CN108751192A - A kind of activated carbon for super capacitors and its preparation method and application - Google Patents
A kind of activated carbon for super capacitors and its preparation method and application Download PDFInfo
- Publication number
- CN108751192A CN108751192A CN201810885112.8A CN201810885112A CN108751192A CN 108751192 A CN108751192 A CN 108751192A CN 201810885112 A CN201810885112 A CN 201810885112A CN 108751192 A CN108751192 A CN 108751192A
- Authority
- CN
- China
- Prior art keywords
- activation
- gas activation
- activated carbon
- preparation
- activator
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 239000003990 capacitor Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 230000004913 activation Effects 0.000 claims abstract description 142
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000012190 activator Substances 0.000 claims abstract description 47
- 239000005539 carbonized material Substances 0.000 claims abstract description 40
- 239000007772 electrode material Substances 0.000 claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 56
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000002028 Biomass Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 235000013399 edible fruits Nutrition 0.000 claims description 9
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011122 softwood Substances 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims 2
- 235000021314 Palmitic acid Nutrition 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 15
- -1 1- ethyl-3-methylimidazoles tetrafluoroborate Chemical class 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000003610 charcoal Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 126
- 239000007789 gas Substances 0.000 description 82
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 238000000034 method Methods 0.000 description 27
- 229960004424 carbon dioxide Drugs 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 238000012360 testing method Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 238000005554 pickling Methods 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000005486 organic electrolyte Substances 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 230000003749 cleanliness Effects 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to absorbent charcoal material preparing technical fields, and in particular to a kind of activated carbon for super capacitors and its preparation method and application.The present invention carries out gas activation twice using different activators to carbonized material, carbonized material is activated into the activated carbon with mesoporous and microcellular structure, the place of large area is provided for the storage of charge, the channel quickly conveyed is provided for electrolyte ion again, is conducive to the specific capacitance for improving ultracapacitor.Embodiment the result shows that, when gained activated carbon of the invention is used for electrode material for super capacitor, using 1- ethyl-3-methylimidazoles tetrafluoroborate/acetonitrile solution of 2mol/L as electrolyte, when it is 5mV/s to sweep speed, the specific capacitance of ultracapacitor reaches 110~186F/g.
Description
Technical field
The invention belongs to absorbent charcoal material preparing technical fields, and in particular to a kind of activated carbon for super capacitors and its system
Preparation Method and application.
Background technology
In recent years, ultracapacitor is as a kind of novel energy storage device, and because having, charge/discharge rates are fast, have extended cycle life
And the advantages that safety non-pollution, has been favored by people, and is widely used in the necks such as electric vehicle, electronic equipment and intelligent grid
Domain.Ultracapacitor is mainly made of electrode material, electrolyte and diaphragm, wherein electrode material is to determine super capacitor electrode
The key factor of chemical energy storage performance.Currently, Carbon Materials are widely used one kind in electrode material for super capacitor, often
Carbon Materials include activated carbon, carbon nanotube, graphene, carbon aerogels, Carbon Materials made from Carbon fibe and metal carbides.
In the above-mentioned Carbon Materials referred to, the advantage that activated carbon is simple with preparation method, of low cost becomes most probable and realizes industry
The electrode material for super capacitor of metaplasia production.
The activated carbon for being currently used as electrode material for super capacitor is mainly prepared by alkali metal compound activation method,
The method can prepare the activated carbon of high-specific surface area so that ultracapacitor can possess higher specific capacitance and energy is close
Degree；But alkali metal compound activation method has very strong corrosivity to equipment, with high costs, environmental pollution is serious, and exists
Serious Safety production questions, therefore alkali metal compound activation method is not suitable for producing on a large scale；Vapor activation or
The activating process of carbon dioxide activation method is simple, and cost is relatively low and cleanliness without any pollution, is suitble to large-scale industrialization application, but living
The activated carbon specific capacitance that change obtains is relatively low, and the mark of industrial practically necessary electrode material for super capacitor is not achieved
It is accurate.It is 1mV/s sweeping speed such as the organic system ultracapacitor activated carbon that Chan Kim et al. are prepared with steam activation bamboo
When, maximum specific capacitance only 60F/g.The organic system ultracapacitor that G.Lota et al. is prepared with steam activation polymer with nitrogen
Activated carbon, when it is 1mV/s to sweep speed, maximum specific capacitance only 114F/g.
Invention content
The purpose of the present invention is to provide a kind of activated carbon for super capacitors and its preparation method and application, and the present invention carries
The preparation method of confession can be obtained there are micropore and mesopore activated carbon, and specific capacitance height is suitable as ultracapacitor, especially
Electrode material as organic bath ultracapacitor uses, and method cleanliness without any pollution provided by the invention, at low cost, fits
Close large-scale production.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of preparation method of activated carbon for super capacitors, includes the following steps：
(1) carbonized material is subjected to first gas activation, obtains primary activation material；The temperature of first gas activation is
800~950 DEG C；The time of the first gas activation is 30~120min；
(2) the primary activation material for obtaining the step (1) carries out second gas activation, and two level activation is obtained after cooling
Material；The temperature of the second gas activation is 800~1000 DEG C, and the time of the second gas activation is 30~180min；
(3) the two level activated material that the step (2) obtains is ground, washed and dried successively, obtain super capacitor
Device activated carbon；
The first gas activation activator includes independently vapor, two with activator with the second gas activation
One or more of carbonoxide, air and ammonia, and the activator difference of gas activation twice.
Preferably, when the first gas activation with activator is vapor, the second gas activation is with activator
Carbon dioxide.
