CN106865546A - A kind of mesoporous micro-pore carbon material and its preparation method and application - Google Patents
A kind of mesoporous micro-pore carbon material and its preparation method and application Download PDFInfo
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- CN106865546A CN106865546A CN201710058532.4A CN201710058532A CN106865546A CN 106865546 A CN106865546 A CN 106865546A CN 201710058532 A CN201710058532 A CN 201710058532A CN 106865546 A CN106865546 A CN 106865546A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 119
- 239000011148 porous material Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- -1 polysiloxane Polymers 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000005554 pickling Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004375 physisorption Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 235000019241 carbon black Nutrition 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000007794 irritation Effects 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
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting 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
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- C01P2006/14—Pore volume
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
This application discloses a kind of mesoporous micro-pore carbon material and its preparation method and application.The mesoporous micro-pore carbon material of the application, pore diameter range is 0.3 20 nanometers, and porosity is 50 90%, and the mesoporous volume ratio with micropore is 2:More than 1, specific surface area is 1500 3200m2/g.The mesoporous micro-pore carbon material of the application, is a kind of brand-new carbon material while having superhigh specific surface area and mesoporous ratio high.The preparation method of the application, mesoporous micro-pore carbon material is prepared by silicon oxide material, the creative highly basic using melting dissolves to the silica in silicon oxide material, and carbon is activated, avoid using chlorine or hydrofluoric acid, produced without toxic gas or liquid, production equipment is more simple, more economical, safe and environment-friendly；In addition, the method is not required to form mesoporous with template, for the preparation of mesoporous micro-pore carbon material provides a kind of new approach.
Description
Technical field
The application is related to porous carbon materials field, more particularly to a kind of mesoporous micro-pore carbon material and preparation method thereof and should
With.
Background technology
Mesoporous material refers to the porous material that average pore size is 2-50 nanometers, and poromerics refers to that average pore size is received less than 2
The porous material of rice.Because poromerics has the aperture smaller than mesoporous material, bigger specific surface area can be provided；Cause
This, the micro-pore carbon material with high-specific surface area is widely used in adsorbing, is catalyzed, ultracapacitor etc. needs bigger serface
Occasion.Traditional high-specific surface area carbon material to be mainly and form activated carbon by carrying out to carbon material activation and prepare, for hole
Footpath is unable to precise control.Additionally, traditional activated carbon is based on micropore, because aperture is too small, many target molecules or ion
Spread in hole in being even unable to access aperture slowly very much, significant portion of specific surface is practically without being utilized, and material property can not
Give full play to.For example when micro-pore carbon material is used as the electrode material of ultracapacitor, organic bath tetrafluoro boric acid
The diameter of the solvation anion/cation in triethylammonium tetrakis is respectively 1.30 nanometers and 1.16 nanometers, less than the size micropore due to
Electrolyte ion can not be accommodated and electric double layer capacitance can not be formed, the surface area inside micropore is invalid.
In order to improve the application performance of high-specific surface area carbon material, the mesoporous micropore carbon materials with classification aperture can be prepared
Material.Mesoporous to be interconnected with micropore in mesoporous micro-pore carbon material, because mesoporous aperture is more than micropore, molecule and ion exist
Diffusion velocity in mesoporous is very fast, and mesoporous is that molecule or ion provide express passway into micropore inner surface.Mesoporous microporous carbon
The high-specific surface area of material can be fully used, therefore performance is better than simple micro-pore carbon material.But, traditional activation
Technique can only prepare simple micro-pore carbon material.In recent years by template introduced in carbon material it is mesoporous turn into one research heat
Point.But, the mould material in template is expendable consumed product, and material cost is high, and complex technical process, it is difficult to realize producing
Industry.Recently, high-specific surface area carbon material is prepared as a kind of new method by carbide material.Ratio high is prepared by carbide
The advantage of surface area carbon material is that be able to can make be accommodated in hole at most by the chemical Composition Control aperture of carbide
Molecule or ion so that improve catalysis, absorption or capacitive property.In all of carbide, carborundum or oxidation of coal
Silicon is lower-cost.Oxycarbide ceramic can be pyrolyzed by polysiloxanes.Silicon oxide material is microcosmic
On to be carbon mutually intert the nano composite structure for being formed with amorphous silicon oxide；Amorphous in removal silicon oxide material
Silicon, you can obtain the carbon material with nano-pore.The main method that the carbide of report prepares microporous carbon recently is at high temperature
Logical chlorine is corroded, or is corroded using hydrofluoric acid at room temperature.Both approaches have certain danger, chlorine
It is a kind of toxic gas with intense irritation smell, a large amount of suctions can be fatal；Hydrofluoric acid has aggressive, and human body connects
Touching a small amount of hydrofluoric acid can belong to severe poisonous chemicals with fatal.And environmentally harmful accessory substance, such as four chlorinations can be formed
Silicon, has corrosivity and irritating hydrogen chloride etc. with vapor generation in atmosphere.Simultaneously as introducing mesoporous, carbon materials
The specific surface area of material can be reduced substantially, there is presently no a kind of i.e. specific surface area with superelevation, while there is mesoporous ratio higher again
The carbon material of example.
