SCIENCE CHINA Materials, Volume 61, Issue 2: 210-232(2018) https://doi.org/10.1007/s40843-017-9154-2

Recent advances in flexible supercapacitors based on carbon nanotubes and graphene

More info
  • ReceivedAug 28, 2017
  • AcceptedOct 31, 2017
  • PublishedDec 15, 2017


Owing to the rapidly growing market for flexible electronics, there is an urgent demand to develop flexible energy storage devices. Flexible supercapacitors have received much attention due to their good flexibility, fast charge/discharge rate and long lifecycle times. Carbon nanotubes (CNTs) and graphene have good mechanical properties, which make them suitable for flexible supercapacitors. Based on different nanostructures of CNTs and graphene, we summarized the recent progress in CNTs- and graphene-based flexible supercapacitors with a brief description of the basic principles for evaluating their performance. Special emphasis was given to fabrication methods, capacitive performance and electrode configurations of different flexible supercapacitors. Furthermore, the remaining challenges and future research directions for CNTs- and graphene-based flexible supercapacitors have also been discussed.

Funded by

the National Natural Scientific Foundation of China(21503116)

Taishan Scholars Program of Shandong Province(tsqn20161004)

the Youth 1000 Talent Program of China.


This work was supported by the National Natural Science Foundation of China (21503116), Taishan Scholars Program of Shandong Province (TSQN20161004) and the Youth 1000 Talent Program of China.

Interest statement

The authors declare that they have no conflict of interests.

Contributions statement

Li K and Zhang J conceived and wrote the paper. All authors discussed and commented on the manuscript.

Author information

Kang Li obtained his bachelor degree from Nanjing University, and now is a graduate student in Shandong University under the supervision of Prof. Jintao Zhang. His research interest focuses on the carbon-based nanomaterials for flexible energy storage devices.

Jintao Zhang obtained his PhD degree from the National University of Singapore in 2012. Prior to joining Shandong University as a full professor, he has been a postdoctoral fellow at Nanyang Technological University and Case Western Reserve University. His research interests include the rational design & synthesis of advanced materials for electrochemical energy storage and conversion devices (e.g., metal-air batteries, supercapacitors and fuel cells) and electrocatalysis.


[1] Liu W, Song MS, Kong B, et al. Flexible and stretchable energy storage: recent advances and future perspectives. Adv Mater, 2017, 29: 1603436 CrossRef PubMed Google Scholar

[2] Wen L, Li F, Cheng HM. Carbon nanotubes and graphene for flexible electrochemical energy storage: from materials to devices. Adv Mater, 2016, 28: 4306-4337 CrossRef PubMed Google Scholar

[3] Zhang J, Zhao XS. On the configuration of supercapacitors for maximizing electrochemical performance. ChemSusChem, 2012, 5: 818-841 CrossRef PubMed Google Scholar

[4] Yu M, Wang Z, Han Y, et al. Recent progress in the development of anodes for asymmetric supercapacitors. J Mater Chem A, 2016, 4: 4634-4658 CrossRef Google Scholar

[5] Ge J, Lan M, Liu W, et al. Graphene quantum dots as efficient, metal-free, visible-light-active photocatalysts. Sci China Mater, 2016, 59: 12-19 CrossRef Google Scholar

[6] Lu K, Hu Z, Xiang Z, et al. Cation intercalation in manganese oxide nanosheets: effects on lithium and sodium storage. Angew Chem, 2016, 128: 10604-10608 CrossRef Google Scholar

[7] Huang Q, Wang D, Zheng Z. Textile-based electrochemical energy storage devices. Adv Energ Mater, 2016, 6: 1600783 CrossRef Google Scholar

[8] Liu L, Niu Z, Chen J. Unconventional supercapacitors from nanocarbon-based electrode materials to device configurations. Chem Soc Rev, 2016, 45: 4340-4363 CrossRef PubMed Google Scholar

[9] Guo K, Yu N, Hou Z, et al. Smart supercapacitors with deformable and healable functions. J Mater Chem A, 2017, 5: 16-30 CrossRef Google Scholar

[10] Gelinck GH, Huitema HEA, van Veenendaal E, et al. Flexible active-matrix displays and shift registers based on solution-processed organic transistors. Nat Mater, 2004, 3: 106-110 CrossRef PubMed ADS Google Scholar

[11] Moonen PF, Yakimets I, Huskens J. Fabrication of transistors on flexible substrates: from mass-printing to high-resolution alternative lithography strategies. Adv Mater, 2012, 24: 5526-5541 CrossRef PubMed Google Scholar

[12] Tee BCK, Wang C, Allen R, et al. An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications. Nat Nanotech, 2012, 7: 825-832 CrossRef PubMed ADS Google Scholar

[13] Hammock ML, Chortos A, Tee BCK, et al. 25th Anniversary Article: the evolution of electronic skin (e-skin): a brief history, design considerations, and recent progress. Adv Mater, 2013, 25: 5997-6038 CrossRef PubMed Google Scholar

[14] Zhang X, Zhang H, Lin Z, et al. Recent advances and challenges of stretchable supercapacitors based on carbon materials. Sci China Mater, 2016, 59: 475-494 CrossRef Google Scholar

[15] Fan Z, Yan J, Zhi L, et al. A three-dimensional carbon nanotube/graphene sandwich and its application as electrode in supercapacitors. Adv Mater, 2010, 22: 3723-3728 CrossRef PubMed Google Scholar