Preferably, when the first gas activation with activator is carbon dioxide, the second gas activation activator
For vapor.
Preferably, when the first gas activation is the mixture of air and water with activator, the second gas activation
It is carbon dioxide with activator.
Preferably, the preparation method of step (1) carbonized material includes：Biomass material and/or coal raw material are subjected to charcoal
Change, obtains carbonized material；The temperature of the charing is 700~1000 DEG C, and the time of the charing is 60~180min.
Preferably, the temperature of the charing is reached by heating, rate≤15 DEG C/min of the heating.
Preferably, the type of the biomass material include one kind in softwood, broadleaf, bamboo wood and hard fruit shell or
It is several.
Preferably, the hard fruit shell includes one or more of cocoanut shell, walnut shell and palm shell.
The present invention also provides the activated carbon for super capacitors that preparation method described in above-mentioned technical proposal is prepared, institutes
The grain size for stating activated carbon for super capacitors is 600~1000 mesh, and micropore volume is 0.40~0.80cm3/ g, total hole volume are
0.85~1.60cm3/g；Specific surface area is 1200~2500m2/g。
The present invention separately provides activated carbon for super capacitors described in above-mentioned technical proposal as electrode of super capacitor material
The application of material.
The preparation method of activated carbon for super capacitors provided by the invention, includes the following steps：By carbonized material 800~
At 950 DEG C, first gas activation is carried out, 30~120min is activated, obtains primary activation material；Gained primary activation material is existed again
Second gas activation is carried out at 800~1000 DEG C, is cooled down after activating 30~180min, is obtained two level activated material；Finally by gained
Two level activated material is ground, washs and dries successively, obtains activated carbon for super capacitors；The activator packet of gas activation
Include one or more of vapor, carbon dioxide, air and ammonia, and the activator difference of gas activation twice.The present invention
Gas activation twice is carried out to carbonized material using different activators, keeps the pore structure of gained activated carbon more flourishing, aperture
Distribution is more reasonable, realizes that micropore and mesoporous coexist, and the place of large area is not only provided for the storage of charge, but also is composition electrolysis
The ion of matter provides the channel quickly transmitted, and is conducive to the specific capacitance for improving ultracapacitor.Embodiment the result shows that, this
Invention gained activated carbon be used for electrode material for super capacitor when, with the 1- ethyl-3-methylimidazoles tetrafluoroborate of 2mol/L/
Acetonitrile solution is electrolyte, and when it is 5mV/s to sweep speed, the specific capacitance of ultracapacitor reaches 110~186F/g.
Description of the drawings
Fig. 1 is nitrogen adsorption-desorption isotherm of 1 gained activated carbon of embodiment；
Fig. 2 is the graph of pore diameter distribution of 1 gained activated carbon of embodiment；
Fig. 3 is cyclic voltammetry curve of the 1 gained activated carbon electrodes of embodiment under different scanning rates；
Fig. 4 is constant current charge-discharge curve of the 1 gained activated carbon electrodes of embodiment under different current densities；
Fig. 5 is multiplying power figure of the 1 gained activated carbon electrodes of embodiment in 2mol/L EMIMBF4/AN organic electrolytes；
Fig. 6 is 1 gained activated carbon electrodes of embodiment in 2mol/LEMIMBF4Nyquist exchanges in/AN organic electrolytes
Impedance diagram；
Fig. 7 is 1 gained activated carbon electrodes of embodiment in 2mol/LEMIMBF4Ragone point diagrams in/AN organic electrolytes.
Specific implementation mode
The present invention provides a kind of preparation methods of activated carbon for super capacitors, include the following steps：
(1) carbonized material is subjected to first gas activation, obtains primary activation material；The temperature of first gas activation is
800~950 DEG C；The time of the first gas activation is 30~120min；
(2) the primary activation material for obtaining the step (1) carries out second gas activation, and two level activation is obtained after cooling
Material；The temperature of the second gas activation is 800~1000 DEG C, and the time of the second gas activation is 30~180min；
(3) the two level activated material that the step (2) obtains is ground, washed and dried successively, obtain super capacitor
Device activated carbon；
The first gas activation activator includes independently vapor, two with activator with the second gas activation
One or more of carbonoxide, air and ammonia, and the activator difference of gas activation twice.
Carbonized material is carried out first gas activation by the present invention, obtains primary activation material.The present invention does not have the carbonized material
Particular/special requirement can be commercial product, can also make by oneself to obtain.In the present invention, the carbonized material, which preferably is selected from, is made.
In the present invention, when providing carbonized material using self-control mode, the preparation method of the carbonized material preferably includes：It will
Biomass material and/or coal raw material are carbonized, and carbonized material is obtained；The temperature of the charing is 700~1000 DEG C, the charing
Time be 60~180min.
The present invention preferably carbonizes biomass material and/or coal raw material, obtains carbonized material.In the present invention, described
The material of biomass material preferably includes one or more of softwood, broadleaf, bamboo wood and hard fruit shell, the softwood
Pine material and/or China fir material are preferably included, the pine material preferably includes masson pine；The broadleaf preferably includes poplar material；
The hard fruit shell preferably includes one or more of cocoanut shell, walnut shell and palm shell.The present invention is to biomass original
The specific size of material does not have particular/special requirement, using size well known to those skilled in the art.In the present invention, the biology
When matter raw material is softwood, broadleaf or bamboo wood, the raw material is preferably dimensioned to be the bar of 1cm × 1cm × 15cm；It is described
When biomass material raw material is hard fruit shell, the hard fruit shell is preferably particulate matter；Grain size of the present invention to the particulate matter
There is no particular/special requirement, using well known to those skilled in the art.