The content of the invention
The purpose of the application is to provide a kind of new mesoporous micro-pore carbon material, and its preparation method and application.
The application employs following technical scheme：
The one side of the application discloses a kind of mesoporous micro-pore carbon material, and the pore diameter range of the mesoporous micro-pore carbon material is
0.3-20 nanometers, porosity is 50-90%, and the mesoporous volume ratio with micropore is 2:More than 1, specific surface area is 1500-3200m2/
g。
The mesoporous micro-pore carbon material of the application can have more than 3000m simultaneously2The specific surface area of/g, also, it is mesoporous and
The volume ratio of micropore is more than 2:1, pore volume is more than 2cm3/g.The mesoporous micro-pore carbon material of the application both has high-ratio surface
Product, and with the mesoporous of controlled quantity so that mesoporous micro-pore carbon material has more excellent performance and wider purposes.This Shen
Ultracapacitor please be used it in a kind of purposes of mesoporous micro-pore carbon material so that capacitive property surmounts and uses import activity
The capacitor of charcoal YP50.
It should be noted that existing high specific area carbon is based on traditional activated carbon.Activated carbon is a kind of simple
Poromerics.Although the specific surface area highest of activated carbon can reach 3000m2/ g, but mainly based on long and narrow micropore.
It is very slow that molecule or ion spread in these long and narrow micropores；Even some big molecules and ion can not enter too small
Micropore.The dynamic performance for showing as material in the application is poor, while effective surface area is less than actual surface area.Although now
It has been reported that have many high-specific surface area carbon materials for having and being classified mesoporous-microcellular structure, but these materials are introducing mesoporous
Afterwards, specific surface area is all decreased obviously to 2000m2/ g is lower, while mesoporous ratio is not high, pore volume is also little.And
The mesoporous micro-pore carbon material of the application can not only obtain 3000m2The specific surface area of/more than g, and mesoporous ratio can be very
It is high.
The method that the another aspect of the application discloses the mesoporous micro-pore carbon material of the application, including at high temperature using molten
The highly basic for melting dissolves to the silica in silicon oxide material, while being activated to carbon, then using pickling, is situated between
Hole micro-pore carbon material.
It should be noted that existing method is using chlorine or hydrofluoric acid corrosion oxidation silicon, porous carbon materials are formed；But
It is that this method has certain danger, and can cause environmental pollution.Therefore, what the application was creative uses melting
Highly basic dissolves to silica, while carbon is activated, to obtain Jie of classification mesoporous-micro-pore carbon material, i.e. the application
Hole micro-pore carbon material.It is appreciated that the application it is critical only that using melting highly basic, and under hot conditions use also for
Ensure that highly basic is in molten condition, therefore, corresponding melt temperature is used according to different highly basic, do not do specific limit herein
It is fixed.First purpose of highly basic is fused silica, and second purpose is that carbon is activated, wherein, carrying out activation to carbon is
Refer to, the carbon in silicon oxide carbide is turned into activated carbon.Highly basic in general chemistry definition may be used to the application, does not do have herein
Body is limited.The purpose of pickling processes is to wash remaining highly basic off, and highly basic and silica product, therefore, as long as energy
The reaction of enough and alkali, and the inorganic acid for being difficult to remain may be used to the application, be not specifically limited herein.But, in order to reach
More preferable effect, in the preferred scheme of the application, the hot conditions of type and highly basic the dissolving silica to highly basic are carried out
It is particularly limited to.
Preferably, in the preparation method of the mesoporous micro-pore carbon material of the application, silicon oxide material is by phenyl polysiloxane
High temperature pyrolysis are carried out in protective atmosphere to form.
It should be noted that phenyl polysiloxane is application propose it is a kind of new for preparing mesoporous micro-pore carbon material
Presoma；It is used as presoma by using the phenyl polysiloxane with different silicon/carbon ratio example, mesoporous micropore can be regulated and controled
The pore-size distribution of carbon material.