[16] Qin J, Zhou F, Xiao H, et al. Mesoporous polypyrrole-based graphene nanosheets anchoring redox polyoxometalate for all-solid-state micro-supercapacitors with enhanced volumetric capacitance. Sci China Mater, 2017, doi: 10.1007/s40843-017-9132-8 CrossRef Google Scholar

[17] Li YX, Gong ZL, Yang Y. Synthesis and characterization of Li2MnSiO4/C nanocomposite cathode material for lithium ion batteries. J Power Sources, 2007, 174: 528-532 CrossRef ADS Google Scholar

[18] Cao AM, Hu JS, Liang HP, et al. Self-assembled vanadium pentoxide (V2O5) hollow microspheres from nanorods and their application in lithium-ion batteries. Angew Chem Int Ed, 2005, 44: 4391-4395 CrossRef PubMed Google Scholar

[19] Cai X, Zhang C, Zhang S, et al. Application of carbon fibers to flexible, miniaturized wire/fiber-shaped energy conversion and storage devices. J Mater Chem A, 2017, 5: 2444-2459 CrossRef Google Scholar

[20] Wu Z, Zhang X. N,O-codoped porous carbon nanosheets for capacitors with ultra-high capacitance. Sci China Mater, 2016, 59: 547-557 CrossRef Google Scholar

[21] Wu S, Zhu Y. Highly densified carbon electrode materials towards practical supercapacitor devices. Sci China Mater, 2017, 60: 25-38 CrossRef Google Scholar

[22] Lu K, Zhang J, Wang Y, et al. Interfacial deposition of three-dimensional nickel hydroxide nanosheet-graphene aerogel on Ni wire for flexible fiber asymmetric supercapacitors. ACS Sustain Chem Eng, 2017, 5: 821-827 CrossRef Google Scholar

[23] Yin H, Tang Z. Ultrathin two-dimensional layered metal hydroxides: an emerging platform for advanced catalysis, energy conversion and storage. Chem Soc Rev, 2016, 45: 4873-4891 CrossRef PubMed Google Scholar

[24] Mendoza-Sánchez B, Gogotsi Y. Synthesis of two-dimensional materials for capacitive energy storage. Adv Mater, 2016, 28: 6104-6135 CrossRef PubMed Google Scholar

[25] Gao Y. Graphene and polymer composites for supercapacitor applications: a review. Nanoscale Res Lett, 2017, 12: 387 CrossRef PubMed ADS Google Scholar

[26] Wang K, Zhang X, Sun X, et al. Conducting polymer hydrogel materials for high-performance flexible solid-state supercapacitors. Sci China Mater, 2016, 59: 412-420 CrossRef Google Scholar

[27] Wang K, Wu H, Meng Y, et al. Conducting polymer nanowire arrays for high performance supercapacitors. Small, 2014, 10: 14-31 CrossRef PubMed Google Scholar

[28] Zhang G, Jin X, Li H, et al. N-doped crumpled graphene: bottom-up synthesis and its superior oxygen reduction performance. Sci China Mater, 2016, 59: 337-347 CrossRef Google Scholar

[29] Shao Y, El-Kady MF, Wang LJ, et al. Graphene-based materials for flexible supercapacitors. Chem Soc Rev, 2015, 44: 3639-3665 CrossRef PubMed Google Scholar

[30] Zhang J, Dai L. Nitrogen, phosphorus, and fluorine tri-doped graphene as a multifunctional catalyst for self-powered electrochemical water splitting. Angew Chem Int Ed, 2016, 55: 13296-13300 CrossRef PubMed Google Scholar

[31] Yu M, Zhou S, Liu Y, et al. Long life rechargeable Li-O2 batteries enabled by enhanced charge transfer in nanocable-like Fe@N-doped carbon nanotube catalyst. Sci China Mater, 2017, 60: 415-426 CrossRef Google Scholar

[32] Ma Z, Tao L, Liu D, et al. Ultrafine nano-sulfur particles anchored on in situ exfoliated graphene for lithium-sulfur batteries. J Mater Chem A, 2017, 5: 9412-9417 CrossRef Google Scholar

[33] Liu Z, Zhao Z, Wang Y, et al. In situ exfoliated, edge-rich, oxygen-functionalized graphene from carbon fibers for oxygen electrocatalysis. Adv Mater, 2017, 29: 1606207 CrossRef PubMed Google Scholar

[34] Wang S, Jiang SP. Prospects of fuel cell technologies. Nat Sci Rev, 2017, : nww099 CrossRef Google Scholar

[35] Yan D, Li Y, Huo J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions. Adv Mater, 2017, 414: 1606459 CrossRef PubMed Google Scholar

[36] Dong L, Xu C, Li Y, et al. Flexible electrodes and supercapacitors for wearable energy storage: a review by category. J Mater Chem A, 2016, 4: 4659-4685 CrossRef Google Scholar

[37] Iijima S. Helical microtubules of graphitic carbon. Nature, 1991, 354: 56-58 CrossRef ADS Google Scholar

[38] De Volder MFL, Tawfick SH, Baughman RH, et al. Carbon nanotubes: present and future commercial applications. Science, 2013, 339: 535-539 CrossRef PubMed ADS Google Scholar