In the present invention, before the biomass material charing, processing is preferably dried, to remove in biomass material
Moisture；The mode of the drying is preferably natural air drying.
In the present invention, the temperature of the biomass material charing is preferably 700~1000 DEG C, more preferably 750~950
DEG C, it is further preferably 800~900 DEG C；The time of the charing is preferably 60~180min, more preferably 80~160min；It is described
The time of charing refers to soaking time of biomass material under the conditions of carbonization temperature.In the present invention, the temperature of the charing is excellent
The mode for gating heating reaches, the rate of the heating preferably≤15 DEG C/min, more preferably 1~15 DEG C/min, further preferably
For 2~5 DEG C/min.The present invention does not have particular/special requirement to the specific implementation mode of the heating, ripe using those skilled in the art
The mode known.In the present invention, the charing carries out preferably in retort.
The present invention has no requirement to the source of the coal raw material, using commercial product well known to those skilled in the art
?.
After charing, the present invention preferably carries out micronization processes to the material after charing, to obtain the smaller carbonized material of size.This
Invention does not have particular/special requirement to the size of the carbonized material, using size well known to those skilled in the art.In the present invention
In, the carbonized material is preferably dimensioned to be 1cm × 1cm × 1.5cm bars or grain size as the particulate matter of 8~20 mesh.The present invention
There is no particular/special requirement to the specific implementation mode of the refinement, the carbonized material of above-mentioned size can be obtained.
In the present invention, the temperature of first gas activation is 800~950 DEG C, preferably 820~900 DEG C, more preferably
It is 840~870 DEG C；The time of first gas activation be 30~120min, preferably 45~90min, more preferably 60~
85min.In the present invention, the first gas activation required temperature is preferably reached by heating, and the rate of the heating is preferred
≤ 15 DEG C/min, more preferably 2~12 DEG C/min are further preferably 5~10 DEG C/min.Specific implementation of the present invention to the heating
Mode does not have particular/special requirement, using mode well known to those skilled in the art.
In the present invention, during being warming up to first gas activation temperature, nitrogen protection preferably is carried out to carbonized material, with
Ablation can be caused to carbonized material by exempting from oxygen present in system.After being warming up to first gas activation temperature, the present invention is preferably to work
Property charcoal where gas activation agent is passed through in system, carry out first gas activation.In the present invention, the first gas activation
Activator includes one or more of vapor, carbon dioxide, air and ammonia, preferably include vapor, carbon dioxide and
One or more of air.The activator of the first gas activation be specifically as follows vapor, carbon dioxide, air,
The mixture of the mixture of vapor and air, carbon dioxide and air.When the activator is the mixture of several components, institute
It is (1~5) that each component, which is stated in mixture, according to volume ratio：(1~5) is mixed.
In the present invention, the time of the first gas activation is calculated since activator is passed through carbonized material.In this hair
In bright, during the first gas activation, carbonized material is 20%-60% in the volume pack completeness of activation pipe volume, more excellent
It is selected as 30%~45%.In the present invention, the activator preferably flows atmosphere, in order to which the gas that reaction generates is discharged in time
Body product, makes activator be come into full contact with carbonized material.The present invention does not have particular/special requirement to the flowing velocity of the activator.
After obtaining primary activation material, the primary activation material is carried out second gas activation by the present invention, and two are obtained after cooling
Grade activated material.In the present invention, the temperature of the second gas activation is 800~1000 DEG C, preferably 850~980 DEG C, more excellent
It is selected as 875~950 DEG C；The time of the second gas activation is 30~180min, preferably 45~150min, more preferably 60
~120min.
In the present invention, the second gas activation is that second gas activation is passed directly into after first gas activates
What required activator carried out；The soak time of the second gas activation is the activation used by being passed through second gas activation
Start to calculate when agent.In the present invention, the activator of the second gas activation include vapor, carbon dioxide, air and
One or more of ammonia preferably includes one or more of vapor, carbon dioxide and ammonia.The second gas is lived
The activator of change is specifically as follows the mixture of vapor, carbon dioxide, ammonia, vapor and carbon dioxide, carbon dioxide
With the mixture of ammonia, the mixture of vapor and ammonia.When the activator is the mixture of several components, the mixture
Middle each component is (1~5) according to volume ratio：(1~5) is mixed.
In the present invention, the activator of the activator of the first gas activation and the second gas activation is not
Together, to obtain the different pore structure in aperture.
In the present invention, when the first gas activation with activator is vapor, the second gas activation activation
Agent is preferably carbon dioxide；
When the first gas activation with activator is carbon dioxide, the second gas activation is preferably water with activator
Steam；
When the first gas activation is the mixture of air and water with activator, the second gas activation activator
Preferably carbon dioxide.
In the present invention, be warming up to during second gas activation temperature, the rate of the heating preferably≤15 DEG C/min,
More preferably 2~12 DEG C/min is further preferably 5~10 DEG C/min.The present invention is to the specific implementation mode of the heating without spy
It is different to require, using mode well known to those skilled in the art.
In the present invention, the activator of the second gas activation preferably flows atmosphere, so that second gas activates
The gas component discharge activation system generated in the process, and then activator is made to be come into full contact with primary activation material.In the present invention,
In the second gas activation process, activator gas flowing velocity uses range well known to those skilled in the art.Institute
During stating second gas activation, volume pack completeness preferably 20%~50% of the carbonized material in activation tube is more excellent
It is selected as 30%~40%.
The present invention under these conditions carries out carbonized material first gas activation and second gas activation successively, by using
The activator of different chemical composition prepares the different pore structure in aperture, and then it is suitable to obtain that micro-, all kinds of holes of mesoporous match
Two level activated material stores and transmits the condition of offer for charge.
