐H2SO4 Gel Electrolyte for Supercapacitors | |
| Geng et al. | Covalent‐induced heterostructure of covalent‐organic frameworks and MXene as advanced electrodes with motivated pseudocapacitance performance | |
| Liang et al. | Ultra-thin highly-wrinkled graphene-like nanosheets for supercapacitor electrodes via 4-nitrocatechol and solvent-induced self-assembly | |
| Huang et al. | B/N co-doped porous carbon nanosheets with high B/N doping contents and excellent supercapacitor performance | |
| Poochai et al. | Facial electrosynthesis of hydrophilic poly (aniline-co-p-phenylenediamine) nanostructures for high performance supercapacitor electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |