CN103723721B - A kind of preparation method of graphene oxide modification activated carbon for super capacitors - Google Patents
A kind of preparation method of graphene oxide modification activated carbon for super capacitors Download PDFInfo
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- CN103723721B CN103723721B CN201310590035.0A CN201310590035A CN103723721B CN 103723721 B CN103723721 B CN 103723721B CN 201310590035 A CN201310590035 A CN 201310590035A CN 103723721 B CN103723721 B CN 103723721B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 105
- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 230000004048 modification Effects 0.000 title claims abstract description 33
- 238000012986 modification Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003610 charcoal Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 12
- 239000002023 wood Substances 0.000 claims description 12
- 235000013399 edible fruits Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- -1 gac Chemical compound 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
Classifications
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- 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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- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of graphene oxide modification activated carbon for super capacitors, belong to electrode materials preparing technical field.The method is for raw material with one or more in traditional shell, wooden and straw-stem active charcoal, through removing impurity, coupling special parameter graphene oxide, high-temperature activation in deionized water solution, utilize ammoniacal liquor and oxammonium hydrochloride that graphene oxide is reduced to Graphene, then obtain modification activated carbon for super capacitors after dewatering and drying.Gac specific surface area 1900m prepared by the present invention
2~ 2010m
2, tap density 0.30 ~ 0.33g/ml, the ultracapacitor made of it, quality reaches more than 305F/g than electric capacity, and volumetric capacitance reaches 193F/cm
2.
Description
Technical field
The invention belongs to electrode materials preparing technical field, be specifically related to a kind of preparation method of graphene oxide modification activated carbon for super capacitors, the method is for raw material with one or more in traditional shell, wooden and straw-stem active charcoal, through removing impurity, coupling special parameter graphene oxide, high-temperature activation in deionized water solution, utilizes ammoniacal liquor and oxammonium hydrochloride that graphene oxide is reduced to Graphene, then obtains Graphene modification activated carbon for super capacitors after dewatering and drying.
Background technology
Ultracapacitor is a kind of model electrochemical energy storage device.Because it is that be therefore otherwise known as electrochemical capacitor, and general reference has the electrical condenser of superpower and high-energy-density according to electrochemical principle design, produced.Ultracapacitor has the advantages such as discharge and recharge is fast, long service life, power density are high, it is simple and convenient to safeguard, economic environmental protection, has more and more important, purposes more and more widely.
Carbon material, particularly sp
2the carbon material of hydridization, becomes the electrode materials of important energy storage device due to the specific surface area of special laminate structure, super large.Carbon material such as decolorizing carbon, gac, graphite etc. have been widely used in lithium cell.
Graphene has higher specific surface area and high specific conductivity because of it, and therefore as having the character more excellent than conventional porous carbon material during capacitor material, but Graphene volumetric capacitance is little, cannot be applied to the electricity devices such as jumbo ultracapacitor.Although the volumetric capacitance of Graphene can be improved to 119.7F/cm with activated carbon modified Graphene
2, but the activation temperature of its modifying process is higher, and Graphene is expensive, simultaneously owing to not preparing the technology of Graphene at present in a large number, can not suitability for industrialized production so prepare electrode for super capacitor material with Graphene.
Gac is that ultracapacitor uses maximum electrode materialss, has the advantages such as specific surface area is high, electrochemical stability good, abundant raw material.But gac electroconductibility is poor, pore size distribution is unreasonable, the microvoid structure of gac contribute to main specific surface area, and the migration resistance of ion in micropore is comparatively large, and in addition, the ultracapacitor heat dispersion that conventional carbon makes is undesirable.Therefore, no matter how its raw material sources change, how preparation technology to improve, and the specific surface area of traditional gac reaches peak value, and the capacitor performance that conventional carbon is produced cannot have been reentried very large breakthrough.
Therefore, how to overcome the deficiencies in the prior art and become the difficult problem that electrode materials preparing technical field needs solution badly.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, provide a kind of preparation method of graphene oxide modification activated carbon for super capacitors, gac specific surface area prepared by the method reaches 1900m
2~ 2010m
2, tap density reaches 0.30 ~ 0.33g/ml, and the ultracapacitor made of it, quality reaches more than 305F/g than electric capacity, and volumetric capacitance reaches 193F/cm
2.
