超级电容器用PVDC基碳电极的研究现状/肖国庆等超级电容器用PVDC基碳电极的研究现状

doi:10.11896/j.issn.1005-023X.2018.19.004

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Abstract Carbon electrode is the key material of super capacitor, which largely determines the performance of super capacitor. Carbon electrode develops towards high specific surface area, high bulk density, high porosity, high conductivity, high purity, high cost performance, and good electrolyte wettability. At present, it has been reported that diverse carbon materials including activated carbon fibers, carbon aerogels, carbon nanotubes and template carbons have been widely investigated as electrode materials for supercapacitors. However, the relatively low specific capacitance and bulk density of these carbon materials seriously block their practical applications in supercapacitor electrodes with high energy demand. To solve these problems, the research of porous carbon materials with high specific surface area has aroused increasing attention in recent years, especially the free-activation methods like blen-ding polymer pyrolysis, microemulsion-templated sol-gel polymerization and template method have received great concern. Yet the preparation of polymer blend, the time-consuming supercritical drying and the removal of the template have made the process even more complicated than conventional methods.
The dechlorination and activation can be accomplished in one step when poly(vinylidene dichloride) (PVDC) is taken as precursors for porous carbon preparation. The superiorities of polyvinyl chloride based carbon as electrode material for supercapacitors can be concluded as follow. Ⅰ. The abundant resource and low cost of PVDC. Ⅱ.Its long-chain configuration with an inherently high carbon density can greatly facilitate aromatic cyclization, lower energy input of carbonization of PVDC is needed compared with other small molecules, and no additional activation process is required. Ⅲ. The porous carbon materials prepared by using PVDC as carbon precursor present considerably higher specific capacitance than the ones prepared by other materials reported up to now, the specific capacitance of PVDC based carbon electrode can reach over 400 F/g. Significantly, carbon electrode materials of high performance supercapacitors not only require high specific surface area, but also need suitable pore size for the electrolyte, while these two factors are restricted by each other. Therefore, the focus of current research is to realize the regulation and optimization of microstructure of carbon materials at a more micro level.
The preparation methods of PVDC-based carbon electrode for supercapacitors can be mainly divided into dechlorination-activation multistep method and dechlorination-activation one-step method. For the former, PVDC is directly mechanically ground or pyrolyzed at a high temperature, and then a porous carbon material with high specific surface is obtained after various activation process. The porous carbon obtained by this method show high specific surface area, but the preparation process is relatively complicated. Additional activation process is not needed for template method, but it still needs two steps. Although the porous carbon materials prepared by template method exhibit many advantages including large specific surface area, large pore volume and hierarchical pore size distribution, its specific capacitance is relatively low which limits its application in supercapacitors. Thanks to the unique structure of PVDC, PVDC-based porous carbon material can be achieved through one-step dechlorination-activation only by adding strong alkali in the process of high temperature pyrolysis or mechanical grinding. This process of dechlorination is simple and efficient, and does not damage the intrinsic structure of PVDC. Besides, the chlorine elements in PVDC connected to vinylidene units are highly active, they can be eliminated with a much lower energy input compared to the N-/O- in N-/O- containing polymers. Thus, dechlorination and carbonization of PVDC can be occurred at a lower temperature. The vacancy after dechlorination is sensitive to heteroatoms and doping can be easily realized.
This article reviews the investigations on the porous structure, specific surface and electrochemical performance of PVDC-based carbon materials for supercapacitors from three aspects, including PVDC dechlorination-activation multistep carbonization, dechlorination-activation one-step carbonization and N-doping. And the future development of PVDC-based carbon electrode for supercapacitors is prospected.

Key words： poly(vinylidene dichloride) supercapacitor carbon electrode porous carbon nitrogen-doping

Published: 18 October 2018

CLC number:	O646
	TM919

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	XIAO Guoqing
	GOU Limin
	DING Donghai

Cite this article:

XIAO Guoqing,GOU Limin,DING Donghai. A State of the art Review on PVDC based Carbon Electrode for Supercapacitors[J]. Materials Reports, 2018, 32(19): 3309-3317.

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http://www.mater-rep.com/EN/10.11896/j.issn.1005-023X.2018.19.004 OR http://www.mater-rep.com/EN/Y2018/V32/I19/3309

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