CN105502391A - Preparation method of special active carbon for water-system super capacitors - Google Patents
Preparation method of special active carbon for water-system super capacitors Download PDFInfo
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- CN105502391A CN105502391A CN201511020373.6A CN201511020373A CN105502391A CN 105502391 A CN105502391 A CN 105502391A CN 201511020373 A CN201511020373 A CN 201511020373A CN 105502391 A CN105502391 A CN 105502391A
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- bamboo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 33
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 21
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 21
- 241001330002 Bambuseae Species 0.000 claims abstract description 21
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 21
- 239000011425 bamboo Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000000571 coke Substances 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- -1 polyoxyethylene Polymers 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 235000019580 granularity Nutrition 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 2
- 239000007833 carbon precursor Substances 0.000 abstract 2
- 239000002006 petroleum coke Substances 0.000 abstract 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method of special active carbon for water-system super capacitors. The preparation method comprises the following steps: pre-oxidizing and carbonizing bamboo to obtain a carbon precursor, and mixing the carbon precursor with petroleum coke, potassium hydroxide and polyethylene glycol, wherein the proportions of the added raw materials are as follows: 75-80 parts of petroleum coke, 15-25 parts of carbonized bamboo, 1-2 parts of polyethylene glycol and 80-480 parts of potassium hydroxide all by mass; under the protection of inert gas, gradually heating the carbon-alkali mixture to 700-800 DEG C at a rate of 20 DEG C per minute, and activating for 1-1.5 hours; cooling to room temperature under the protection of inert gas, and washing with water to neutrality; and drying for 15 hours in a drying oven at 100 DEG C. The active carbon obtained by the method has high microporosity; and meanwhile, since the active carbon contains abundant mesoporous systems of bamboo-based active carbon while the mesoporous systems serve as ion conveying channels, the specific capacity and multiplying power of the super capacitors are enhanced. Therefore, the water-system super capacitors based on the active carbon material integrate high specific capacity and high multiplying power.
Description
Technical field
The present invention relates to capacitor material preparing technical field, be specifically related to a kind of preparation method of aqueous super capacitor special-purpose activated charcoal.
Background technology
Ultracapacitor is the novel energy-storing device that 20 th century later grow up, and with traditional secondary cell as compared with lithium ion battery, lead-acid cell etc., it is large that it has specific volume, and power density is high, has extended cycle life, the advantages such as environmental protection.In recent years along with countries in the world are to the high speed development in the fields such as the input of renewable energy source and environmental protection industry and the adjustment of power house power grid energy, green public transport, intelligent electric meter, ultracapacitor advantage shows especially, has become the focus of international energy field research and development.
Ultracapacitor generally adopts absorbent charcoal material as the active material of its electrode, the scientific research of ultracapacitor is shown, when ionic diameter in active carbon electrode material aperture and pore volume and electrolytic solution is suitable, active material specific storage is maximum, thus, when aperture pore volume and electrolytic solution intermediate ion diameter matches, ion easily can enter body phase contributions internal electrochemistry capacitance, and absorbent charcoal material Fabric utilization is the highest simultaneously.From electrolyte system, electrolytic solution for super capacitor mainly contains water system and organic system.Wherein, in aqueous electrolyte, the microvoid structure (1 ~ 4nm) of the corresponding gac of diameter of K+ ion, be less than organic salt ionic diameter order of magnitude, but now commercially available absorbent charcoal material is all for organic system electrolyte design, major part is homogeneous texture, based on mesopore hole system (5 ~ 100nm), relatively be applicable to organic system electrolytic solution environment, but it is serious easily to cause the aqueous super capacitor specific storage of assembling to be lost, and thus can not meet the forthright requirement taking into account height ratio capacity of aqueous super capacitor high power.
Summary of the invention
Technical problem solved by the invention is the preparation method providing a kind of aqueous super capacitor special-purpose activated charcoal, to solve the defect in above-mentioned technical background.
Technical problem solved by the invention realizes by the following technical solutions:
A preparation method for aqueous super capacitor special-purpose activated charcoal, specifically comprises the following steps:
1,3 years raw bamboo woods are cleaned be crushed to 100 ~ 200 object granularities, dry, then the bamboo wood after oven dry is carried out insulation carbonization in carbide furnace, carbonization holding temperature is 500 DEG C, carbonization time is 40 ~ 60 minutes, then in rare gas element, be cooled to room temperature, the gac obtained be crushed to and be less than 100 μm, obtain bamboo matrix activated carbon.
