CN103723722B - A kind of preparation method of Graphene modification activated carbon for super capacitors - Google Patents
A kind of preparation method of Graphene modification activated carbon for super capacitors Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 250
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003990 capacitor Substances 0.000 title description 5
- 238000012986 modification Methods 0.000 title description 3
- 230000004048 modification Effects 0.000 title description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 58
- 239000002006 petroleum coke Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 239000007772 electrode material Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 graphene-activated carbon composites Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 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
本发明公开了一种石墨烯改性超级电容器用活性炭的制备方法，属于电极材料制备技术领域。该方法是以石油焦活性炭为原料，经过去除杂质，匹配特定参数石墨烯，在高温活化，再去除有机溶剂后得到石墨烯改性超级电容器用活性炭。本发明制备的活性炭比表面积1600~2020m2，振实密度0.3008g/ml，具有各种特定的超级电容器用活性炭参数，用它制作的超级电容器，质量比电容达320F/g以上，体积比电容达198F/cm2。
The invention discloses a method for preparing activated carbon for a graphene-modified supercapacitor, belonging to the technical field of electrode material preparation. The method uses petroleum coke activated carbon as a raw material, removes impurities, matches graphene with specific parameters, activates at high temperature, and removes organic solvents to obtain graphene-modified activated carbon for supercapacitors. The activated carbon prepared by the present invention has a specific surface area of 1600-2020m2 , a tap density of 0.3008g/ml, and various specific activated carbon parameters for supercapacitors. The supercapacitor made with it has a mass specific capacitance of more than 320F/g and a volume specific capacitance. Up to 198F/cm 2 .
Description
技术领域 technical field
本发明属于电极材料制备技术领域，具体涉及一种石墨烯改性超级电容器用活性炭的制备方法，本发明涉及到一种石墨烯改性超级电容器用活性炭的制备方法，它是将活性炭去杂质后添加石墨烯在有机溶剂中进行高温活化，再去除有机溶剂得到石墨烯改性超级电容用活性炭。 The invention belongs to the technical field of electrode material preparation, and in particular relates to a method for preparing activated carbon for graphene-modified supercapacitors. The invention relates to a method for preparing activated carbon for graphene-modified supercapacitors. Adding graphene in an organic solvent for high-temperature activation, and then removing the organic solvent to obtain graphene-modified activated carbon for supercapacitors.
背景技术 Background technique
超级电容器是一种新型电化学储能装置。由于它是根据电化学原理设计、制造出来的，因此又被称为电化学电容器，泛指具有高功率和高能量密度的电容器。超级电容器具有充放电快、使用寿命长、功率密度高、维护简单方便、经济环保等优点，有着越来越重要、越来越广泛的用途。 Supercapacitor is a new type of electrochemical energy storage device. Because it is designed and manufactured based on electrochemical principles, it is also called an electrochemical capacitor, which generally refers to a capacitor with high power and high energy density. Supercapacitors have the advantages of fast charging and discharging, long service life, high power density, simple and convenient maintenance, economical and environmental protection, etc., and they have become more and more important and widely used.
碳材料，特别是sp2杂化的碳材料，由于特殊的层状结构、超大的比表面积而成为重要储能装置的电极材料。碳材料如无定形碳、活性炭、石墨等已经广泛用于锂电池中。 Carbon materials, especially sp 2 hybridized carbon materials, have become important electrode materials for energy storage devices due to their special layered structure and large specific surface area. Carbon materials such as amorphous carbon, activated carbon, graphite, etc. have been widely used in lithium batteries.
石墨烯因其拥有较高的比表面积和高的电导率，因此在作为电容器材料时具有比传统多孔碳材料更优异的性质，但是石墨烯体积比电容小，无法应用于大容量的超级电容器等电学器件。虽然用活性炭改性石墨烯可以提高石墨烯的体积比电容至119.7F/cm2，但其改性过程的活化温度较高，且石墨烯价格昂贵，同时由于目前没有大量制备石墨烯的技术，所以用石墨烯制备超级电容器用电极材料不能工业化生产。 Because of its high specific surface area and high electrical conductivity, graphene has better properties than traditional porous carbon materials when used as a capacitor material, but graphene has a small specific capacitance and cannot be applied to large-capacity supercapacitors, etc. electrical devices. Although the modification of graphene with activated carbon can increase the volume specific capacitance of graphene to 119.7F/cm 2 , the activation temperature of the modification process is relatively high, and graphene is expensive. Therefore, the use of graphene to prepare electrode materials for supercapacitors cannot be industrialized.