[39] Park S, Vosguerichian M, Bao Z. A review of fabrication and applications of carbon nanotube film-based flexible electronics. Nanoscale, 2013, 5: 1727-1752 CrossRef PubMed ADS Google Scholar

[40] Yang F, Wang X, Zhang D, et al. Chirality-specific growth of single-walled carbon nanotubes on solid alloy catalysts. Nature, 2014, 510: 522-524 CrossRef PubMed ADS Google Scholar

[41] Niu Z, Luan P, Shao Q, et al. A “skeleton/skin” strategy for preparing ultrathin free-standing single-walled carbon nanotube/polyaniline films for high performance supercapacitor electrodes. Energ Environ Sci, 2012, 5: 8726-8733 CrossRef Google Scholar

[42] Kang YJ, Chung H, Han CH, et al. All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes. Nanotechnology, 2012, 23: 289501 CrossRef ADS Google Scholar

[43] Niu Z, Dong H, Zhu B, et al. Highly stretchable, integrated supercapacitors based on single-walled carbon nanotube films with continuous reticulate architecture. Adv Mater, 2013, 25: 1058-1064 CrossRef PubMed Google Scholar

[44] Zeng S, Chen H, Cai F, et al. Electrochemical fabrication of carbon nanotube/polyaniline hydrogel film for all-solid-state flexible supercapacitor with high areal capacitance. J Mater Chem A, 2015, 3: 23864-23870 CrossRef Google Scholar

[45] Yu J, Lu W, Pei S, et al. Omnidirectionally stretchable high-performance supercapacitor based on isotropic buckled carbon nanotube films. ACS Nano, 2016, 10: 5204-5211 CrossRef Google Scholar

[46] Lv T, Yao Y, Li N, et al. Highly stretchable supercapacitors based on aligned carbon nanotube/molybdenum disulfide composites. Angew Chem Int Ed, 2016, 55: 9191-9195 CrossRef PubMed Google Scholar

[47] Li J, Lu W, Yan Y, et al. High performance solid-state flexible supercapacitor based on Fe3O4/carbon nanotube/polyaniline ternary films. J Mater Chem A, 2017, 5: 11271-11277 CrossRef Google Scholar

[48] Zhao J, Chen J, Xu S, et al. Hierarchical nimn layered double hydroxide/carbon nanotubes architecture with superb energy density for flexible supercapacitors. Adv Funct Mater, 2014, 24: 2938-2946 CrossRef Google Scholar

[49] Zhao MQ, Ren CE, Ling Z, et al. Flexible Mxene/carbon nanotube composite paper with high volumetric capacitance. Adv Mater, 2015, 27: 339-345 CrossRef PubMed Google Scholar

[50] Yuksel R, Sarioba Z, Cirpan A, et al. Transparent and flexible supercapacitors with single walled carbon nanotube thin film electrodes. ACS Appl Mater Interfaces, 2014, 6: 15434-15439 CrossRef PubMed Google Scholar

[51] Du L, Yang P, Yu X, et al. Flexible supercapacitors based on carbon nanotube/MnO2 nanotube hybrid porous films for wearable electronic devices. J Mater Chem A, 2014, 2: 17561-17567 CrossRef Google Scholar

[52] Chen Y, Du L, Yang P, et al. Significantly enhanced robustness and electrochemical performance of flexible carbon nanotube-based supercapacitors by electrodepositing polypyrrole. J Power Sources, 2015, 287: 68-74 CrossRef ADS Google Scholar

[53] Yu M, Zhang Y, Zeng Y, et al. Water surface assisted synthesis of large-scale carbon nanotube film for high-performance and stretchable supercapacitors. Adv Mater, 2014, 26: 4724-4729 CrossRef PubMed Google Scholar

[54] de Souza VHR, Oliveira MM, Zarbin AJG. Thin and flexible all-solid supercapacitor prepared from novel single wall carbon nanotubes/polyaniline thin films obtained in liquid-liquid interfaces. J Power Sources, 2014, 260: 34-42 CrossRef ADS Google Scholar

[55] Shin SR, Farzad R, Tamayol A, et al. A bioactive carbon nanotube-based ink for printing 2D and 3D flexible electronics. Adv Mater, 2016, 28: 3280-3289 CrossRef PubMed Google Scholar

[56] Song L, Cao X, Li L, et al. General method for large-area films of carbon nanomaterials and application of a self-assembled carbon nanotube film as a high-performance electrode material for an all-solid-state supercapacitor. Adv Funct Mater, 2017, 27: 1700474 CrossRef Google Scholar

[57] Chen C, Cao J, Lu Q, et al. Foldable all-solid-state supercapacitors integrated with photodetectors. Adv Funct Mater, 2017, 27: 1604639 CrossRef Google Scholar

[58] Lee H, Kim H, Cho MS, et al. Fabrication of polypyrrole (PPy)/carbon nanotube (CNT) composite electrode on ceramic fabric for supercapacitor applications. Electrochim Acta, 2011, 56: 7460-7466 CrossRef Google Scholar

[59] Lu X, Dou H, Yuan C, et al. Polypyrrole/carbon nanotube nanocomposite enhanced the electrochemical capacitance of flexible graphene film for supercapacitors. J Power Sources, 2012, 197: 319-324 CrossRef ADS Google Scholar

[60] Huang F, Vanhaecke E, Chen D. In situ polymerization and characterizations of polyaniline on MWCNT powders and aligned MWCNT films. Catal Today, 2010, 150: 71-76 CrossRef Google Scholar