2, refinery coke is crushed to particle diameter and is less than 100 μm, the bamboo matrix activated carbon obtained by step 1 and refinery coke, potassium hydroxide, polyoxyethylene glycol mixes, the mass parts that wherein each raw material adds is: refinery coke 75 ~ 80 parts, carbonization bamboo wood 15 ~ 25 parts, polyoxyethylene glycol 1 ~ 2 part, 80 ~ 480 parts, potassium hydroxide, under the protection of rare gas element, carbon alkali mixture is warmed up to 700 ~ 800 DEG C gradually with the speed of 20 DEG C/min, activate 1 ~ 1.5 hour, room temperature is cooled under protection of inert gas, then neutrality is washed to, at the drying oven inner drying 15 hours of 100 DEG C, namely finished product is obtained.
The parameter of aqueous super capacitor special-purpose activated charcoal prepared by the present invention is: specific surface area is 5000 ~ 6500m
2/ g, iodine sorption value is 3000 ~ 4200mg/g, and average micro-pore diameter is 3.8nm, and the micropore size of 70% concentrates on 2 ~ 5.3nm, also has the central hole structure of 15% simultaneously, and these central hole structure apertures are 6 ~ 50nm.
Gac of the present invention is the absorbent charcoal material that central hole structure enriches, and mesopore communicates with internal capillary and material interface as mesoporous, has widened ion transportation passage.By this micropore-central hole structure, ionic adsorption and desorption action can rapid translating, be convenient to transporting of aqueous electrolyte ion, the KOH aqueous super capacitor assembled with this absorbent charcoal material on average promotes 35% compared with the aqueous super capacitor specific storage based on active Carbon Materials, current ratio is substantially suitable simultaneously, obvious to aqueous super capacitor performance boost.
Beneficial effect: the absorbent charcoal material that the present invention enriches for the preparation of a kind of central hole structure, this absorbent charcoal material is applied in aqueous super capacitor, and its mesopore communicates with internal capillary and material interface as mesoporous, can effectively widen ion transportation passage; And by this micropore-central hole structure, ionic adsorption and desorption action can rapid translating, the use properties of aqueous super capacitor can be significantly improved.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
3 years raw bamboo woods cleaned and be crushed to 100 ~ 200 object granularities, dry, then 500 DEG C of insulation carbonizations 40 ~ 60 minutes in carbide furnace, are cooled to room temperature in rare gas element.Then the gac obtained is crushed to and is less than 100 μm of acquisition bamboo matrix activated carbons.
Refinery coke is crushed to and is less than 100 μm; the bamboo matrix activated carbon obtained in step (1) is mixed with refinery coke, potassium hydroxide, polyoxyethylene glycol; the mass parts that wherein each raw material adds is: refinery coke 80 parts; carbonization bamboo wood 18 parts; polyoxyethylene glycol 2 parts, 160 parts, potassium hydroxide, under the protection of rare gas element; carbon alkali mixture is warmed up to 750 DEG C gradually with the speed of 20 DEG C/min, activates 1 hour.Room temperature is cooled under protection of inert gas.Be washed to neutrality, at 100 DEG C, drying 15 hours, obtains gac.
The gac specific surface area prepared through above-mentioned steps is 6200m
2/ g, iodine sorption value is 3800mg/g, and average micro-pore diameter is 3.02nm, and the micropore size of 70% concentrates on 2 ~ 3.3nm.
Embodiment 2
3 years raw bamboo woods are cleaned and is crushed to 100 ~ 200 object granularities, dry, then 500 DEG C of insulation carbonizations 40 ~ 60 minutes in carbide furnace.Room temperature is cooled in rare gas element.Then the gac obtained is crushed to and is less than 100 μm of acquisition bamboo matrix activated carbons.
Refinery coke is crushed to and is less than 100 μm; the bamboo matrix activated carbon obtained in step (1) is mixed with refinery coke, potassium hydroxide, polyoxyethylene glycol; the mass parts that wherein each raw material adds is: refinery coke 75 parts; carbonization bamboo wood 24 parts; polyoxyethylene glycol 1 part, 450 parts, potassium hydroxide, under the protection of rare gas element; carbon alkali mixture is warmed up to 750 DEG C gradually with the speed of 20 DEG C/min, activates 1.5 hours.Room temperature is cooled under protection of inert gas.Be washed to neutrality, at 100 DEG C, drying 15 hours, obtains gac.