Also, it should be noted that the preparation method of the application, can be directly using the silicon oxide carbide timber-used for preparing in system
Standby mesoporous micro-pore carbon material, it would however also be possible to employ the raw material of silicon oxide material, i.e. phenyl polysiloxane, prepares mesoporous micropore
Carbon material.Specifically, carrying out high temperature pyrolysis to phenyl polysiloxane in being included in protective atmosphere, silicon oxide material is obtained,
Then phenyl polysiloxane high temperature pyrolysis product is processed using the highly basic of melting at high temperature, then using pickling, i.e.,
Obtain mesoporous micro-pore carbon material.
Preferably, phenyl polysiloxane is polyphenyl methyl siloxane or the silica column containing phenyl hydroxyl.
It should be noted that wherein polyphenyl methyl siloxane, is using poly- second in a kind of implementation of the application
Alkenyl phenyl siloxane and polymethyl hydrogen siloxane react and obtain.
Preferably, the temperature of high temperature pyrolysis is carried out to phenyl polysiloxane for 1000-1200 DEG C, protective atmosphere is nitrogen
Or argon gas.
Preferably, the high-temperature temperature that highly basic is dissolved to the silica in silicon oxide material is 700-900 DEG C.
Preferably, highly basic is NaOH or potassium hydroxide.
Preferably, the acid that pickling processes are used is inorganic acid.
It is furthermore preferred that inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
Preferably, oven for drying is used after being additionally included in pickling processes.
Preferably, the temperature for using oven for drying is 80-120 DEG C, and drying time is 3-5 hours.
It should be noted that the purpose of oven for drying is removal liquid residue, therefore, as long as temperature is to mesoporous micropore carbon materials
Material is not damaged in itself, and the time dried, also only needing to can effectively to remove liquid residue can.
Preferably, the present processes are specifically included, by silicon oxide carbide and excessive highly basic mixed grinding, then in inertia
Heating melts highly basic under atmosphere, the silica in silicon oxide material is dissolved using the highly basic of melting, while to carbon
Activated, pickling is then carried out again, obtained the mesoporous micro-pore carbon material of the application.
It should be noted that the preferred scheme of the application, in advance mixes silicon oxide material with the strong basic solid of excess
Grinding, then unification is heated again, melts highly basic, and so operation can be safer；It is of course also possible to highly basic is melted in advance
Melt, then silicon oxide material is dispersed in the highly basic of melting and is reacted.
It should be noted that the preparation method of existing activated carbon, is extremely difficult to carry out precise control to aperture, can not
Introduce mesoporous；And using the preparation method of the application on the premise of template is not used, 3 nanometers of average pore size can be prepared,
Pore volume 2.4cm3/ g, the volume ratio of mesoporous/micropore is 3.6:1, BET specific surface area 3200m2The mesoporous micro-pore carbon material of/g.
The another aspect of the application discloses the mesoporous micro-pore carbon material of the application in sorbing material, catalysis material or super
Application in level capacitor.
It is appreciated that the mesoporous micro-pore carbon material of the application, both with specific surface area higher, and with larger proportion
It is mesoporous, therefore, can be completely applied in sorbing material, catalysis material or ultracapacitor, its high-specific surface area can keep
Good imbibition and liquid-keeping property, and its mesoporous ratio high can have more preferable percent of pass.
The another aspect of the application discloses a kind of ultracapacitor of the mesoporous micro-pore carbon material of use the application, mesoporous
Water system specific capacitance of the micro-pore carbon material in ultracapacitor is higher than 300F/g, and organic system specific capacitance is higher than 150F/g, and power is close
Degree energy density in 30kW/kg reaches 20Wh/kg, and power density energy density in 372W/kg reaches 40Wh/kg.
It should be noted that because the mesoporous micro-pore carbon material of the application has a superhigh specific surface area, and electric capacity and material
Specific surface area positive correlation, it is achieved thereby that specific capacitance high.Because the mesoporous micro-pore carbon material of the application has big hole again
Volume and mesoporous ratio, ion spread quickly in the material, accelerate the charge-discharge velocity of electric capacity.Sum it up, the application
Mesoporous micro-pore carbon material is the energy density that increased ultracapacitor, and the power density of ultracapacitor is increased again.