The technical solution used in the present invention is as follows:
Activated carbon raw material is added graphene oxide aqueous dispersions by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after washing, supersound process, after being heated to 60 DEG C ~ 100 DEG C, constant temperature is stirred to and mixes fully, add ammoniacal liquor again and hydrochloric acid hydrogen amine mixing solutions reduces, finally reaction system to be filtered and drying and processing obtains graphene oxide modification activated carbon for super capacitors; Wherein the mass ratio of gac and graphene oxide aqueous dispersions is 1:1 ~ 1:100, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:10 ~ 5:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:0.5 ~ 1:5, and graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 1 ‰ ~ 20%.
Further preferably described activated carbon raw material refers to by the composition of one or more in active fruit shell carbon, wood activated charcoal and straw-stem active charcoal, and its concrete ratio does not do requirement.
Further preferably described activated carbon raw material granularity is 900 ~ 10000 orders.
Further preferably described washing refers to and utilizes deionized water to carry out at least 2 washings to activated carbon raw material.
The sheet footpath of further preferably described graphene oxide is 90nm ~ 600 μm.
The time of further preferably described supersound process is 0.5h ~ 10h.
Under further preferably described heated constant temperature condition, churning time is 0.5h ~ 10h.
Further preferably described drying time is 1h ~ 24h.
Further preferably described washing times is 2 ~ 5 times.
compared with prior art, its beneficial effect is in the present invention:the present invention is by introducing graphene oxide, define the network configuration of Graphene and gac formation, first the specific surface area of gac is made to be fully used, utilization ratio reaches more than 98%, next has increased substantially the electroconductibility of gac, fundamentally change the problem that ion migration resistance is large, again, the heat conductivility of Graphene excellence makes the heat dispersion of device improve 40%.The present invention uses a small amount of Graphene, avoids using higher activation temperature that the Properties of Activated Carbon of acquisition can be made significantly to improve, and comprehensive use cost is low, and added value is high, is easy to suitability for industrialized production.The gac ratio capacitance data of modification are more current than the world best high by 52.8%.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum figure of graphene oxide modification activated carbon for super capacitors prepared by embodiment 5.
Specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
900 object active fruit shell carbons are added graphene oxide aqueous dispersions by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 2 times, supersound process 0.5h, after being heated to 60 DEG C, constant temperature stirs 0.5h, add ammoniacal liquor again and oxammonium hydrochloride mixing solutions reduces, finally reaction system is filtered and the drying and processing of 1h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mass ratio of active fruit shell carbon and graphene oxide aqueous dispersions is 1:1, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:2, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:0.5, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 1 ‰, and the sheet footpath of graphene oxide is 90nm.
Embodiment 2
10000 object wood activated charcoals are added graphene oxide aqueous dispersions by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 5 times, supersound process 10h, after being heated to 100 DEG C, constant temperature stirs 10h, add ammoniacal liquor again and oxammonium hydrochloride mixing solutions reduces, finally reaction system is filtered and the drying and processing of 16h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mass ratio of wood activated charcoal and graphene oxide aqueous dispersions is 1:100, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 5:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:5, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 20%, and the sheet footpath of graphene oxide is 600 μm.
Embodiment 3
1000 object straw-stem active charcoals are added graphene oxide aqueous dispersions by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 4 times, supersound process 2h, after being heated to 90 DEG C, constant temperature stirs 5h, add ammoniacal liquor again and oxammonium hydrochloride mixing solutions reduces, finally reaction system is filtered and the drying and processing of 20h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mass ratio of straw-stem active charcoal and graphene oxide aqueous dispersions is 1:30, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 2:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:1, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 3%, and the sheet footpath of graphene oxide is 100nm.
Embodiment 4
2000 object active fruit shell carbons and wood activated charcoal mass ratio are added graphene oxide aqueous dispersions by the mixture of 1:1 by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 6 times, supersound process 4h, after being heated to 70 DEG C, constant temperature stirs 4h, add ammoniacal liquor again and hydrochloric acid hydrogen amine mixing solutions reduces, finally reaction system is filtered and the drying and processing of 15h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mixture of active fruit shell carbon and wood activated charcoal and the mass ratio of graphene oxide aqueous dispersions are 1:50, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:1, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 6%, and the sheet footpath of graphene oxide is 500nm.
Embodiment 5
2000 object active fruit shell carbons and straw-stem active charcoal mass ratio are added graphene oxide aqueous dispersions by the mixture of 1:1 by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 4 times, supersound process 7h, after being heated to 85 DEG C, constant temperature stirs 4h, add ammoniacal liquor again and hydrochloric acid hydrogen amine mixing solutions reduces, finally reaction system is filtered and the drying and processing of 9h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mixture of active fruit shell carbon and straw-stem active charcoal and the mass ratio of graphene oxide aqueous dispersions are 1:50, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:1, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 6%, and the sheet footpath of graphene oxide is 500nm;
The Electronic Speculum figure of the graphene oxide modification activated carbon for super capacitors that the present embodiment obtains as shown in Figure 1.As can be seen from the figure the form of graphene oxide and gac compound.