After obtaining two level activated material, the two level activated material is ground, washed and dried by the present invention successively, is surpassed
Grade capacitor activated carbon.The present invention does not have particular/special requirement to the specific implementation mode of the grinding, can obtain this field skill
The size of activated carbon for super capacitors known to art personnel.After grinding, the present invention carries out the material after the grinding
Washing, the ash content after being ground with removal in resulting material.In the present invention, the washing preferably include the pickling that carries out successively and
Deionized water is washed, and adopted spent pickling acid includes hydrochloric acid, sulfuric acid or and acetic acid；The concentration of the spent pickling acid is preferably 0.05~
0.5mol/L, more preferably 0.1~0.2mol/L；The pickling preferably carries out under ultrasound condition；The frequency of the ultrasound is excellent
It is selected as 200~800Hz, more preferably 300~500Hz；The time of the pickling is preferably 2~3h, more preferably 2h.
After pickling, the present invention preferably carries out deionized water washing to the material after the pickling, to remove the acid in material
Component makes the μ S/cm of the conductivity of cleaning solution≤20.The present invention does not have particular/special requirement to the specific implementation mode of the washing, adopts
With mode well known to those skilled in the art.
After washing, the material after the washing is dried in the present invention, obtains activated carbon for super capacitors.In this hair
In bright, the temperature of the drying is preferably 100~120 DEG C, more preferably 110~115 DEG C；The time of the drying is preferably 24
~26h, more preferably 24~25h.The present invention does not have particular/special requirement to the specific implementation mode of the drying, using this field skill
Mode known to art personnel.In embodiments of the present invention, the drying carries out preferably in air dry oven.
The present invention separately provides the activated carbon for super capacitors that preparation method described in above-mentioned technical proposal is prepared, institute
The grain size for stating activated carbon for super capacitors is 600~1000 mesh；Micropore volume is 0.40~0.80cm3/ g, total hole volume are
0.85~1.60cm3/g；Mesoporous is 5~55% with total hole volume ratio；Specific surface area is 1200~2500m2/g；With 2mol/L's
1- ethyl-3-methylimidazoles tetrafluoroborate/acetonitrile solution is that electrolyte utilizes above-mentioned activated carbon system when it is 5mV/s to sweep speed
The specific capacitance of standby ultracapacitor reaches 110~186F/g.
In the present invention, the quality of quality/carbonized material of yield (%)=activated carbon for super capacitors, the super electricity
The yield of container activated carbon is 10.0~45.0%；The conductivity of the activated carbon for super capacitors is 0.2~2.0 Ω
cm。
The present invention also provides activated carbon for super capacitors described in above-mentioned technical proposal as electrode of super capacitor material
The application of material.The present invention does not have particular/special requirement to the application mode of the activated carbon for super capacitors, using art technology
Mode known to personnel.
In embodiments of the present invention, in order to analyze the performance that activated carbon for super capacitors stores electric energy, gained is super
Capacitor is fabricated to electrode with activated carbon, detects the correlated performance of activated carbon electrodes.In the present invention, the activated carbon electrodes
Production method is as follows：
According to activated carbon：Acetylene black：Ptfe emulsion (w%=60%)=8:1:The ratio of 1 (mass ratio) is by three
Person is uniformly mixed the disk that diameter 11mm is made, and wafer presser is made in the nickel foam of same diameter under the pressure of 10MPa
Then it is spare to be dried under vacuum to constant weight at 110 DEG C for electrode slice.
Using the electrode slice group capacitor of above-mentioned preparation, method is as follows：Take two panels electrode slice, centre be put into polypropylene every
Then film is added 1- ethyl-3-methylimidazoles tetrafluoroborate/acetonitrile electrolyte of a few drop 2mol/L, is assembled into double layer capacity
Device.
Using Arbin companies of the U.S. production high accuracy battery monomer test system (BT-G-5V-5A-4) to capacitor into
Row constant current charge-discharge is tested；Life test is tested under the current density of 2A/g using constant current charge-discharge.With
Zennium types electrochemical workstation (German ZHAHER companies) carries out cyclic voltammetry to assembled capacitor and exchange hinders
Anti- test, wherein the frequency range of ac impedance measurement is 10mHz-200KHz, and the AC signal amplitude of application is 5mV.By following
Ring volt-ampere curve can calculate the specific capacitance of activated carbon according to formula (1).
C=4 × ∮ D [I (U) × du]/[Δ u × m × (2s)] (1)
In formula (1), C indicates that quality specific capacitance, D integrate for closed curve, and integral area is obtained by cyclic voltammetry curve
It arrives, I (U) indicates that the relationship of electric current (I) and voltage window (U), du indicate differential potential difference, and u is potential difference, and s is sweep speed, m
For the quality of active constituent activated carbon in capacitor bipolar electrode, unit g.
The energy density of capacitor is calculated by formula (2),
E=1/2 × CU2 (2)
In formula (2), E indicates energy density, unit symbol Wh/kg；C is the mass ratio electricity capacitance of capacitor, unit symbol
Number be F/g；U is voltage window, unit symbol V.
The pore structure of activated carbon is measured using nitrogen adsorption desorption instrument.Before test, each activated carbon deaerates at 300 DEG C
12h.According to nitrogen adsorption isotherm, using the specific surface area of Brunauer-Emmet-Teller (BET) equation calculation activated carbon
(SBET), the nitrogen adsorption capacity for being 0.99 by relative pressure calculates the total pore volume (Vtot) of sample, uses Dubinin-
Micropore volume (the V of Radushkevic equation calculation samplesmic), total pore volume subtracts Micropore volume and obtains mesopore volume (Vmes), in
Kong Kongrong divided by total pore volume just obtain mesopore proportion (Vmes/VT).Pore-size distribution passes through quenched solid density
Functionaltheory (QSDFT) equations are analyzed to obtain.