The beneficial effect of the application is：
The mesoporous micro-pore carbon material of the application, while having superhigh specific surface area and mesoporous ratio high, this is one kind
The preceding new carbon without appearance.The preparation method of the mesoporous micro-pore carbon material of the application, is prepared by silicon oxide material and divided
Mesoporous-the micro-pore carbon material of level, the creative highly basic using melting is dissolved and right to the silica in silicon oxide material
Carbon is activated, it is to avoid the use of chlorine or hydrofluoric acid；Due to that need not prevent the leakage of toxic gas or liquid, production from setting
It is standby more simple so that whole procedure is more economical, safer, more environmentally friendly；In addition, the method need not be formed using template
It is mesoporous, provide a kind of new environmentally friendly, safe, economic preparation on the way to prepare mesoporous micro-pore carbon material by silicon oxide material
Footpath.Also, the ultracapacitor of the mesoporous micro-pore carbon material using the application, with energy density and power density higher.
Brief description of the drawings
Fig. 1 be in the embodiment of the present application one 1200 degrees Celsius of pyrolysis silicon oxide carbides of double-component silica gel at 800 degrees Celsius with hydrogen
The nitrogen physisorption isotherms of mesoporous micro-pore carbon material prepared by oxidation sodium corrosion；
Fig. 2 be in the embodiment of the present application one 1200 degrees Celsius of pyrolysis silicon oxide carbides of double-component silica gel at 800 degrees Celsius with hydrogen
The graph of pore diameter distribution of mesoporous micro-pore carbon material prepared by oxidation sodium corrosion；
Fig. 3 be in the embodiment of the present application two 1200 degrees Celsius of pyrolysis silicon oxide carbides of single component silica gel at 800 degrees Celsius with hydrogen
The nitrogen physisorption isotherms of mesoporous micro-pore carbon material prepared by oxidation sodium corrosion；
Fig. 4 be in the embodiment of the present application two 1200 degrees Celsius of pyrolysis silicon oxide carbides of single component silica gel at 800 degrees Celsius with hydrogen
The graph of pore diameter distribution of mesoporous micro-pore carbon material prepared by oxidation sodium corrosion；
Fig. 5 is the water system electric capacity high rate performance figure of the intermediary hole micro-pore carbon material charcoal of the embodiment of the present application three；
Fig. 6 is the organic system electric capacity pair of the intermediary hole micro-pore carbon material of the embodiment of the present application four and Japanese import YP50 activated carbons
Than figure；
Fig. 7 is the energy density and work(of the intermediary hole micro-pore carbon material of the embodiment of the present application four and Japanese import YP50 activated carbons
Rate density comparison diagram.
Specific embodiment
The preparation method of the porous carbon materials of existing more advanced controllable bore diameter be exactly by silicon oxide material, it is molten
Silica therein is solved, porous carbon materials are formed；But, existing method is all to carry out corrosion oxidation using logical chlorine under high temperature
Silicon, or hydrofluoric acid corrosion oxidation silicon is utilized at room temperature.These methods what is common is that, first, there is potential safety hazard；The
Two, the accessory substance of corrosion has pollution to environment.In this regard, present inventor is by substantial amounts of practical studies, creative carries
Go out, highly basic is melted, silica is dissolved using the highly basic of melting, while being activated to carbon, then using pickling, go
Except highly basic and the product of highly basic and silica；Hydrofluoric acid or chlorine, safety and environmental protection need not be used；And without using template.
The mesoporous micro-pore carbon material obtained by the preparation method of the application, compared with mesoporous poromerics prepared by existing method, this Shen
Preparation specific surface area 1500-3200m that please be controllable2The mesoporous micro-pore carbon material of/g, that is to say, that the application's is mesoporous micro-
Hole carbon material, its specific surface area can reach 3000m2/ more than g, with superhigh specific surface area, at the same time, Jie of the application
Hole micro-pore carbon material also has mesoporous ratio very high, and the mesoporous volume ratio with micropore is 2:More than 1, a kind of realization of the application
It is mesoporous to reach 4.4 with micropore volume ratio in mode:1.
It should be noted that the specific surface area (abbreviation S) of material is inversely proportional with aperture (abbreviation d), therefore, existing carbon materials
Material specific surface area when introducing mesoporous can be reduced substantially；And pass through research and find, specific surface area and pore volume (abbreviation V) into
Direct ratio, i.e. S=4V/d, the mesoporous micro-pore carbon material of the application while introducing mesoporous, improve pore volume, therefore this Shen
Please obtain the mesoporous micro-pore carbon material of mesoporous ratio high and high-specific surface area.
The application is described in further detail below by specific embodiment.Following examples only are entered to advance to the application
The explanation of one step, should not be construed as the limitation to the application.