Embodiment 6
2000 object wood activated charcoals and straw-stem active charcoal mass ratio are added graphene oxide aqueous dispersions by the mixture of 1:1 by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 7 times, supersound process 8h, after being heated to 75 DEG C, constant temperature stirs 5h, add ammoniacal liquor again and hydrochloric acid hydrogen amine mixing solutions reduces, finally reaction system is filtered and the drying and processing of 6h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mixture of wood activated charcoal and straw-stem active charcoal and the mass ratio of graphene oxide aqueous dispersions are 1:50, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:1, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 6%, and the sheet footpath of graphene oxide is 500nm.
Embodiment 7
2000 object active fruit shell carbons, wood activated charcoal and straw-stem active charcoal mass ratio are added graphene oxide aqueous dispersions by the mixture of 1:1:1 by a kind of preparation method of graphene oxide modification activated carbon for super capacitors after deionized water wash 3 times, supersound process 9h, after being heated to 80 DEG C, constant temperature stirs 6.5h, add ammoniacal liquor again and hydrochloric acid hydrogen amine mixing solutions reduces, finally reaction system is filtered and the drying and processing of 5h, namely obtain the present embodiment graphene oxide modification activated carbon for super capacitors; Wherein, the mixture of active fruit shell carbon, wood activated charcoal and straw-stem active charcoal and the mass ratio of graphene oxide aqueous dispersions are 1:80, the molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:1, the mass ratio of graphene oxide and oxammonium hydrochloride is 1:1, graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 5 ‰, and the sheet footpath of graphene oxide is 500nm.
Comparative example
Take 2000 object wood activated charcoals and each 0.5g mixing of straw-stem active charcoal respectively, 50g deionized water is added after deionized water wash 3 times, supersound process 9h, after being heated to 80 DEG C, constant temperature stirs 6.5h, add 1.5g ammoniacal liquor and 3g hydrochloric acid hydrogen amine mixing solutions again, finally mixture is filtered and the drying and processing of 5h, obtain gac.
The processing parameter of the embodiment of the present invention 1 ~ 7 and comparative example and products thereof performance detection data is as shown in table 1.
The processing parameter of table 1 embodiment of the present invention 1 ~ 7 and comparative example and products thereof performance detection data
| Graphene oxide | Dispersion liquid | Active fruit shell carbon | Wood activated charcoal | Straw-stem active charcoal | Ammoniacal liquor | Oxammonium hydrochloride | Quality compares electric capacity | Volumetric capacitance | |
| Embodiment 1 | 0.5g | 500.0g | 500.0g | 0g | 0g | 0.63g | 2.5g | 191.2F/cm 2 | 299.6F/g |
| Embodiment 2 | 1.0g | 5.0g | 0g | 0.05g | 0g | 12.6g | 5.0g | 193.7F/cm 2 | 298.4F/g |
| Embodiment 3 | 3.0g | 100.0g | 0g | 0g | 3.3g | 3.0g | 3.0g | 198.1F/cm 2 | 306.1F/g |
| Embodiment 4 | 3.0g | 50.0g | 0.5g | 0.5g | 0g | 1.5g | 3.0g | 197.6F/cm 2 | 310.3F/g |
| Embodiment 5 | 1.5g | 25.0g | 0.25g | 0g | 0.25g | 0.76g | 1.5g | 199.0F/cm 2 | 308.5F/g |
| Embodiment 6 | 3.0g | 50.0g | 0g | 0.5g | 0.5g | 1.5g | 3.0g | 194.2F/cm 2 | 305.9F/g |
| Embodiment 7 | 3.0g | 50.0g | 0.33g | 0.33g | 0.33g | 1.5g | 3.0g | 196.5F/cm 2 | 306.4F/g |
| Comparative example | 0.0g | 50.0g | 0g | 0.5g | 0.5g | 1.5g | 3.0g | 110.7F/cm 2 | 198.3F/g |
As can be seen from above-described embodiment, the activated carbon for super capacitors that graphene oxide is modified, volumetric capacitance and quality than electric capacity, have and promote significantly compared with the gac not adding graphene oxide.