The resistivity of activated carbon measures the resistivity of activated carbon using semiconductor powder resistivity measurement platform.
In order to further illustrate the present invention, ultracapacitor activity is provided to the present invention with reference to the accompanying drawings and examples
Charcoal and its preparation method and application is described in detail, but cannot they be interpreted as limiting the scope of the present invention.
Embodiment 1
300g pines (1cm × 1cm × 15cm) after drying are placed in retort, are warming up to according to 10 DEG C/min speed
900 DEG C, 120min is carbonized under nitrogen protection, obtains carbonized material；
900 DEG C of carbonized material 15g are weighed, is put into activation furnace and is activated.The temperature programming stage is passed through nitrogen and protects
Gas, heating rate are set as 10 DEG C/min.After actual temperature reaches 850 DEG C in burner hearth, nitrogen is closed, is passed through at this temperature
Steam activation 60min.After steam activation, close vapor, be passed through CO immediately2Gas.Then activation furnace is again with 10
DEG C/rate of min is warming up to 900 DEG C, 120min, CO are activated at 900 DEG C2Flow velocity is 0.2L/min.CO2After activation terminates,
Cut off CO2Gas passage, changes logical nitrogen protection immediately, and activation furnace starts Temperature fall.Until actual temperature is down to room in burner hearth
Wen Shi closes nitrogen, takes out the material after activation, claims its quality, and calculate yield of activation.
2h is washed by the ground 600 mesh sieve of material after activation, then with the hydrochloric ultrasonic wave of 0.1mol/L, uses deionization later
Repeatedly washing to filtrate conductivity is less than 20 μ S/m to water.Then drying for 24 hours, obtains super electricity in 110 DEG C of air dry oven
Container activated carbon.
Embodiment 2~10
Embodiment 2~10 carbonizes the activation method of preparation method for material and carbonized material with embodiment 1, the difference is that twice
The parameter of gas activation is different, is specifically listed in Table 1 below.
Embodiment 11
300g poplars (1cm × 1cm × 15cm) after drying are placed in retort, are warming up to according to 10 DEG C/min speed
900 DEG C, 120min is carbonized under nitrogen protection, obtains carbonized material；
900 DEG C of carbonized material 15g are weighed, is put into activation furnace and is activated.The temperature programming stage is passed through nitrogen and protects
Gas, heating rate are set as 10 DEG C/min.After actual temperature reaches 850 DEG C in burner hearth, nitrogen is closed, is passed through at this temperature
Carbon dioxide activation 120min.After carbon dioxide activation, carbon dioxide is closed, vapor is passed through.Then activation furnace again with
The rate of 10 DEG C/min is warming up to 900 DEG C, 120min is activated at 900 DEG C, the flow velocity of vapor is 0.2L/min.Vapor is lived
After change terminates, change logical nitrogen protection immediately, activation furnace starts Temperature fall.Until actual temperature is down to room temperature in burner hearth,
Nitrogen is closed, the material after activation is taken out, claims its quality, and calculate yield of activation.
2h is washed by the ground 600 mesh sieve of material after activation, then with the hydrochloric ultrasonic wave of 0.1mol/L, uses deionization later
Repeatedly washing to filtrate conductivity is less than 20 μ S/m to water.Then drying for 24 hours, obtains super electricity in 110 DEG C of air dry oven
Container activated carbon.
Embodiment 12
300g pines (1cm × 1cm × 15cm) after drying are placed in retort, are warming up to according to 10 DEG C/min speed
900 DEG C, 120min is carbonized under nitrogen protection, obtains carbonized material；
900 DEG C of carbonized material 15g are weighed, is put into activation furnace and is activated.The temperature programming stage is passed through nitrogen and protects
Gas, heating rate are set as 10 DEG C/min.After actual temperature reaches 800 DEG C in burner hearth, nitrogen is closed, is passed through at this temperature
(by volume, the flow-rate ratio of vapor and air is 1 for air and vapor：1) 30min is activated.After activation, closes water and steam
Gas and air, are passed through carbon dioxide.Then activation furnace is warming up to 900 DEG C with the rate of 10 DEG C/min again, is activated at 900 DEG C
120min, CO2Flow velocity is 0.2L/min.After carbon dioxide activation terminates, change logical nitrogen protection immediately, activation furnace starts nature
Cooling.Until actual temperature is down to room temperature in burner hearth, nitrogen is closed, the material after activation is taken out, claims its quality, and calculate work
Change yield.
2h is washed by the ground 600 mesh sieve of material after activation, then with the hydrochloric ultrasonic wave of 0.1mol/L, uses deionization later
Repeatedly washing to filtrate conductivity is less than 20 μ S/m to water.Then drying for 24 hours, obtains super electricity in 110 DEG C of air dry oven
Container activated carbon.
Embodiment 13
Raw material uses coconut husk, and charring process is same as Example 1, and gas activation technique is shown in Table 1.
Embodiment 14
Raw material uses bamboo wood, and charring process is same as Example 1, and gas activation technique is shown in Table 1.
Embodiment 15
The activation method of preparation method for material and carbonized material is carbonized with embodiment 1, is a difference in that the carbonization temperature of raw material is
800℃.
Comparative example 1
The preparation method is the same as that of Example 1 for carbonized material, and activating process is to activate 1h at 800 DEG C in steam activation.