Embodiment one
This example forms silicon oxide carbide using double-component silicon in 1200 degree of pyrolysis, then recycles the highly basic of melting to dissolve carbon
Silica in silica, forms the mesoporous micro-pore carbon material of this example.The highly basic of this example uses NaOH, the acid of pickling processes
Using hydrochloric acid.Specific preparation method is as follows：
15 microlitres of platinum catalyst is dissolved in 20 grams of polyvinyl phenyl siloxane, 1 gram of poly- methyl hydrogen is then added
Siloxanes, stirs 5 minutes, and hybrid reaction is obtained solid silicone, i.e. polyphenyl methyl siloxane, and solid silicone is shredded, in pipe
1200 DEG C of prepared silicon oxide carbide powder are fired to the heating rate of 5 DEG C/min in formula stove nitrogen atmosphere.
The silicon oxide carbide and NaOH in mass ratio 1 that will be prepared:4 are ground, it is necessary to illustrate, NaOH
Purpose is dissolving silica and carbon is activated.This example specific in mass ratio 1:4 additions, that is, add and be four times in silicon oxide carbide
NaOH；800 DEG C are fired in tube furnace nitrogen atmosphere after well mixed to be reacted, 3 hours are incubated, after reaction terminates
Reactant is transferred in the hydrochloric acid of 2mol/L and is sufficiently stirred for washing, then filtered, cyclic washing filter 23 time places product
In vacuum drying oven, dried 4 hours at 100 DEG C, obtain the mesoporous micro-pore carbon material of this example.
The specific surface area of the mesoporous micro-pore carbon material prepared to this example using nitrogen physisorption method, porosity and aperture
Tested.
Test result as shown in figure 1, result shows, mesoporous micro-pore carbon material prepared by this example, its BET specific surface area is
3120m2/ g, pore volume is 2.4cm3/ g, mesoporous and micro pore volume ratio is 3.6：1, average pore size is 3 nanometers.Prepared by this example
The pore-size distribution of mesoporous micro-pore carbon material is as shown in Figure 2, it is seen that the mesoporous micro-pore carbon material of this example, and its aperture is mainly distributed on 2-
10 nanometers of small macropore ranges in interval, distributed area is narrow, and aperture is more uniform.
Embodiment two
This example forms silicon oxide carbide using one pack system silica gel in 1200 degree of pyrolysis, then recycles the highly basic of melting to dissolve carbon
Silica in silica, forms mesoporous micro-pore carbon material.The highly basic of this example uses the acid of NaOH, pickling processes to use salt
Acid.Specific preparation method is as follows：
By 20 grams of silica column powder containing phenyl hydroxyl, with the heating rate of 5 DEG C/min in tube furnace argon atmosphere
It is fired to 1200 DEG C of prepared silicon oxide carbide powder.
Silicon oxide carbide and the NaOH in mass ratio 1 of excess prepared by this example：4 are ground, be well mixed after
800 DEG C are fired in tube furnace argon atmosphere to be reacted, 3 hours are incubated, and reactant is transferred to 2mol/L by reaction after terminating
Hydrochloric acid in be sufficiently stirred for washing, be positioned over product in vacuum drying oven and dried at 100 DEG C by filtering, cyclic washing filter 23 time
4 hours, obtain the mesoporous micro-pore carbon material of this example.
The specific surface area of the mesoporous micro-pore carbon material prepared to this example using nitrogen physisorption method, porosity and aperture
Tested.
As shown in figure 3, result shows, classification prepared by this example is mesoporous-micro-pore carbon material, its BET specific surface for test result
Product is 1549m2/ g, pore volume is 1.8cm3/ g, mesoporous and micropore ratio is 4.4：1, average pore size is 4.5 nanometers.It is prepared by this example
Mesoporous micro-pore carbon material pore-size distribution it is as shown in Figure 4, it is seen that the mesoporous micro-pore carbon material of this example, its aperture is mainly distributed on
2-50 nanometers of interval macropore range, distributed area is relatively wide, and pore-size distribution relatively disperses.Although mesoporous microporous carbon prepared by this example
Material, its specific surface area is relatively low, but has remained in that mesoporous and micropore ratio very high, while in the preparation method of this example,
The single component silica gel for being used, cost is lower, and preparation method is simpler.