活性炭是超级电容器使用最多的电极材料，具有比表面积高、电化学稳定性好、原料丰富等优点。但是活性炭导电性较差、孔径分布不合理，活性炭的微孔结构贡献了主要的比表面积，而离子在微孔中的迁移阻力较大，另外，传统活性炭制作的超级电容器散热性能不理想。因此，无论它的原料来源如何变化、制备工艺如何改进，传统的活性炭的比表面积已经达到了峰值，传统活性炭生产的电容器性能已经无法再获得很大的突破。 Activated carbon is the most widely used electrode material for supercapacitors, which has the advantages of high specific surface area, good electrochemical stability, and abundant raw materials. However, activated carbon has poor conductivity and unreasonable pore size distribution. The microporous structure of activated carbon contributes the main specific surface area, and the migration resistance of ions in the micropores is relatively large. In addition, the heat dissipation performance of supercapacitors made of traditional activated carbon is not ideal. Therefore, no matter how its source of raw materials changes and how its preparation process is improved, the specific surface area of traditional activated carbon has reached its peak, and the performance of capacitors produced by traditional activated carbon can no longer achieve great breakthroughs.
因此，如何克服现有技术的不足已成为电极材料制备技术领域亟需解决的难题。 Therefore, how to overcome the deficiencies of the prior art has become an urgent problem to be solved in the technical field of electrode material preparation.
发明内容 Contents of the invention
本发明的目的是为了解决现有技术的不足，提供一种氧化石墨烯改性超级电容器用活性炭的制备方法，该方法制备的活性炭比表面积达1600m2~2020m2，振实密度达0.3008g/ml，用它制作的超级电容器，质量比电容达320F/g以上，体积比电容达198F/cm2。 The purpose of the present invention is to solve the deficiencies of the prior art, and to provide a method for preparing activated carbon for graphene oxide modified supercapacitors. The activated carbon prepared by the method has a specific surface area of 1600m 2 ~2020m 2 and a tap density of 0.3008g/ ml, the supercapacitor made with it has a mass specific capacitance of over 320F/g and a volume specific capacitance of 198F/cm 2 .
本发明采用的技术方案如下： The technical scheme that the present invention adopts is as follows:
一种石墨烯改性超级电容器用活性炭的制备方法是将活性炭原料经水洗后加入石墨烯有机溶剂分散液，超声处理，加热至60℃~100℃后，恒温搅拌至混合均匀充分，再经过过滤和离心处理得到石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:1~1:80，石墨烯有机溶剂分散液为石墨烯和有机溶剂的质量比为1‰~5%的混合物； A method for preparing activated carbon for graphene-modified supercapacitors is to wash the activated carbon raw material with water, add graphene organic solvent dispersion, ultrasonically treat, heat to 60 ° C ~ 100 ° C, stir at constant temperature until the mixture is uniform and sufficient, and then filter and centrifugal treatment to obtain activated carbon for graphene-modified supercapacitor; wherein, the mass ratio of activated carbon and graphene organic solvent dispersion is 1:1 ~ 1:80, and the graphene organic solvent dispersion is the mass ratio of graphene and organic solvent It is a mixture of 1‰~5%;
所述的有机溶剂为二甲基碳酸酯、甲乙基碳酸酯、碳酸乙烯酯、碳酸丙烯酯和γ-丁内酯中的一种或几种的组合物，其具体比例不作要求。选用有机溶剂，与去离子水相比，其浸润性能的差异导致石墨烯-活性炭组装结构不同，从而使获得的石墨烯活性炭复合物的体积比电容和质量比电容更高。 The organic solvent is one or a combination of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and γ-butyrolactone, and the specific ratio is not required. Compared with deionized water, the difference in wetting properties of organic solvents leads to different assembly structures of graphene-activated carbon, so that the obtained graphene-activated carbon composites have higher volume specific capacitance and mass specific capacitance.
