A State of the art Review on PVDC based Carbon Electrode for Supercapacitors
XIAO Guoqing1, GOU Limin1, DING Donghai1,2,3
1 College of Materials and Mineral Resources, Xi’an University of Architecture and Technology, Xi’an 710055; 2 Postdoctoral Mobile Research Station of Materials Science and Engineering, Xi’an University of Architectureand Technology, Xi’an 710055; 3 State Key Laboratory of Advanced Refractories, Sinosteel LuoyangInstitute of Refractories Research Co., Ltd., Luoyang 471039
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.
肖国庆, 勾黎敏, 丁冬海. 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[J]. 材料导报, 2018, 32(19): 3309-3317.
XIAO Guoqing, GOU Limin, DING Donghai. A State of the art Review on PVDC based Carbon Electrode for Supercapacitors. Materials Reports, 2018, 32(19): 3309-3317.
1 Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors[J].Chemical Society Reviews,2012,43(18):797. 2 Du S H, Wang L Q, Fu X T, et al. Hierarchical porous carbon microspheres derived from porous starch for use in high-rate electrochemical double-layer capacitors[J].Bioresource Technology,2013,139(13):406. 3 Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors[J].Carbon,2001,39(6):937. 4 Xu B, Chen Y F, Wei G, et al. Activated carbon with high capacitance prepared by NaOH activation for supercapacitors[J].Materials Chemistry & Physics,2010,124(1):504. 5 Jiang Q, Qu M Z, Zhang B L, et al. Progress of research on electrode materials for electrochemical supercapacitors[J].Journal of Inorganic Materials,2002,174(4):649(in Chinese). 江奇,瞿美臻,张伯兰,等.电化学超级电容器电极材料的研究进展[J].无机材料学报,2002,174(4):649. 6 Zhang Y, Feng H, Wu X B, et al. Progress of electrochemical capacitor electrode materials: A review[J].International Journal of Hydrogen Energy,2009,34(11):4889. 7 Hulicovajurcakova D, Puziy A M, Poddubnaya O I, et al. Highly stable performance of supercapacitors from phosphorus-enriched carbons[J].Journal of the American Chemical Society,2009,131(14):5026. 8 Feng C C, Wu A M, Huang H. Recent progress of N-doped porous carbon materials with applications to supercapacitor electrde[J].Materials Review A: Review Papers,2016,30(1):143(in Chinese). 冯晨辰,吴爱民,黄昊.超级电容器电极用N-掺杂多孔碳材料的研究进展[J].材料导报:综述篇,2016,30(1):143. 9 Francois B, Elzbieta F.超级电容器:材料、系统及应用[M].北京:机械工业出版社,2014. 10 Xu B, Wu F, Chen S, et al. High-capacitance carbon electrode prepared by PVDC carbonization for aqueous EDLCs[J].Electrochimica Acta,2009,54(8):2185. 11 Frackowiak E. Carbon materials for supercapacitor application[J].Physical Chemistry Chemical Physics,2007,9(15):1774. 12 Lobato B, Suarez L, Guardia L, et al. Capacitance and surface of carbons in supercapacitors[J].Carbon,2017,122:434. 13 Xu B, Zhang H, Cao G P, et al. Carbon materials for supercapacitors[J].Process in Chemistry,2011(2):605(in Chinese). 徐斌,张浩,曹高萍,等.超级电容器炭电极材料的研究[J].化学进展,2011(2):605. 14 Yang J, Bao Y Z, Pan P Q. Preparation of hierarchical porous carbons from amphiphilic poly(vinylidene chloride-co-methyl acrylate)-b-poly(acrylic acid) copolymers by self-templating and one-step carbonization method[J].Microporous & Mesoporous Materials,2014,196:199. 15 Wu D G, Fu R W, Dresselhaus M S, et al. Fabrication and nano-structure control of carbon aerogels via a microemulsion-templated sol-gel polymerization method[J].Carbon,2006,44(4):675. 16 Sun F, Gao J H, Liu X, et al. Porous carbon with a large surface area and an ultrahigh carbon purity via templating carbonization coupling with KOH activation as excellent supercapacitor electrode materials[J].Applied Surface Science,2016,387:857. 17 Xu B, Hou S H, Chu M, et al. An activation-free method for preparing microporous carbon by the pyrolysis of poly(vinylidene fluo-ride)[J].Carbon,2010,48(10):2812. 18 Kim D N, Buchholz D B, Casillas G, et al. Hierarchical design for fabricating cost-effective high performance supercapacitors[J].Advanced Functional Materials,2014,24(26):4186. 19 Robertson C, Mokaya R. Microporous activated carbon aerogels via a simple subcritical drying route for CO2 capture and hydrogen storage[J].Microporous & Mesoporous Materials,2013,179(17):151. 20 Zhang G X, Wang L, Hao Y C, et al. Unconventional carbon: Alkaline dehalogenation of Polymers yields N-doped carbon electrode for high-performance capacitive energy storage[J].Advanced Functional Materials,2016,26(19):3340. 21 Ferrero G A, Fuertes A B, Sevilla M. N-doped microporous carbon microspheres for high volumetric performance supercapacitors[J].Electrochimica Acta,2015,168:320. 22 González A, Goikolea E, Barrena J A, et al. Review on supercapacitors: Technologies and materials[J].Renewable & Sustainable Energy Reviews,2016,58(2016):1189. 23 Zhang L L, Zhao X S. Carbon-based materials as supercapacitor electrodes[J].Chemical Society Reviews,2009,38(9):2520. 