Embodiment three
The mesoporous micro-pore carbon material that will be prepared in embodiment one, conductive agent Super P carbon blacks, mass fraction be 60% it is viscous
Knot agent polytetrafluoroethylene (PTFE) (abbreviation PTFE) is 80 in mass ratio：10：10 ratio is weighed, and is transferred in mortar, is added appropriate
Ethanol carries out being fully ground mixing, with the volatilization of ethanol, slurry gradually retrogradation, then stir compacting repeatedly, make slurry final into
The slurry-mud of semi-solid state.Roll squeezer suitable distance, roll-in slurry-mud are adjusted so that it becomes 100-150 microns of thick, superficial compaction
Smooth electrode film, electrode film is finally struck out the circular pole piece of a diameter of 10mm with sheet-punching machine, is positioned over vacuum drying chamber
In 80 DEG C dry 24h.Length about 50mm, width about 15mm are cut, thickness is the nickel foam of 1mm as the afflux of working electrode
Body.Circular pole piece is positioned in foamed nickel current collector, and it is with roll squeezer that it is integral with collector roll-in, it is made work electricity
Pole.Working electrode, mercury oxide reference electrode, platinum are placed in there-necked flask to electrode, 6M KOH solutions is added as electrolyte,
Capacity measurement is carried out in 0-1V voltage ranges, test result is as shown in Figure 5.
Result shows that, when current density is 0.5A/g, specific capacitance has reached 320F/g；Even if current density reaches
During 50A/g, specific capacitance still has 170F/g.It can be seen that, capacitor being prepared using the mesoporous micro-pore carbon material of embodiment one, can obtain
Specific capacitance very high, even if can also keep high specific capacitance under high current, illustrates that the high rate performance of electric capacity is superior.Electric capacity be by
Zwitterion form electric double layer in conductor material surface and produces because electrostatic interaction is adsorbed.It is common, conductor material surface
Product is bigger, and the electric double layer capacitance that can be produced is higher.Mesoporous micro-pore carbon material prepared by embodiment one has specific surface very high
Product, therefore, it is possible to produce specific capacitance very high.In addition, it is different from traditional micro-pore carbon material, it is mesoporous prepared by embodiment one
Micro-pore carbon material has a high proportion of mesoporous.The size of zwitterion is respectively less than mesopore size, is not in due to ion size
The phenomenon of micropore is cannot be introduced into very much greatly, and migration resistance of the ion in mesoporous is small, and material can be rapidly achieved under high current
Material surface forms electric double layer, shows as superior high rate performance.It can be seen that, the mesoporous micro-pore carbon material ratio high prepared by embodiment one
The characteristics of surface area and mesoporous ratio high, be the key of the capacitive property for realizing superior.
Example IV
The energy density of ultracapacitor is directly proportional to specific capacitance, to square being directly proportional for voltage range.Improve energy
Density, should as much as possible increase voltage range.Therefore, practical ultracapacitor is broader organic molten usually using voltage range
Liquid is used as electrolyte.This example demonstrates mesoporous micro-pore carbon material answering in the ultracapacitor with organic solution as electrolyte
With.
The mesoporous micro-pore carbon material that will be prepared in embodiment one, conductive agent Super P carbon blacks, mass fraction be 60% it is viscous
Knot agent polytetrafluoroethylene (PTFE) (abbreviation PTFE) is 80 in mass ratio：10：10 ratio is weighed, and is transferred in mortar, is added appropriate
Ethanol carries out being fully ground mixing, with the volatilization of ethanol, slurry gradually retrogradation, then stir compacting repeatedly, make slurry final into
The slurry-mud of semi-solid state.Roll squeezer suitable distance, roll-in slurry-mud are adjusted so that it becomes 100-150 microns of thick, superficial compaction
Smooth electrode film, electrode film is finally struck out the circular pole piece of a diameter of 10mm with sheet-punching machine, is positioned over vacuum drying chamber
In 80 DEG C dry 24h.Using CR2032 button cells component assemble ultracapacitor, two panels pole piece respectively as both positive and negative polarity, in
Between separated by polyethylene battery barrier film, electrolyte for 1M concentration ttraethylammonium tetrafluoroborate/acetonitrile solution.Comprise the concrete steps that：Will
Smooth pole piece is placed in the center of negative electrode casing, and 40 μ L electrolyte are added dropwise, and is put into polyethylene battery barrier film, then 40 μ L electrolysis are added dropwise
Liquid, makes barrier film complete wetting, then another pole piece is positioned on barrier film, and adjustment good position is located at center, then by pad and
Shell fragment is successively placed on pole piece top, to strengthen the smooth derivation of inside battery contact tight type and electric current, finally covers anode cover,
Sealed with packaging machine, complete the assembling of ultracapacitor.It is electric into button using the nickel foam of adhesive electrodes material as electrode assembling
Pond.Capacity measurement is carried out in 0-2.5V voltage ranges.