Comparative example 2
Method for preparation of active carbon is with comparative example 1, the difference is that activating 1h at 850 DEG C.
Comparative example 3
For method for preparation of active carbon with comparative example 1, activating process is carbon dioxide activation, and 1.5h is activated at 900 DEG C.
The performance test results
The specific surface area of 1~3 gained activated carbon of embodiment 1~15 and comparative example, pore structure and conductivity are carried out
Test；Wherein specific surface area, pore structure are obtained using nitrogen adsorption-desorption experimental test；Conductivity utilizes semiconductor powder
Resistivity measurement platform is tested, and test result parameter is shown in Table 2, Fig. 1 and Fig. 2.Fig. 1 is the nitrogen adsorption-of 1 gained activated carbon of embodiment
Desorption isotherm, as shown in Figure 1,1 gained activated carbon of embodiment can adsorb a large amount of nitrogen, and surface activity carbon has larger ratio
Surface area；Fig. 2 is the graph of pore diameter distribution of 1 gained activated carbon of embodiment, and activated carbon obtained by the present embodiment has higher as shown in Figure 2
Mesoporous of the aperture of ratio in 2~5nm, it may have flourishing micropore provides good channel and storage space for electrolyte.
2~15 test result of embodiment is similar to Example 1, and design parameter is listed in Table 2 below.
1~3 activating process parameter of 1 embodiment 1~15 of table and comparative example
The physical function parameter table of 1~3 gained activated carbon of 2 embodiment 1~15 of table and comparative example
In table 2：SBETFor specific surface area；VTFor total hole volume；VmicFor micropore volume；Vmes/VT：Middle pore volume and total pore volume
Long-pending ratio；ρ is conductivity.By 2 test result of table it is found that two steps gas activation provided by the invention is steamed relative to single water
For vapour activation method or carbon dioxide activation method, specific surface area, total hole volume, micropore volume, the middle pore volume of gained activated carbon
Proportion and conductivity are obviously improved, and pore structure is reasonable, are suitable for electrode material for super capacitor use.
Embodiment 1~15 and 1~3 gained activated carbon of comparative example are prepared into ultracapacitor, preparation method is as follows：According to
Activated carbon：Acetylene black：Ptfe emulsion (w%=60%)=8:1:Three is uniformly mixed by the ratio of 1 (mass ratio), system
At the disk of diameter 11mm, wafer presser is made to electrode slice under the pressure of 10MPa in the nickel foam of same diameter, is then existed
It is spare that drying to constant weight in 110 DEG C of air dry oven.When group capacitor, electrode slice similar in two tablet qualities, centre is taken to put
Enter polypropylene diaphragm, 1- ethyl-3-methylimidazoles tetrafluoroborate/acetonitrile electrolyte of a few drop 2mol/L is then added
(EMIMBF4/ AN), it is assembled into double layer capacitor, two electrode systems is used in combination to carry out electrochemical property test.Test the electrode obtained material
The chemical property of material, test result are shown in Table 3 and Fig. 3~7.
Fig. 3 is the cyclic voltammetry curve under different scanning rates using the electrode material of the activated carbon preparation of embodiment 1,
From the figure 3, it may be seen that the cyclic voltammetry curve of the present embodiment the electrode obtained material has preferable class rectangle shape, show that it has typical case
Double layer characteristic；And rectangularity is still preferable under big sweep speed, shows that its high rate performance is preferable.2~15 gained of embodiment
The test result of electrode material is close with embodiment 1, and it is preferable to show that 2~15 gained activated carbon of embodiment can prepare high rate performance
Electrode material for super capacitor.
Fig. 4 is constant current charge-discharge curve of the 1 the electrode obtained material of embodiment under different current densities, as shown in Figure 4
The constant current charge-discharge curve of the electrode material shows symmetrical isosceles triangle shape, shows the electrode material in charge and discharge
Have good invertibity, coulombic efficiency higher in the process.The electrode material test result of embodiment 2~15 and 1 phase of embodiment
Closely, show the good reversibility of 2~15 the electrode obtained material of embodiment, coulombic efficiency is high, can be used for ultracapacitor.
Fig. 5 is 1 the electrode obtained material of embodiment in 2mol/L EMIMBF4Multiplying power figure in/AN organic electrolytes, by Fig. 5
Known to when sweep speed increases to 100mV/s, the specific capacitance of electrode material still has a 138F/g, conservation rate 74.2%, times
Rate function admirable.The test result of 2~15 electrode material of embodiment is shown in Table 3.
Fig. 6 is 1 the electrode obtained material of embodiment in 2mol/LEMIMBF4Nyquist exchange resistances in/AN organic electrolytes
Anti- figure and partial enlarged view, the as shown in Figure 6 internal resistance of electrode material are conducive to carrying for high rate performance in 2 Ω hereinafter, internal resistance is smaller
It is high.The test result of 2~15 electrode material of embodiment is shown in Table 3.
Fig. 7 is 1 the electrode obtained material of embodiment in 2mol/L EMIMBF4Ragone point diagrams in/AN organic electrolytes,
The maximum energy-density of the present embodiment the electrode obtained material can reach 40.4Wh/kg as shown in Figure 7, and energy density is higher.Implement
The test result of 2~15 electrode material of example is shown in Table 3.
Quality specific capacitance, internal resistance and the energy density test result of comparative example 1~3 are shown in Table 3.