进一步优选的是所述的活性炭原料为石油焦活性炭。 Further preferably, the activated carbon raw material is petroleum coke activated carbon.
进一步优选的是所述的活性炭原料粒度为800~12000目。 It is further preferred that the particle size of the activated carbon raw material is 800-12000 mesh.
进一步优选的是所述的石墨烯片径为100nm~500μm。 It is further preferred that the diameter of the graphene sheet is 100nm-500μm.
进一步优选的是所述的超声处理的时间为0.5h~10h。 Further preferably, the time of the ultrasonic treatment is 0.5h~10h.
进一步优选的是所述的加热恒温条件下搅拌时间为0.5h~10h。 It is further preferred that the stirring time under the heating and constant temperature condition is 0.5h~10h.
进一步优选的是所述的去除有机溶剂的方式是离心分离。 Further preferably, the method for removing the organic solvent is centrifugation.
本发明与现有技术相比，其有益效果为：本发明通过引入石墨烯，形成了石墨烯和活性炭构成的网路结构，首先使活性炭的比表面积得到充分利用，利用率高达99%；其次大幅度提高了活性炭的导电性，从根本上改变了离子迁移阻力大的问题；再次，石墨烯优异的导热性能使器件的散热性能提高55%。本发明使用少量的石墨烯，避免使用较高活化温度即可使获得的活性炭性能大幅度改良，综合使用成本低，附加值高，可应用于工业化生产。选择有机溶剂作分散液，改性的活性炭比电容数据，比国际目前最好的高60.1%。 Compared with the prior art, the present invention has the beneficial effects as follows: the present invention forms a network structure composed of graphene and activated carbon by introducing graphene, firstly the specific surface area of activated carbon is fully utilized, and the utilization rate is as high as 99%; secondly The conductivity of activated carbon has been greatly improved, and the problem of high ion migration resistance has been fundamentally changed; thirdly, the excellent thermal conductivity of graphene has improved the heat dissipation performance of the device by 55%. The present invention uses a small amount of graphene and avoids using a higher activation temperature to greatly improve the performance of the obtained activated carbon, has low comprehensive use cost and high added value, and can be applied to industrial production. The specific capacitance data of the modified activated carbon is 60.1% higher than the current best in the world by choosing an organic solvent as the dispersion liquid.
附图说明 Description of drawings
图1为本发明实施例8制备的石墨烯改性超级电容器用活性炭的电镜图。 Fig. 1 is the electron micrograph of the graphene-modified supercapacitor activated carbon prepared in Example 8 of the present invention.
具体实施例 specific embodiment
下面结合实施例对本发明作进一步的详细描述。 The present invention will be further described in detail below in conjunction with the examples.
本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。 This embodiment is carried out on the premise of the technical solution of the present invention, and the detailed implementation and specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
实施例1 Example 1
一种石墨烯改性超级电容器用活性炭的制备方法是将800目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理0.5h，加热至60℃后，恒温搅拌0.5h，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:1，石墨烯有机溶剂分散液为石墨烯和二甲基碳酸酯的质量比为1‰的混合物，石墨烯片径为100nm。 A preparation method of activated carbon for graphene-modified supercapacitors is to wash 800-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 0.5h, heat to 60°C, stir at constant temperature for 0.5h, and then centrifuge Separation and removal of the organic solvent obtains the activated carbon for the graphene-modified supercapacitor of this embodiment; wherein the mass ratio of the activated carbon to the graphene organic solvent dispersion is 1:1, and the graphene organic solvent dispersion is graphene and dimethyl The mass ratio of carbonate is a mixture of 1‰, and the graphene sheet diameter is 100nm.
实施例2 Example 2
一种石墨烯改性超级电容器用活性炭的制备方法是将12000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理10h，加热至100℃后，恒温搅拌10h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:80，石墨烯有机溶剂分散液为石墨烯和甲乙基碳酸酯的质量比为5%的混合物，石墨烯片径为500μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to add 12,000-mesh petroleum coke activated carbon into the graphene organic solvent dispersion after washing with water, ultrasonically treat for 10 hours, heat to 100°C, stir at constant temperature for 10 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for the graphene-modified supercapacitor of this embodiment; wherein, the mass ratio of the activated carbon and the graphene organic solvent dispersion is 1:80, and the graphene organic solvent dispersion is graphene and A and B The mass ratio of base carbonate is 5%, and the graphene sheet diameter is 500 μm.