The gac specific surface area prepared through above-mentioned steps is 5000m
2/ g, iodine sorption value is 3200mg/g, and average micro-pore diameter is 3.76nm, and the micropore size of 70% concentrates on 3 ~ 6.9nm.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (2)
1. a preparation method for aqueous super capacitor special-purpose activated charcoal, specifically comprises the following steps:
1. 3 years raw bamboo woods are cleaned and be crushed to 100 ~ 200 object granularities, dry, then the bamboo wood after oven dry is carried out insulation carbonization in carbide furnace, carbonization holding temperature is 500 DEG C, carbonization time is 40 ~ 60 minutes, then in rare gas element, be cooled to room temperature, the gac obtained be crushed to and be less than 100 μm, obtain bamboo matrix activated carbon;
2. refinery coke is crushed to particle diameter and is less than 100 μm, the bamboo matrix activated carbon that 1. step is obtained and refinery coke, potassium hydroxide, polyoxyethylene glycol mixes, the mass parts that wherein each raw material adds is: refinery coke 75 ~ 80 parts, carbonization bamboo wood 15 ~ 25 parts, polyoxyethylene glycol 1 ~ 2 part, 80 ~ 480 parts, potassium hydroxide, under the protection of rare gas element, carbon alkali mixture is warmed up to 700 ~ 800 DEG C gradually with the speed of 20 DEG C/min, activate 1 ~ 1.5 hour, room temperature is cooled under protection of inert gas, then neutrality is washed to, at the drying oven inner drying 15 hours of 100 DEG C, namely finished product is obtained.
2. the preparation method of a kind of aqueous super capacitor special-purpose activated charcoal according to claim 1, is characterized in that, the gac parameter using the method to prepare is: specific surface area is 5000 ~ 6500m
2/ g, iodine sorption value is 3000 ~ 4200mg/g, and average micro-pore diameter is 3.8nm, and the micropore size of 70% concentrates on 2 ~ 5.3nm, also has the central hole structure of 15% simultaneously, and these central hole structure apertures are 6 ~ 50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511020373.6A CN105502391B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method of aqueous super capacitor special-purpose activated charcoal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511020373.6A CN105502391B (en) | 2015-12-30 | 2015-12-30 | A kind of preparation method of aqueous super capacitor special-purpose activated charcoal |
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| CN105502391A true CN105502391A (en) | 2016-04-20 |
| CN105502391B CN105502391B (en) | 2018-01-30 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663450A (en) * | 2013-12-19 | 2014-03-26 | 中国科学院过程工程研究所 | Carbon microspheres with high specific surface area and preparation method for carbon microspheres with high specific surface area |
| CN103771414A (en) * | 2014-01-13 | 2014-05-07 | 大连大学 | Method for preparing activated carbon with large specific surface area through rapid activation |
| CN103979536A (en) * | 2014-05-16 | 2014-08-13 | 宁夏宝塔石化科技实业发展有限公司 | Preparation method of special active carbon for adsorbing dioxin |
| CN104891488A (en) * | 2015-05-27 | 2015-09-09 | 合肥卓元科技服务有限公司 | High-temperature carbonization preparation method of bamboo activated carbon with high yield |
-
2015
- 2015-12-30 CN CN201511020373.6A patent/CN105502391B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663450A (en) * | 2013-12-19 | 2014-03-26 | 中国科学院过程工程研究所 | Carbon microspheres with high specific surface area and preparation method for carbon microspheres with high specific surface area |
| CN103771414A (en) * | 2014-01-13 | 2014-05-07 | 大连大学 | Method for preparing activated carbon with large specific surface area through rapid activation |
| CN103979536A (en) * | 2014-05-16 | 2014-08-13 | 宁夏宝塔石化科技实业发展有限公司 | Preparation method of special active carbon for adsorbing dioxin |
| CN104891488A (en) * | 2015-05-27 | 2015-09-09 | 合肥卓元科技服务有限公司 | High-temperature carbonization preparation method of bamboo activated carbon with high yield |
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| Publication number | Publication date |
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| CN105502391B (en) | 2018-01-30 |
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Denomination of invention: Preparation method of special active carbon for water-system super capacitors Effective date of registration: 20180920 Granted publication date: 20180130 Pledgee: Postal Savings Bank of China Limited by Share Ltd Yiyang branch Pledgor: YIYANG WANJINGYUAN ELECTRONICS CO., LTD. Registration number: 2018430000073 |
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