Test result is as shown in A curves in Fig. 6.Result shows that, when current density is 0.5A/g, specific capacitance reaches
162F/g.Even if current density has reached 50A/g, specific capacitance still has 100F/g.It can be seen that, using the mesoporous micropore of embodiment one
Carbon material prepares capacitor, can obtain specific capacitance very high, even if can also keep high specific capacitance under high current, illustrates electricity
The high rate performance of appearance is superior.Zwitterion size of the zwitterion of ttraethylammonium tetrafluoroborate than KOH is big, so in unit plane
The number of ions that can be adsorbed in product reduces, and shows as specific capacitance and is less than example in the specific capacitance with the KOH aqueous solution as electrolyte.
Even so, because the voltage range in ttraethylammonium tetrafluoroborate/acetonitrile is 0-2.5V, far above the 0-1V of the KOH aqueous solution, institute
It is higher with energy density.Because the size of ttraethylammonium tetrafluoroborate zwitterion is larger, aperture is more likely cannot be introduced into too small
Micropore, or migration velocity in hole is very slow.It is different from traditional micro-pore carbon material, it is mesoporous micro- prepared by embodiment one
Hole carbon material has a high proportion of mesoporous.The size of ttraethylammonium tetrafluoroborate zwitterion be less than mesopore size, be not in by
Cannot be introduced into very much the phenomenon of micropore greatly in ion size, and migration resistance of the ion in mesoporous is small, can be with high current
It is rapidly achieved material surface and forms electric double layer, shows as superior high rate performance.It can be seen that, the mesoporous micropore prepared by embodiment one
The characteristics of carbon material high-specific surface area and mesoporous ratio high, be the key of the capacitive property for realizing superior.
At the same time, this example is entered as a comparison using the mesoporous micro-pore carbon material of the YP50 alternative embodiments one of Japanese import
Row experiment.Wherein, the YP50 of Japanese import is a kind of high grade activated carbon for being widely used in ultracapacitor in industrial quarters, YP50
Specific surface area be 1750m2/ g, pore volume is 1.3cm3/ g, mesoporous and micropore ratio is 0.8：1.It can be seen that YP50 is still with micropore
Main, mesoporous is secondary.
Japanese import YP50 activated carbons are assembled into ultracapacitor with same method using CR2032 button cells component, is used
Same method testing capacitor.Test result is as shown in B curves in Fig. 6.Result shows, when current density is 0.5A/g, than electricity
Hold and there was only 97F/g.More obviously, when current density has reached 50A/g, specific capacitance drops to only 10F/g.Performance is much low
In mesoporous micro-pore carbon material prepared by the embodiment one of curve A.Because the specific surface area of YP50 is more mesoporous than prepared by embodiment one
Micro-pore carbon material specific surface area is small, so specific capacitance is also accordingly reduced.Further, since the chi of ttraethylammonium tetrafluoroborate zwitterion
It is very little larger, and YP50 causes ion to cannot be introduced into too small micropore based on less than 2 nanometers of micropore, or migrated in hole
Very slow, electric capacity declines clearly under being presented as high current, and high rate performance is poor.Contrasted from this, prepared by embodiment one
Mesoporous micro-pore carbon material there is high-specific surface area and mesoporous ratio high to embody the electricity for being much better than the carbon material based on micropore
Capacitive energy.
According to the test result of Fig. 6, the two corresponding power density-energy density figure of materials (Ragone Plot) are drawn,
As shown in Figure 7.It can be seen that, mesoporous micro-pore carbon material prepared by embodiment one reaches the maximum energy-density of 30Wh/kg, or
The maximum power density of 40kW/kg.And Japanese import YP50 activated carbons only reach the maximum energy-density of 20Wh/kg, or
The maximum power density of 8kW/kg.The maximum energy-density of mesoporous micro-pore carbon material prepared by embodiment one is higher than YP50 by 50%,
Maximum power density is 5 times of YP50.Also, mesoporous micro-pore carbon material prepared by embodiment one is in the power density of 30kW/kg
Under, remain able to reach the energy density of 20Wh/kg；Under the power density of 372W/kg, it may be possible to reach 40Wh/kg's
Energy density；This is that YP50 activated carbons cannot be reached.
On the basis of above example, acid of the application further to highly basic and pickling processes is tested.As a result
It has been shown that, in addition to NaOH, potassium hydroxide can also reach the effect that identical dissolves silica；Also, NaOH
All it is relatively common, cheap highly basic with potassium hydroxide；For the temperature of high temperature, primarily to make highly basic melt or
Melting is kept, therefore, temperature all may be used at 700-900 DEG C.Pickling aspect, in addition to hydrochloric acid, sulfuric acid and nitric acid can also be used
In the application, it is also possible to the highly basic and highly basic of effective removal residual and the product of silica.Dried as after pickling
Temperature and drying time, according to the difference of the mesoporous micro-pore carbon material being finally made, 80-120 DEG C of temperature, time 3-5 hours
Substantially mesoporous micro-pore carbon material can effectively be dried.