实施例3 Example 3
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理2h，加热至70℃后，恒温搅拌4h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:20，石墨烯有机溶剂分散液为石墨烯和碳酸乙烯酯的质量比为9‰的混合物，石墨烯片径为100μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 2 hours, heat to 70°C, stir at constant temperature for 4 hours until the mixture is uniform and sufficient, and then The organic solvent is removed by centrifugation to obtain the activated carbon for the graphene modified supercapacitor of this embodiment; wherein, the mass ratio of the activated carbon to the graphene organic solvent dispersion is 1:20, and the graphene organic solvent dispersion is graphene and carbonic acid The mass ratio of vinyl ester is a mixture of 9‰, and the graphene sheet diameter is 100 μm.
实施例4 Example 4
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理4h，加热至80℃后，恒温搅拌5h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:30，石墨烯有机溶剂分散液为石墨烯和碳酸丙烯酯的质量比为1%的混合物，石墨烯片径为100μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 4 hours, heat to 80°C, stir at constant temperature for 5 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for graphene-modified supercapacitors in this embodiment; wherein the mass ratio of activated carbon to the graphene organic solvent dispersion is 1:30, and the graphene organic solvent dispersion is graphene and carbonic acid The mass ratio of acrylate is 1% mixture, and the diameter of graphene sheet is 100 μm.
实施例5 Example 5
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理7h，加热至90℃后，恒温搅拌8h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:78，石墨烯有机溶剂分散液为石墨烯和γ-丁内酯的质量比为2%的混合物，石墨烯片径为100μm。 A preparation method of activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 7 hours, heat to 90°C, stir at constant temperature for 8 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for graphene-modified supercapacitors in this embodiment; wherein, the mass ratio of activated carbon to the graphene organic solvent dispersion is 1:78, and the graphene organic solvent dispersion is graphene and γ - a mixture in which the mass ratio of butyrolactone is 2%, and the graphene sheet diameter is 100 μm.
实施例6 Example 6
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理9h，加热至75℃后，恒温搅拌6h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:40，石墨烯有机溶剂分散液为石墨烯、二甲基碳酸酯和甲乙基碳酸酯和有机溶剂的质量比为2:34:66的混合物，石墨烯片径为100μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 9 hours, heat to 75°C, stir at constant temperature for 6 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for the graphene-modified supercapacitor of this embodiment; wherein, the mass ratio of the activated carbon and the graphene organic solvent dispersion is 1:40, and the graphene organic solvent dispersion is graphene, di The mass ratio of methyl carbonate, methyl ethyl carbonate and organic solvent is a mixture of 2:34:66, and the graphene sheet diameter is 100 μm.
实施例7 Example 7
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理3h，加热至60℃~100℃后，恒温搅拌5h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:45，石墨烯有机溶剂分散液为石墨烯、甲乙基碳酸酯、碳酸乙烯酯和碳酸丙烯酯的质量比为2:25:40:35的混合物，石墨烯片径为100μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 3 hours, heat to 60 ℃ ~ 100 ℃, and stir at constant temperature for 5 hours until the mixture is uniform Enough, then remove the organic solvent through centrifugation, promptly obtain the activated carbon for the graphene modified supercapacitor of this embodiment; Wherein, the mass ratio of activated carbon and graphene organic solvent dispersion is 1:45, and graphene organic solvent dispersion is graphite The mass ratio of alkene, methyl ethyl carbonate, ethylene carbonate and propylene carbonate is a mixture of 2:25:40:35, and the graphene sheet diameter is 100 μm.