[61] Zhang H, Cao G, Yang Y. Carbon nanotube arrays and their composites for electrochemical capacitors and lithium-ion batteries. Energ Environ Sci, 2009, 2: 932-943 CrossRef Google Scholar

[62] Cai Z, Li L, Ren J, et al. Flexible, weavable and efficient microsupercapacitor wires based on polyaniline composite fibers incorporated with aligned carbon nanotubes. J Mater Chem A, 2013, 1: 258-261 CrossRef Google Scholar

[63] Yu D, Goh K, Wang H, et al. Scalable synthesis of hierarchically structured carbon nanotube-graphene fibres for capacitive energy storage. Nat Nanotech, 2014, 9: 555-562 CrossRef PubMed ADS Google Scholar

[64] Huang F, Lou F, Chen D. Exploring aligned-carbon-nanotubes@polyaniline arrays on household Al as supercapacitors. ChemSusChem, 2012, 5: 888-895 CrossRef PubMed Google Scholar

[65] Lin H, Li L, Ren J, et al. Conducting polymer composite film incorporated with aligned carbon nanotubes for transparent, flexible and efficient supercapacitor. Sci Rep, 2013, 3: 1353 CrossRef PubMed ADS Google Scholar

[66] Chen T, Peng H, Durstock M, et al. High-performance transparent and stretchable all-solid supercapacitors based on highly aligned carbon nanotube sheets. Sci Rep, 2014, 4: 3612 CrossRef PubMed ADS Google Scholar

[67] Pan S, Lin H, Deng J, et al. Novel wearable energy devices based on aligned carbon nanotube fiber textiles. Adv Energ Mater, 2015, 5: 1401438 CrossRef Google Scholar

[68] Malik R, Zhang L, McConnell C, et al. Three-dimensional, free-standing polyaniline/carbon nanotube composite-based electrode for high-performance supercapacitors. Carbon, 2017, 116: 579-590 CrossRef Google Scholar

[69] Cherusseri J, Kar KK. Ultra-flexible fibrous supercapacitors with carbon nanotube/polypyrrole brush-like electrodes. J Mater Chem A, 2016, 4: 9910-9922 CrossRef Google Scholar

[70] Zhang G, Song Y, Zhang H, et al. Radially aligned porous carbon nanotube arrays on carbon fibers: a hierarchical 3D carbon nanostructure for high-performance capacitive energy storage. Adv Funct Mater, 2016, 26: 3012-3020 CrossRef Google Scholar

[71] Reit R, Nguyen J, Ready W. Growth time performance dependence of vertically aligned carbon nanotube supercapacitors grown on aluminum substrates. Electrochim Acta, 2013, 91: 96-100 CrossRef Google Scholar

[72] Zhao W, Li Y, Wu S, et al. Highly stable carbon nanotube/polyaniline porous network for multifunctional applications. ACS Appl Mater Interfaces, 2016, 8: 34027-34033 CrossRef Google Scholar

[73] Li P, Kong C, Shang Y, et al. Highly deformation-tolerant carbon nanotube sponges as supercapacitor electrodes. Nanoscale, 2013, 5: 8472-8479 CrossRef PubMed ADS Google Scholar

[74] Cheng X, Gui X, Lin Z, et al. Three-dimensional α-Fe2O3/carbon nanotube sponges as flexible supercapacitor electrodes. J Mater Chem A, 2015, 3: 20927-20934 CrossRef Google Scholar

[75] Li P, Shi E, Yang Y, et al. Carbon nanotube-polypyrrole core-shell sponge and its application as highly compressible supercapacitor electrode. Nano Res, 2013, 7: 209-218 CrossRef Google Scholar

[76] Wang K, Meng Q, Zhang Y, et al. High-performance two-ply yarn supercapacitors based on carbon nanotubes and polyaniline nanowire arrays. Adv Mater, 2013, 25: 1494-1498 CrossRef PubMed Google Scholar

[77] Zhang D, Miao M, Niu H, et al. Core-spun carbon nanotube yarn supercapacitors for wearable electronic textiles. ACS Nano, 2014, 8: 4571-4579 CrossRef PubMed Google Scholar

[78] Shang Y, Wang C, He X, et al. Self-stretchable, helical carbon nanotube yarn supercapacitors with stable performance under extreme deformation conditions. Nano Energ, 2015, 12: 401-409 CrossRef Google Scholar

[79] Li P, Yang Y, Shi E, et al. Core-double-shell, carbon nanotube@polypyrrole@MnO2 sponge as freestanding, compressible supercapacitor electrode. ACS Appl Mater Interfaces, 2014, 6: 5228-5234 CrossRef PubMed Google Scholar

[80] Dong Z, Jiang C, Cheng H, et al. Facile fabrication of light, flexible and multifunctional graphene fibers. Adv Mater, 2012, 24: 1856-1861 CrossRef PubMed Google Scholar

[81] Cong HP, Ren XC, Wang P, et al. Wet-spinning assembly of continuous, neat and macroscopic graphene fibers. Sci Rep, 2012, 2: 613 CrossRef PubMed ADS Google Scholar

[82] Li X, Zhao T, Chen Q, et al. Flexible all solid-state supercapacitors based on chemical vapor deposition derived graphene fibers. Phys Chem Chem Phys, 2013, 15: 17752-17757 CrossRef PubMed ADS Google Scholar