Above content is to combine the further description that specific embodiment is made to the application, it is impossible to assert this Shen
Specific implementation please is confined to these explanations.For the application person of an ordinary skill in the technical field, do not taking off
On the premise of conceiving from the application, some simple deduction or replace can also be made, should all be considered as belonging to the protection of the application
Scope.
Claims (10)
1. a kind of mesoporous micro-pore carbon material, it is characterised in that：The pore diameter range of the mesoporous micro-pore carbon material is 0.3-20 nanometers,
Porosity is 50-90%, and the mesoporous volume ratio with micropore is 2:More than 1, specific surface area is 1500-3200m2/g。
2. a kind of method of the mesoporous micro-pore carbon material prepared described in claim 1, it is characterised in that：Including using at high temperature
The highly basic of melting dissolves to the silica in silicon oxide material, while being activated to carbon, then using pickling, obtains
The mesoporous micro-pore carbon material.
3. method according to claim 2, it is characterised in that：The silicon oxide material is by phenyl polysiloxane in protection
High temperature pyrolysis are carried out in property atmosphere to form.
4. method according to claim 3, it is characterised in that：The phenyl polysiloxane be polyphenyl methyl siloxane or
Silica column containing phenyl hydroxyl.
5. the method for mesoporous micro-pore carbon material according to claim 3, it is characterised in that：The temperature of the high temperature pyrolysis is
1000-1200 DEG C, the protective atmosphere is nitrogen or argon gas.
6. method according to claim 2, it is characterised in that：The temperature of the high temperature is 700-900 DEG C.
7. method according to claim 2, it is characterised in that：The highly basic is NaOH or potassium hydroxide, the acid
It is hydrochloric acid, sulfuric acid or nitric acid to wash the acid for using.
8. the method according to claim any one of 2-7, it is characterised in that：Methods described is specifically included, by silicon oxide carbide
With excessive highly basic mixed grinding, then heating melts highly basic under an inert atmosphere, using the highly basic of melting to silicon oxide carbide
Silica in material is dissolved, while being activated to carbon, pickling is then carried out again, obtains the mesoporous micropore carbon materials
Material.
9. mesoporous micro-pore carbon material according to claim 1 is in sorbing material, catalysis material or ultracapacitor
Using.
10. a kind of ultracapacitor of the mesoporous micro-pore carbon material described in use claim 1, the mesoporous micro-pore carbon material exists
Water system specific capacitance in ultracapacitor is higher than 300F/g, and organic system specific capacitance is higher than 150F/g, and power density is in 30kW/kg
Energy density reaches 20Wh/kg, and power density energy density in 372W/kg reaches 40Wh/kg.
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| CN107628597A (en) * | 2017-10-16 | 2018-01-26 | 河南师范大学 | One kind utilizes SiO2Cladding process prepares the method with micropore and meso-hole structure biomass carbon material |
| CN108345766A (en) * | 2018-01-11 | 2018-07-31 | 大连理工大学 | A method of porous material microcellular structure is characterized based on imbibition purging process |
| KR20220096326A (en) * | 2020-12-31 | 2022-07-07 | 한국세라믹기술원 | Porous carbaon and manufacturing method of the same |
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| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
| CN105271176A (en) * | 2015-11-17 | 2016-01-27 | 南通绿业中试技术研究院有限公司 | Mesoporous carbon material and manufacturing method thereof |
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| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
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| CN107628597A (en) * | 2017-10-16 | 2018-01-26 | 河南师范大学 | One kind utilizes SiO2Cladding process prepares the method with micropore and meso-hole structure biomass carbon material |
| CN108345766A (en) * | 2018-01-11 | 2018-07-31 | 大连理工大学 | A method of porous material microcellular structure is characterized based on imbibition purging process |
| CN108345766B (en) * | 2018-01-11 | 2021-05-18 | 大连理工大学 | Method for characterizing porous material microporous structure based on liquid absorption and gas dispelling processes |
| KR20220096326A (en) * | 2020-12-31 | 2022-07-07 | 한국세라믹기술원 | Porous carbaon and manufacturing method of the same |
| KR102581150B1 (en) | 2020-12-31 | 2023-09-20 | 한국세라믹기술원 | Manufacturing method of porous carbaon |
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