实施例8 Example 8
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理7h，加热至88℃后，恒温搅拌4h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:35，石墨烯有机溶剂分散液为石墨烯、二甲基碳酸酯、甲乙基碳酸酯、碳酸乙烯酯、碳酸丙烯酯和γ-丁内酯的质量比为2:25:25:25:25:25的混合物，石墨烯片径为100μm； A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 7 hours, heat to 88 ° C, stir at constant temperature for 4 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for the graphene-modified supercapacitor of this embodiment; wherein, the mass ratio of the activated carbon and the graphene organic solvent dispersion is 1:35, and the graphene organic solvent dispersion is graphene, di The mass ratio of methyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and gamma-butyrolactone is a mixture of 2:25:25:25:25:25, and the graphene sheet diameter is 100 μm;
本实施例制得的适用于超级电容器的石墨烯改性活性炭的电镜图如图1所示。图中可以看出石墨烯与活性炭复合的形态。 The electron microscope image of the graphene-modified activated carbon suitable for supercapacitors prepared in this example is shown in Figure 1. The composite form of graphene and activated carbon can be seen in the figure.
实施例9 Example 9
一种石墨烯改性超级电容器用活性炭的制备方法是将1000目的石油焦活性炭经水洗后加入石墨烯有机溶剂分散液，超声处理7h，加热至66℃后，恒温搅拌7h至混合均匀充分，再经离心分离去除有机溶剂，即得到本实施例石墨烯改性超级电容器用活性炭；其中，活性炭和石墨烯有机溶剂分散液的质量比为1:75，石墨烯有机溶剂分散液为石墨烯、二甲基碳酸酯、甲乙基碳酸酯、碳酸丙烯酯和γ-丁内酯的质量比为1:25:25:25:25的混合物，石墨烯片径为100μm。 A method for preparing activated carbon for graphene-modified supercapacitors is to wash 1000-mesh petroleum coke activated carbon with water, add graphene organic solvent dispersion, ultrasonically treat for 7 hours, heat to 66 ° C, stir at constant temperature for 7 hours until the mixture is uniform and sufficient, and then Remove the organic solvent through centrifugation to obtain the activated carbon for the graphene-modified supercapacitor of this embodiment; wherein, the mass ratio of the activated carbon and the graphene organic solvent dispersion is 1:75, and the graphene organic solvent dispersion is graphene, di The mass ratio of methyl carbonate, methyl ethyl carbonate, propylene carbonate and γ-butyrolactone is a mixture of 1:25:25:25:25, and the graphene sheet diameter is 100 μm.
对比实施例 comparative example
称取1000目的石油焦活性炭1.43g，经水洗后加入50g质量比为1:1:1:1:1二甲基碳酸酯、甲乙基碳酸酯、碳酸乙烯酯、碳酸丙烯酯和γ-丁内酯混合有机溶剂，超声处理7h，加热至88℃后，恒温搅拌4h至混合均匀充分，再经离心分离去除有机溶剂得到活性炭。 Weigh 1.43g of 1000-mesh petroleum coke activated carbon, add 50g of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and γ-butyrol in a mass ratio of 1:1:1:1:1 after washing with water The ester is mixed with an organic solvent, ultrasonically treated for 7 hours, heated to 88°C, stirred at a constant temperature for 4 hours until the mixture is uniform and fully mixed, and then the organic solvent is removed by centrifugation to obtain activated carbon.
本发明实施例1~9和对比实施例的工艺参数及其产品性能检测数据如表1所示。 The process parameters and product performance testing data of Examples 1 to 9 of the present invention and comparative examples are as shown in Table 1.
表1本发明实施例1~9和对比实施例的工艺参数及其产品性能检测数据 Table 1 embodiment of the present invention 1～9 and the processing parameter of comparative example and product performance detection data thereof
从上述实施例可以看出，石墨烯改性后的超级电容器用活性炭，体积比电容和质量比电容都有显著地提升。 It can be seen from the above examples that the volume specific capacitance and mass specific capacitance of the graphene-modified activated carbon for supercapacitors are significantly improved.
同时对实施例8制备的石墨烯改性超级电容器用活性炭的含量及成分进行检测，其检测数据如表2所示。 At the same time, the content and composition of the activated carbon for the graphene-modified supercapacitor prepared in Example 8 were detected, and the detection data are shown in Table 2.
表2实施例8制备的石墨烯改性超级电容器用活性炭的检测数据 The detection data of the graphene-modified supercapacitor activated carbon that table 2 embodiment 8 prepares
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