[83] Li X, Zhao T, Wang K, et al. Directly drawing self-assembled, porous, and monolithic graphene fiber from chemical vapor deposition grown graphene film and its electrochemical properties. Langmuir, 2011, 27: 12164-12171 CrossRef PubMed Google Scholar

[84] Meng Y, Zhao Y, Hu C, et al. All-graphene core-sheath microfibers for all-solid-state, stretchable fibriform supercapacitors and wearable electronic textiles. Adv Mater, 2013, 25: 2326-2331 CrossRef PubMed Google Scholar

[85] Li Y, Sheng K, Yuan W, et al. A high-performance flexible fibre-shaped electrochemical capacitor based on electrochemically reduced graphene oxide. Chem Commun, 2013, 49: 291-293 CrossRef PubMed Google Scholar

[86] Hu Y, Cheng H, Zhao F, et al. All-in-one graphene fiber supercapacitor. Nanoscale, 2014, 6: 6448-6451 CrossRef PubMed ADS Google Scholar

[87] McDonough JR, Choi JW, Yang Y, et al. Carbon nanofiber supercapacitors with large areal capacitances. Appl Phys Lett, 2009, 95: 243109 CrossRef ADS Google Scholar

[88] Kim JH, Kang SH, Zhu K, et al. Ni-NiO core-shell inverse opal electrodes for supercapacitors. Chem Commun, 2011, 47: 5214-5216 CrossRef PubMed Google Scholar

[89] Chen S, Ma W, Cheng Y, et al. Scalable non-liquid-crystal spinning of locally aligned graphene fibers for high-performance wearable supercapacitors. Nano Energ, 2015, 15: 642-653 CrossRef Google Scholar

[90] Cheng H, Dong Z, Hu C, et al. Textile electrodes woven by carbon nanotube-graphene hybrid fibers for flexible electrochemical capacitors. Nanoscale, 2013, 5: 3428-3434 CrossRef PubMed ADS Google Scholar

[91] Ma Y, Li P, Sedloff JW, et al. Conductive graphene fibers for wire-shaped supercapacitors strengthened by unfunctionalized few-walled carbon nanotubes. ACS Nano, 2015, 9: 1352-1359 CrossRef PubMed Google Scholar

[92] Chen Q, Meng Y, Hu C, et al. MnO2-modified hierarchical graphene fiber electrochemical supercapacitor. J Power Sources, 2014, 247: 32-39 CrossRef ADS Google Scholar

[93] Wang S, Liu N, Su J, et al. Highly stretchable and self-healable supercapacitor with reduced graphene oxide based fiber springs. ACS Nano, 2017, 11: 2066-2074 CrossRef Google Scholar

[94] Wang G, Sun X, Lu F, et al. Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors. Small, 2012, 8: 452-459 CrossRef PubMed Google Scholar

[95] Yang X, Zhu J, Qiu L, et al. Bio-inspired effective prevention of restacking in multilayered graphene films: towards the next generation of high-performance supercapacitors. Adv Mater, 2011, 23: 2833-2838 CrossRef PubMed Google Scholar

[96] Cheng Y, Lu S, Zhang H, et al. Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors. Nano Lett, 2012, 12: 4206-4211 CrossRef PubMed ADS Google Scholar

[97] El-Kady MF, Strong V, Dubin S, et al. Laser scribing of high-performance and flexible graphene-based electrochemical capacitors. Science, 2012, 335: 1326-1330 CrossRef PubMed ADS Google Scholar

[98] Cong HP, Ren XC, Wang P, et al. Flexible graphene-polyaniline composite paper for high-performance supercapacitor. Energ Environ Sci, 2013, 6: 1185 CrossRef Google Scholar

[99] Yoo JJ, Balakrishnan K, Huang J, et al. Ultrathin planar graphene supercapacitors. Nano Lett, 2011, 11: 1423-1427 CrossRef PubMed ADS Google Scholar

[100] Liu F, Song S, Xue D, et al. Folded structured graphene paper for high performance electrode materials. Adv Mater, 2012, 24: 1089-1094 CrossRef PubMed Google Scholar

[101] Li N, Lv T, Yao Y, et al. Compact graphene/MoS2 composite films for highly flexible and stretchable all-solid-state supercapacitors. J Mater Chem A, 2017, 5: 3267-3273 CrossRef Google Scholar

[102] Lu X, Dou H, Gao B, et al. A flexible graphene/multiwalled carbon nanotube film as a high performance electrode material for supercapacitors. Electrochim Acta, 2011, 56: 5115-5121 CrossRef Google Scholar

[103] Pham DT, Lee TH, Luong DH, et al. Carbon nanotube-bridged graphene 3D building blocks for ultrafast compact supercapacitors. ACS Nano, 2015, 9: 2018-2027 CrossRef PubMed Google Scholar

[104] Du P, Hu X, Yi C, et al. Self-powered electronics by integration of flexible solid-state graphene-based supercapacitors with high performance perovskite hybrid solar cells. Adv Funct Mater, 2015, 25: 2420-2427 CrossRef Google Scholar

[105] El-Kady MF, Ihns M, Li M, et al. Engineering three-dimensional hybrid supercapacitors and microsupercapacitors for high-performance integrated energy storage. Proc Natl Acad Sci USA, 2015, 112: 4233-4238 CrossRef PubMed ADS Google Scholar