The electrochemical property test knot for the electrode material that table 3 is prepared using embodiment 1~15 and 1~3 activated carbon of comparative example
Fruit
By 3 test result of table it is found that embodiment 1~15 is for comparative example 1~3, the electrode material of activated carbon preparation
Material still has higher quality specific capacitance under higher sweep speed；And the internal resistance of electrode material is smaller, current density compared with
Height is suitable for electrode material for super capacitor use.
As seen from the above embodiment, two steps gas activation provided by the invention can utilize the work of different chemical constituents
The pore structure of agent activated micropore and mesoporous in carbonized material, improves the specific surface area of activated carbon, is the storage of electronics
With transmission offer condition；Using gained activated carbon as electrode material in use, electrode material has excellent quality specific capacitance
And high rate performance, meet requirement of the ultracapacitor to electrode material chemical property.
The present invention carries out admixture activation using gas, and activation process not etching apparatus, cleanliness without any pollution, cost is relatively low, and
Gained activated carbon specific surface area is higher, higher than the specific surface area of activated carbon prepared by conventional physical activation method；Gained of the invention is living
Property charcoal micropore, mesoporous coexist, and not only provide the place of large area for the storage of charge, but for charge transmission provide it is advantageous
Channel；The temperature and time that method provided by the invention can be activated by regulating and controlling each activated gas, to the hole of activated carbon
Structure and specific surface area are regulated and controled；The present invention is derived from a wealth of sources using conventional wood as raw material, renewable, and environmental-friendly.It utilizes
Activated carbon produced by the present invention prepares electrode material, and the chemical property of electrode material reaches activated carbon obtained by chemical activation method
Chemical property is horizontal.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiment according to the present embodiment under the premise of without creativeness, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of preparation method of activated carbon for super capacitors, includes the following steps：
(1) carbonized material is subjected to first gas activation, obtains primary activation material；The temperature of first gas activation is 800~
950℃；The time of the first gas activation is 30~120min；
(2) the primary activation material for obtaining the step (1) carries out second gas activation, and two level activated material is obtained after cooling；Institute
The temperature for stating second gas activation is 800~1000 DEG C, and the time of the second gas activation is 30~180min；
(3) the two level activated material that the step (2) obtains is ground, washed and dried successively, obtain ultracapacitor use
Activated carbon；
The first gas activation activator includes independently vapor, titanium dioxide with activator with the second gas activation
One or more of carbon, air and ammonia, and the activator difference of gas activation twice.
2. preparation method as described in claim 1, which is characterized in that the first gas activation is vapor with activator
When, the second gas activation is carbon dioxide with activator.
3. preparation method as described in claim 1, which is characterized in that the first gas activation is carbon dioxide with activator
When, the second gas activation is vapor with activator.
4. preparation method as described in claim 1, which is characterized in that the first gas activation is air and water with activator
Mixture when, the second gas activation is carbon dioxide with activator.
5. preparation method as described in claim 1, which is characterized in that the preparation method of step (1) carbonized material includes：It will
Biomass material and/or coal raw material are carbonized, and carbonized material is obtained；The temperature of the charing is 700~1000 DEG C, the charing
Time be 60~180min.
6. preparation method as claimed in claim 5, which is characterized in that the temperature of the charing is reached by heating, the liter
Rate≤15 DEG C/min of temperature.
7. preparation method as claimed in claim 5, which is characterized in that the type of the biomass material includes softwood, wealthy
One or more of Ye Cai, bamboo wood and hard fruit shell.
8. preparation method as claimed in claim 7, which is characterized in that the hard fruit shell includes cocoanut shell, walnut shell and palm fibre
One or more of palmitic acid shell.
9. the activated carbon for super capacitors that any one of claim 1~8 preparation method is prepared, the super capacitor
The grain size of device activated carbon is 600~1000 mesh, and micropore volume is 0.40~0.80cm3/ g, total hole volume be 0.85~
1.60cm3/g；Specific surface area is 1200~2500m2/g。
10. application of the activated carbon for super capacitors described in claim 9 as electrode material for super capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810885112.8A CN108751192A (en) | 2018-08-06 | 2018-08-06 | A kind of activated carbon for super capacitors and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810885112.8A CN108751192A (en) | 2018-08-06 | 2018-08-06 | A kind of activated carbon for super capacitors and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108751192A true CN108751192A (en) | 2018-11-06 |
Family
ID=63968921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810885112.8A Pending CN108751192A (en) | 2018-08-06 | 2018-08-06 | A kind of activated carbon for super capacitors and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108751192A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502584A (en) * | 2018-12-22 | 2019-03-22 | 滑县大潮林物产有限责任公司 | A kind of super capacitor carbon preparation method |
| CN109592680A (en) * | 2019-01-25 | 2019-04-09 | 浙江大学 | A kind of super capacitor active carbon and three one-step physical process for preparing activated |