24 Solodovnichenko V S, Kryazhev Y G, Arbuzov A B, et al. Polyvinyl chloride as precursor for low-temperature synthesis of carbon materials[J].Russian Chemical Bulletin,2016,65(11):2712. 25 Lin S K, March J. March’s advanced organic chemistry: Reactions, mechanisms, and structure, 5th Edition[J].Molecules,2001,6(12):1064. 26 Li X Q, Chang L, Zhao S L, et al. Research on carbon-based electrode materials for supercapacitors[J].Acta Physico-Chimica Sinica,2017,33(1):130(in Chinese). 李雪芹,常琳,赵慎龙,等.基于碳材料的超级电容器电极材料的研究[J].物理化学学报,2017,33(1):130. 27 Xie X Y, Zhang C, Yang Q H. The development of electrode mate-rials for supercapacitors[J].Chemical Industry & Engineering,2014,31(1):63(in Chinese). 谢小英,张辰,杨全红.超级电容器电极材料研究进展[J].化学工业与工程,2014,31(1):63. 28 Pandolfo A G, Hollenkamp A F. Carbon properties and their role in supercapacitors[J].Journal of Power Sources,2006,157(1):11. 29 Kim Y J, Masutzawa Y, Ozaki S, et al. PVDC-based carbon mate-rial by chemical activation and its application to nonaqueous EDLC[J].Journal of the Electrochemical Society,2004,151(6):E199. 30 Obreja V V N. On the performance of supercapacitors with electrodes based on carbon nanotubes and carbon activated material—A review[J].Physica E: Low-dimensional Systems and Nanostructures,2008,40(7):2596. 31 Xu B, Wu F, Mu D B, et al. Activated carbon prepared from PVDC by NaOH activation as electrode materials for high performance EDLCs with non-aqueous electrolyte[J].International Journal of Hydrogen Energy,2010,35(2):632. 32 Eliad L, Plollak L, Levy N, et al. Assessing optimal pore-to-ion size relations in the design of porous poly(vinylidene chloride) carbons for EDL capacitors[J].Applied Physics A,2006,82(4):607. 33 Cai J J, Lv X X, Xing Y L, et al. Carbon dioxide adsorption on poly(vinylidene chloride)-based carbons with ultrahigh microporosities prepared by facile carbonization[J].Materials Letters,2014,114(1):37. 34 Kryazhev Y G, Solodovinchenko V S, Antonicheva N V, et al. Evolution of the structures and sorption properties of dehydrochlorinated chloropolymers during their thermal conversions[J].Protection of Metals & Physical Chemistry of Surfaces,2009,45(4):398. 35 Cheng L X, Zhang L, Chen X Y, et al. Efficient conversion of waste polyvinyl chloride into nanoporous carbon incorporated with MnOx exhibiting superior electrochemical performance for supercapacitor application[J].Electrochimica Acta,2015,176:197. 36 Qiao W M, Song Y, Yoon S H, et al. Carbonization of waste PVC to develop porous carbon material without further activation[J].Waste Management,2006,26(6):592. 37 Solodovnichenko V S, Polyboyarov V A, Zhdanok A A, et al. Synthesis of carbon materials by the short-term mechanochemical activation of polyvinyl chloride[J].Procedia Engineering,2016,152:747. 38 Endo M, Kim Y J, Kakeda T, et al. Poly(vinylidene chloride)-based carbon as an electrode material for high power capacitors with an aqueous electrolyte[J].Folia Primatologica,2001,148(10):A1135. 39 Zheng D F, Jia M Q, Xu B, et al. The simple preparation of a hierarchical porous carbon with high surface area for high perfor-mance supercapacitors[J].Materials New Carbon 2013,28(2):151(in Chinese). 郑冬芳,贾梦秋,徐斌,等.高性能超级电容器用高比表面积、层次孔结构炭材料的简便制备[J].新型炭材料,2013,28(2):151. 40 Kim J I, Park S. A study of ion charge transfer on electrochemical behaviors of poly(vinylidene fluoride)-derived carbon electrodes[J].Journal of Analytical and Applied Pyrolysis,2012,98(10):22. 41 Xu B, Wu F, Chen S, et al. A simple method for preparing porous carbon by PVDC pyrolysis[J].Colloids & Surfaces A: Physicochemical & Engineering Aspects,2008,316(1):85. 42 Zhang G X, Wang J D, Qin B C, et al. Room-temperature rapid synthesis of metal-free doped carbon materials[J].Carbon,2017,115:28. 43 Zhang G X, Luo H X, Li H Y, et al. ZnO-promoted dechlorination for hierarchically nanoporous carbon as superior oxygen reduction electrocatalyst[J].Nano Energy,2016,26:241. 44 Hu J C, Zhang G X, Li H Y, et al. Thin sandwich graphene oxide@N-doped carbon composites for high-performance supercapacitors[J].RSC Advances,2017,7(36):22071. 45 Zhang C, Zhang G X, Li H Y, et al. Interfacial dehalogenation-enabled hollow N-doped carbon network as bifunctional catalysts for rechargeable Zn-air battery[J].Electrochimica Acta,2017,247:1044. 46 Xu B, Yue S F, Qiao N, et al. Easy preparation of nitrogen-doped porous carbon nanospheres and their application in supercapacitors[J].Materials Letters,2014,131(8):49. 47 Kim K S, Park S J. Synthesis of nitrogen doped microporous carbons prepared by activation-free method and their high electrochemical performance[J].Electrochimica Acta,2011,56(27):10130.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2018, Vol. 32 