[106] Xie B, Wang Y, Lai W, et al. Laser-processed graphene based micro-supercapacitors for ultrathin, rollable, compact and designable energy storage components. Nano Energ, 2016, 26: 276-285 CrossRef Google Scholar

[107] Xiong Z, Liao C, Han W, et al. Mechanically tough large-area hierarchical porous graphene films for high-performance flexible supercapacitor applications. Adv Mater, 2015, 27: 4469-4475 CrossRef PubMed Google Scholar

[108] Xie J, Sun X, Zhang N, et al. Layer-by-layer β-Ni(OH)2/graphene nanohybrids for ultraflexible all-solid-state thin-film supercapacitors with high electrochemical performance. Nano Energ, 2013, 2: 65-74 CrossRef Google Scholar

[109] Wu ZS, Tan YZ, Zheng S, et al. Bottom-up fabrication of sulfur-doped graphene films derived from sulfur-annulated nanographene for ultrahigh volumetric capacitance micro-supercapacitors. J Am Chem Soc, 2017, 139: 4506-4512 CrossRef PubMed Google Scholar

[110] Ai W, Luo Z, Jiang J, et al. Nitrogen and sulfur codoped graphene: multifunctional electrode materials for high-performance Li-ion batteries and oxygen reduction reaction. Adv Mater, 2014, 26: 6186-6192 CrossRef PubMed Google Scholar

[111] Wu ZS, Winter A, Chen L, et al. Three-dimensional nitrogen and boron co-doped graphene for high-performance all-solid-state supercapacitors. Adv Mater, 2012, 24: 5130-5135 CrossRef PubMed Google Scholar

[112] Chen X, Chen X, Xu X, et al. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials. Nanoscale, 2014, 6: 13740-13747 CrossRef PubMed ADS Google Scholar

[113] Dong XC, Xu H, Wang XW, et al. 3D graphene-cobalt oxide electrode for high-performance supercapacitor and enzymeless glucose detection. ACS Nano, 2012, 6: 3206-3213 CrossRef PubMed Google Scholar

[114] Choi BG, Yang MH, Hong WH, et al. 3D macroporous graphene frameworks for supercapacitors with high energy and power densities. ACS Nano, 2012, 6: 4020-4028 CrossRef PubMed Google Scholar

[115] Xu Y, Lin Z, Huang X, et al. Flexible solid-state supercapacitors based on three-dimensional graphene hydrogel films. ACS Nano, 2013, 7: 4042-4049 CrossRef PubMed Google Scholar

[116] Shi JL, Du WC, Yin YX, et al. Hydrothermal reduction of three-dimensional graphene oxide for binder-free flexible supercapacitors. J Mater Chem A, 2014, 2: 10830 CrossRef Google Scholar

[117] Shao Y, El-Kady MF, Lin CW, et al. 3D freeze-casting of cellular graphene films for ultrahigh-power-density supercapacitors. Adv Mater, 2016, 28: 6719-6726 CrossRef PubMed Google Scholar

[118] Deville S. Freeze-casting of porous ceramics: a review of current achievements and issues. Adv Eng Mater, 2008, 10: 155-169 CrossRef Google Scholar

[119] Yu P, Zhao X, Huang Z, et al. Free-standing three-dimensional graphene and polyaniline nanowire arrays hybrid foams for high-performance flexible and lightweight supercapacitors. J Mater Chem A, 2014, 2: 14413-14420 CrossRef Google Scholar

[120] Jurewicz K, Vix-Guterl C, Frackowiak E, et al. Capacitance properties of ordered porous carbon materials prepared by a templating procedure. J Phys Chem Solids, 2004, 65: 287-293 CrossRef ADS Google Scholar

[121] Álvarez S, Blanco-López MC, Miranda-Ordieres AJ, et al. Electrochemical capacitor performance of mesoporous carbons obtained by templating technique. Carbon, 2005, 43: 866-870 CrossRef Google Scholar

[122] Li HQ, Luo JY, Zhou XF, et al. An ordered mesoporous carbon with short pore length and its electrochemical performances in supercapacitor applications. J Electrochem Soc, 2007, 154: A731 CrossRef Google Scholar

[123] Zhi J, Zhao W, Liu X, et al. Highly conductive ordered mesoporous carbon based electrodes decorated by 3D graphene and 1D silver nanowire for flexible supercapacitor. Adv Funct Mater, 2014, 24: 2013-2019 CrossRef Google Scholar

[124] Qin T, Wan Z, Wang Z, et al. 3D flexible O/N co-doped graphene foams for supercapacitor electrodes with high volumetric and areal capacitances. J Power Sources, 2016, 336: 455-464 CrossRef ADS Google Scholar

  • Figure 1

    Schematic illustration of a two-electrode supercapacitor.

  • Figure 2

    (a) Schematic illustration for preparing buckled SWCNT film on PDMS. Reproduced with permission from Ref. [43]. Copyright 2013, Wiley-VCH. (b) Photograph of the fabricated supercapacitors without carbon paste current collectors. Reproduced with permission from Ref. [50]. Copyright 2014, the American Chemical Society. SEM images of buckled structures formed in CNT films at different levels of omnidirectional pre-strain (c) 50%, (d) 100%, (e) 150%, and (f) 200%. (g) Photos of buckled CNT film at various stretching states. Reproduced with permission from Ref. [45]. Copyright 2014, the American Chemical Society.