| CN109850892A (en) * | 2019-01-25 | 2019-06-07 | 浙江大学 | A kind of activation industrialized process for preparing twice of super capacitor high conductivity cocoanut active charcoal |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113372737A (en) * | 2021-07-22 | 2021-09-10 | 四川轻化工大学 | Preparation method of waste tire thermal cracking carbon black electrode material for super capacitor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071685A (en) * | 2007-05-29 | 2007-11-14 | 王国华 | Method for preparing high mesoporous content active carbon electrode material for ultra capacitor |
| CN104628001A (en) * | 2013-11-09 | 2015-05-20 | 山东泰然新能源有限公司 | Preparation method of active coke |
| CN105366675A (en) * | 2015-11-25 | 2016-03-02 | 上海杉杉科技有限公司 | Developed-mesopore active carbon for super capacitor electrode and preparation method thereof |
| CN106145110A (en) * | 2016-07-05 | 2016-11-23 | 中国矿业大学 | A kind of activated carbon two step process for preparing activated and the application in ultracapacitor thereof |
| CN106219546A (en) * | 2016-08-09 | 2016-12-14 | 中山市天美能源科技有限公司 | A kind of bagasse active carbon and preparation method thereof |
| CN107875815A (en) * | 2017-12-19 | 2018-04-06 | 山东佳星环保科技有限公司 | A kind of waste gas adsorption treatment method caused by oil plant |
-
2018
- 2018-08-06 CN CN201810885112.8A patent/CN108751192A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071685A (en) * | 2007-05-29 | 2007-11-14 | 王国华 | Method for preparing high mesoporous content active carbon electrode material for ultra capacitor |
| CN104628001A (en) * | 2013-11-09 | 2015-05-20 | 山东泰然新能源有限公司 | Preparation method of active coke |
| CN105366675A (en) * | 2015-11-25 | 2016-03-02 | 上海杉杉科技有限公司 | Developed-mesopore active carbon for super capacitor electrode and preparation method thereof |
| CN106145110A (en) * | 2016-07-05 | 2016-11-23 | 中国矿业大学 | A kind of activated carbon two step process for preparing activated and the application in ultracapacitor thereof |
| CN106219546A (en) * | 2016-08-09 | 2016-12-14 | 中山市天美能源科技有限公司 | A kind of bagasse active carbon and preparation method thereof |
| CN107875815A (en) * | 2017-12-19 | 2018-04-06 | 山东佳星环保科技有限公司 | A kind of waste gas adsorption treatment method caused by oil plant |
Non-Patent Citations (5)
| Title |
|---|
| 刘玉荣: "《碳材料在超级电容器中的应用》", 31 January 2013 * |
| 耿新等: "二次活化对椰壳基活性炭电化学性能的影响", 《沈阳农业大学学报》 * |
| 陈昆柏等: "《农业固体废物处理与处置》", 30 November 2016 * |
| 陈梁等: "木质素制备活性炭的工艺及其吸附性能研究", 《江汉大学学报（自然科学版）》 * |
| 陈莉晶等: "二次水蒸气活化制备离子液体超级电容器活性炭的研究", 《林产化学与工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502584A (en) * | 2018-12-22 | 2019-03-22 | 滑县大潮林物产有限责任公司 | A kind of super capacitor carbon preparation method |
| CN109592680A (en) * | 2019-01-25 | 2019-04-09 | 浙江大学 | A kind of super capacitor active carbon and three one-step physical process for preparing activated |
| CN109850892A (en) * | 2019-01-25 | 2019-06-07 | 浙江大学 | A kind of activation industrialized process for preparing twice of super capacitor high conductivity cocoanut active charcoal |
| CN112216518A (en) * | 2020-09-15 | 2021-01-12 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113372737A (en) * | 2021-07-22 | 2021-09-10 | 四川轻化工大学 | Preparation method of waste tire thermal cracking carbon black electrode material for super capacitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108751192A (en) | A kind of activated carbon for super capacitors and its preparation method and application | |
| Wei et al. | Large scale production of biomass-derived nitrogen-doped porous carbon materials for supercapacitors | |
| Jia et al. | Nitrogen-doped microporous carbon derived from a biomass waste-metasequoia cone for electrochemical capacitors | |
| Guo et al. | NiCo 2 O 4 nanosheets grown on interconnected honeycomb-like porous biomass carbon for high performance asymmetric supercapacitors | |
| CN104201001B (en) | Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof | |
| Zhao et al. | High performance N-doped porous activated carbon based on chicken feather for supercapacitors and CO 2 capture | |
| Xu et al. | Nanoporous activated carbon derived from rice husk for high performance supercapacitor | |
| CN106115652B (en) | A kind of B and/or P, N codope perilla leaf porous carbon and preparation method thereof | |
| Guo et al. | N-Doped hierarchical porous carbon prepared by simultaneous-activation of KOH and NH 3 for high performance supercapacitors | |
| CN107522200B (en) | Preparation method and application of active biomass carbon material | |
| WO2018188422A1 (en) | Garlic skin-based activated carbon electrode material for use with supercapacitor and preparation method | |
| WO2007088163A1 (en) | Carbonized biopolymers | |
| Sun et al. | Soybean-waste-derived activated porous carbons for electrochemical-double-layer supercapacitors: effects of processing parameters | |
| CN105439143B (en) | A kind of classifying porous activated carbon and preparation method for ultracapacitor | |
| CN106744803A (en) | A kind of method and porous carbon for preparing porous carbon | |
| CN106910638A (en) | A kind of is carbon material and its preparation method and application of template based on Zr MOFs composites | |
| Pang et al. | “Water-in-salt” electrolyte enhanced high voltage aqueous supercapacitor with carbon electrodes derived from biomass waste-ground grain hulls | |
| CN105118688A (en) | Preparation and application of bacterial cellulose/active carbon fiber/graphene film material | |
| CN109422263A (en) | A kind of fibrination mesoporous activated carbon and the preparation method and application thereof | |
| CN105914048A (en) | Porous carbon-graphene-metal oxide composite material and preparation method and application thereof | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN108439402A (en) | A kind of ultracapacitor ginger stalk matrix activated carbon and preparation method thereof | |
| CN108557819A (en) | Garlic base waste prepares the methods and applications of porous carbon material | |
| Lobato-Peralta et al. | Sponge-like nanoporous activated carbon from corn husk as a sustainable and highly stable supercapacitor electrode for energy storage | |
| CN107689303A (en) | Electrode for capacitors based on nitrogen sulphur codope porous carbon microsphere composite and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181106 |