Claims (6)
1. the preparation method of a graphene oxide modification activated carbon for super capacitors, activated carbon raw material is it is characterized in that to add graphene oxide aqueous dispersions after washing, supersound process, after being heated to 60 DEG C ~ 100 DEG C, constant temperature is stirred to and mixes, add ammoniacal liquor again and oxammonium hydrochloride mixing solutions reduces, finally to filter reaction system and drying and processing obtains graphene oxide modification activated carbon for super capacitors, the specific surface area of this gac reaches 1900m
2~ 2010m
2, tap density reaches 0.30 ~ 0.33g/ml;
Wherein the mass ratio of gac and graphene oxide aqueous dispersions is 1:1 ~ 1:100;
The molar mass of ammoniacal liquor and oxammonium hydrochloride is than being 1:2 ~ 5:1;
The mass ratio of graphene oxide and oxammonium hydrochloride is 1:0.5 ~ 1:5;
Graphene oxide aqueous dispersions is the mass ratio of graphene oxide and deionized water is the mixture of 1 ‰ ~ 20%;
Described activated carbon raw material refers to the composition by one or more in active fruit shell carbon, wood activated charcoal and straw-stem active charcoal;
Described activated carbon raw material granularity is 900 ~ 10000 orders;
The sheet footpath of described graphene oxide is 90nm ~ 600 μm.
2. the preparation method of graphene oxide modification activated carbon for super capacitors according to claim 1, is characterized in that described washing refers to and utilizes deionized water to carry out at least 2 washings to activated carbon raw material.
3. the preparation method of graphene oxide modification activated carbon for super capacitors according to claim 1, is characterized in that the time of described supersound process is 0.5h ~ 10h.
4. the preparation method of graphene oxide modification activated carbon for super capacitors according to claim 1, is characterized in that described constant temperature churning time is 0.5h ~ 10h.
5. the preparation method of graphene oxide modification activated carbon for super capacitors according to claim 1, is characterized in that described drying time is 1h ~ 24h.
6. the preparation method of graphene oxide modification activated carbon for super capacitors according to claim 2, is characterized in that: washing times is 2 ~ 5 times.
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| CN105321726B (en) * | 2014-07-21 | 2019-02-05 | 中国科学院大连化学物理研究所 | High magnification active carbon/Activated Graphite alkene combination electrode material and preparation method thereof |
| CN104599861A (en) * | 2014-12-31 | 2015-05-06 | 江苏江大环保科技开发有限公司 | Preparation method of graphene/xylogen-based active carbon |
| CN104851611A (en) * | 2015-04-03 | 2015-08-19 | 安徽江威精密制造有限公司 | Low-resistance straw-based electrode material and preparation method thereof |
| CN105405673B (en) * | 2015-11-05 | 2017-07-28 | 宁波中车新能源科技有限公司 | Double layer capacitor using sandwich composite carbon electrode material and preparation method thereof |
| CN106082210A (en) * | 2016-06-20 | 2016-11-09 | 山东欧铂新材料有限公司 | A kind of compound active fruit shell carbon and preparation method thereof, application |
| CN106082213B (en) * | 2016-06-20 | 2019-04-26 | 山东欧铂新材料有限公司 | A kind of compound petroleum coke matrix activated carbon and preparation method thereof, supercapacitor |
| CN107185489A (en) * | 2016-12-30 | 2017-09-22 | 常州碳星科技有限公司 | The preparation method of the sorbing material of Atmospheric Organic Pollutants |
| CN108996501B (en) * | 2017-06-06 | 2021-02-26 | 济南圣泉集团股份有限公司 | Modified activated carbon material, preparation method and application |
| CN109559897A (en) * | 2017-09-26 | 2019-04-02 | 财团法人工业技术研究院 | The electrode and its manufacturing method of composite material and its manufacturing method and application composite material |
| CN109665524A (en) * | 2017-10-16 | 2019-04-23 | 山东欧铂新材料有限公司 | A kind of preparation method and supercapacitor of small particle graphene composite stone oil coke matrix activated carbon |
| CN111170307B (en) * | 2020-01-14 | 2023-04-28 | 江西省纳米技术研究院 | Nanocarbon modified hollow activated carbon microtube and preparation method and application thereof |
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| CN102757040B (en) * | 2012-07-25 | 2014-07-09 | 哈尔滨工业大学 | Graphene-based hydrogel and preparation method thereof as well as preparation method and application of supercapacitor electrode taking graphene-based hydrogel as active material |
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