  • Figure 3

    (a) Schematic illustration for the assembly of CNTs on copper and photographs of the copper foils before and after the deposition of CNTs. (b) SA-CNT films transferred to different substrates: glass (left), PET (middle), paper (right). Reproduced with permission from Ref. [56]. Copyright 2017, Wiley-VCH. (c) Schematic diagram showing the GelMA/DNA-coated MWCNT inks formed though hydrogen bonding, hydrophobic interactions, and π–π stacking interactions between MWCNT and GelMA/DNA. (d) Photograph of black conductive ink and high-resolution TEM image of individual or bundled GelMA/DNA-wrapped MWCNTs. (e) Fluorescence images of cardiac fibroblasts cultured on ink patterns printed on PEG-coated PET film. F-actin and cell nuclei were immunostained and fluorescently labeled green and blue, respectively. Reproduced with permission from Ref. [55]. Copyright 2016, Wiley-VCH.

  • Figure 4

    (a) SEM image of a single layer of SWCNT bundles peeled off from a thick film. (b) The sketch diagrams of a single layer film based on (left) continuous SWCNT/PANI reticulate structure and (right) randomly overlapped SWCNT/PANI bundles. “Blue” and “brown” parts represent SWCNT bundle skeleton and PANI skin. Reproduced with permission from [41]. Copyright 2012, the Royal Society of Chemistry. (c) Scheme of re-expanding process of CNT film. Reproduced with permission from Ref. [44]. Copyright 2015, the Royal Society of Chemistry. (d) Ragone plots of the supercapacity device (inset is 53 blue LEDs powered by a flexible SC pack consisting of 4 series-connected supercapacity devices). Reproduced with permission from Ref. [52] Copyright 2015, Elsevier. (e) Cross-sectional SEM images of Ti3C2Tx/MWCNT papers. Reproduced with permission from Ref. [49]. Copyright 2014, Wiley-VCH. (f) SEM images of aligned CNT/MoS2 composite films with 3.1 wt.% amounts of MoS2. Reproduced with permission from Ref. [46]. Copyright 2016, Wiley-VCH. (g) Cross-sectional SEM image of the freestanding CNT/MnO2 NT hybrid film. Reproduced with permission from Ref. [51]. Copyright 2014, the Royal Society of Chemistry.

  • Figure 5

    (a) Digital photograph of the flexible symmetric supercapacitor with a filtration paper as separator. Reproduced with permission from Ref. [64]. Copyright 2012, Wiley-VCH. SEM images of bare aligned MWCNTs at low (b) and high (c) resolution. The supercapacitor wire woven into other CNT fibers (d) and a textile composed of aramid fibers (e). The red arrows show the wire. Reproduced with permission from Ref. [62]. Copyright 2013, the Royal Society of Chemistry. (f) Photograph of multilayered clothes. (g) Schematic illustration to the integrated energy textile. The enlarged view shows the working mechanism. Reproduced with permission from Ref. [67]. Copyright 2014, Wiley-VCH.

  • Figure 6

    SEM images of CNT arrays before (a) and after (b) PANI deposition. Reproduced with permission from Ref. [68] Copyright 2017, Elsevier. Low (c) and high (d) magnification SEM images of the PCNTAs@CFs. (e) Photographs of PCNTAs@CFs symmetric device at different bending states. (f) Cycle stability tested at different bending states with the inset showing CV curves obtained at different bending states at a scan rate of 500 mV s−1. Reproduced with permission from Ref. [70]. Copyright 2016, Wiley-VCH.

  • Figure 7

    (a) CV curves of the CNT@Fe2O3 sponge under different compressed conditions (0, 10%, 30%, 50% and 70%) at 5 mV s−1. The inset shows the specific capacitance of the samples under different compressive strains at a scan rate of 5 mV s−1. Reproduced with permission from Ref. [74]. Copyright 2015, the Royal Society of Chemistry. (b) Continuous spinning of Pt/CNT core/sheath yarns: photograph of the flyer spinner and schematics of working elements. (c) Schematic showing formation of the core/sheath yarn structure. Reproduced with permission from Ref. [77]. Copyright 2014, the American Chemical Society.

  • Figure 8

    (a) Cross-section view of a GF@3D-G showing the core GF surrounding with standing graphene sheets. Photos of the textile embedded with two GF@3D-G fiber supercapacitors in flat (b) and bending (c) state, respectively. (d) CV curves of two GF@3D-G fiber supercapacitors as the textile in flat (b) and bending (c) states with a scan rate of 50 mV s−1. Reproduced with permission from Ref. [84]. Copyright 2013, Wiley-VCH. (e) The scheme of the RGO-GO-RGO supercapacitor device, where RGO layers were in contact with the Au sheets. The thin plastic layer of polyvinylidene chloride (PVDC) was partially coated on the Au surface to prevent the short circuit of two Au electrodes. Reproduced with permission from Ref. [86]. Copyright 2014, the Royal Society of Chemistry.

  • Figure 9

    SEM images of the cross-section and the surface of RGO fibers prepared by NLC (a) and LC (b) spinning. R represent the jet stretch ratio. (c) Photo of a 3 V yarn supercapacitor assembled from six bundles of RGO fibers. This device was sewed into a textile and could power a red light-emission diode (LED) for 5 min after being charged to 3 V at a scan rate of 10 mV s−1 for (5 min). Reproduced with permission from Ref. [89]. Copyright 2015, Elsevier. (d) Schematic diagrams of the stretchable and self-healable mechanism. Reproduced with permission from Ref. [93]. Copyright 2017, the American Chemical Society.

  • Figure 10

    (a) Cross-sectional SEM image of the original GP without CB. (b) Cross sectional HIM images of the pillared GP with the addition of 20 vol.% CB. Reproduced with permission from Ref. [94]. Copyright 2012, Wiley-VCH. (c) Schematic of the 3D SWCNT-bridged graphene block. KOH activation generates nanoscale pores in the graphene layers. (d) Cross-sectional SEM image containing dangling SWCNTs (magnified in the inset). Reproduced with permission from Ref. [103]. Copyright 2015, the American Chemical Society. (e) Schematic illustration of ultrathin laser-processed graphene based micro-planar supercapacitors. (f) Photographic image of LPG-MPS arrays. (Inset is a single unit). Reproduced with permission from Ref. [106]. Copyright 2016, Elsevier.

  • Figure 11

    (a) SEM images of the RGO films. Reproduced with permission from Ref. [107]. Copyright 2015, Wiley-VCH. (b) Schematic illustration of the formation mechanism of layer-by-layer b-Ni(OH)2/graphene nanohybrids. (c) HR-TEM image and the structural model of the layer-by-layer nanohybrids. Reproduced with permission from Ref. [108]. Copyright 2012, Elsevier.

  • Figure 12

    (a) Schematic diagram and photographs of the fabrication process of flexible solid-state supercapacitors based on graphene hydrogel films. (b) CV curves of the flexible solid-state device at 10 mV s−1 for different bending angles. Reproduced with permission from Ref. [115]. Copyright 2013, the American Chemical Society. (c) Two devices connected in series can power the digital temperature and humidity meter at both a normal (right) and bending (left) state. Reproduced with permission from Ref. [116]. Copyright 2014, the Royal Society of Chemistry. (d) Cross-section SEM image of a 3D porous RGO film after long-term reduction. (e) CV curves of an all solid-state supercapacitor tested at a scan rate of 50 mV s−1 under different bending angles. (f) The device retains about 91% of the initial capacitance after 500 cycles when tested under the bent state. Reproduced with permission from Ref. [117]. Copyright 2016, Wiley-VCH.

  • Table 1   Comparison of the performance of graphene-based flexible supercapacitors



    (S cm−1)


    Specific capacitance

    (F g−1)

    Areal capacitance (mF cm−2)

    Energy density

    Power density

    Capacitance retention in flexibility test







    0.4–1.7×10−7 W h cm−2

    6–100×10−6 W cm−2


    RGO on Au wire







    90% (1000 cycles at 90°)


    RGO-GO-RGO fiber


    1-Butyl-3-methylimidazolium tetra-fluoroborate



    2–5.4×10−4 W h cm−2

    3.6–9×10−2 W cm−2

    ~100% (160 bending test)


    RGO fiber


    1 mol L−1 H2SO4



    5.76 W h kg−1

    47.3 W kg−1

    91% (1000 times bending from 0–180°)


    CNT/graphene fiber


    1 mol L−1 Na2SO4





    ~50% (1000 bending cycles)


    GO/FWCNT fiber




    38.8 F cm−3

    3.4 mW h cm−3

    0.7 W cm−3








    1.46 ×

    10−3 mW h cm−2

    2.94 mW cm−2










    ~105% (1000 straight-bend cycles)


    RGO/MWCNTs/PPy fiber




    25.9 F cm−3

    0.94 mW h cm−3

    7.32 mW cm−3

    82.4% (stretched to 200%)


    CB pillared graphene paper


    6 mol L−1 KOH



    26 W h kg−1

    5.1 kW kg−1



    GN/MWCNT film


    6 mol L−1 KOH







    CNT-bridged graphene


    1-Ethyl-3-methylimidazolium tetrafluoroborate



    117.2 W h L−1

    424 kW L−1



    SSG film





    8.01 W h kg−1

    5.97 kW kg−1



    LSG film





    1.36 mW h cm−3

    20 W cm−3

    95% (1000 bending cycles)




    1 mol L−1 Na2SO4



    22–42 W h L−1

    10 kW L−1








    0.98 mW h cm−3

    300 mW cm−3



    RGO film


    1 mol L−1 H2SO4



    4.9 µW h cm −2

    40,000 µW cm−2

    96.7% (5,000 bending cycles)


    Graphene-PANI paper

    15 Ω sq−1

    1 mol L−1 H2SO4














    ~100% (500 bending cycles)


    Sulfur-doped graphene



    553 μF cm−2

    3.1 mW h cm−3

    1191 W cm−3


    Graphene hydrogel





    0.61 W h kg−1

    0.67 kW kg−1



    3D H-RGO


    6 mol L−1 KOH





    80% (120° 10,000 cycles)


    Cellular graphene films





    1.11 W h L−1

    7.8–14.3 kW kg−1

    91% (500 bending cycles)


    RGO-F/PANI foam


    1 mol L−1 H2SO4



    17.6 W h kg−1

    98 kW kg−1





    6 mol L−1 KOH


    4.5 W h kg−1

    5040 W kg−1

    92% (200 bending cycles at 90°)


    O/N codoped graphene foam


    1 mol L−1 H2SO4


    375 μF cm−2

    16 W h kg−1

    17 kW kg−1



Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有