Compact self-standing layered film assembled by V2O5·nH2O/CNTs 2D/1D composites for high volumetric capacitance flexible supercapacitors

More info
  • ReceivedNov 9, 2018
  • AcceptedDec 17, 2018
  • PublishedJan 17, 2019


Funded by

the National Natural Science Foundation of China(51702048,21603157)

the National Basic Research Program of China(2015CB932600)

the Jiangxi Provincial Department of Education(GJJ170459,GJJ170457)


This work was supported by the National Natural Science Foundation of China (51702048 and 21603157), the National Basic Research Program of China (2015CB932600), and Jiangxi Provincial Department of Education (GJJ170459 and GJJ170457).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Guo K performed the experiments; Li Y and Li C conducted the characterization; Yu N and Li H performed the data analysis; all authors contributed to the discussion and preparation of the manuscript. The final version of the manuscript was approved by all authors.

Author information

Kai Guo received his PhD degree in material science from Huazhong University of Science and Technology in 2017 and then joined the School of Chemistry, Biology and Materials Science, East China University of Technology. His research interest focuses on material synthesis and device design of flexible supercapacitors and aqueous batteries.

Neng Yu received her PhD degree from Huazhong University of Science and Technology in 2015. Currently, she works in the School of Chemistry, Biology and Materials Science, East China University of Technology. Her research interest is in the field of electrochemical energy materials and devices, with a focus on hybrid nanomaterials, supercapacitors and lithium ion batteries.

Huiqiao Li received her BSc degree in chemistry from Zhengzhou University in 2003, and then received her PhD degree in physical chemistry from Fudan University in 2008. Afterwards, she worked for 4 years at Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Japan. Currently, she is a full Professor of School of Materials Science and Engineering, Huazhong University of Science and Technology (HUST). Her research interest includes energy storage materials and electrochemical power sources such as lithium-ion batteries, sodium-ion batteries and supercapacitors.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Wang X, Lu X, Liu B, et al. Flexible energy-storage devices: design consideration and recent progress. Adv Mater, 2014, 26: 4763-4782 CrossRef PubMed Google Scholar

[2] Wang Y, Xia Y. Recent progress in supercapacitors: from materials design to system construction. Adv Mater, 2013, 25: 5336-5342 CrossRef PubMed Google Scholar

[3] Xue Q, Sun J, Huang Y, et al. Recent progress on flexible and wearable supercapacitors. Small, 2017, 13: 1701827-1701837 CrossRef PubMed Google Scholar

[4] Huang Y, Zhu M, Huang Y, et al. Multifunctional energy storage and conversion devices. Adv Mater, 2016, 28: 8344-8364 CrossRef PubMed Google Scholar

[5] Yu N, Yin H, Zhang W, et al. High-performance fiber-shaped all-solid-state asymmetric supercapacitors based on ultrathin MnO2 nanosheet/carbon fiber cathodes for wearable electronics. Adv Energy Mater, 2016, 6: 1501458 CrossRef Google Scholar

[6] 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

[7] Guo K, Wang X, Hu L, et al. Highly stretchable waterproof fiber asymmetric supercapacitors in an integrated structure. ACS Appl Mater Interfaces, 2018, 10: 19820-19827 CrossRef Google Scholar

[8] 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

[9] Lu X, Yu M, Wang G, et al. Flexible solid-state supercapacitors: design, fabrication and applications. Energy Environ Sci, 2014, 7: 2160-2181 CrossRef Google Scholar

[10] Lv Z, Luo Y, Tang Y, et al. Editable supercapacitors with customizable stretchability based on mechanically strengthened ultralong MnO2 nanowire composite. Adv Mater, 2018, 30: 1704531 CrossRef PubMed Google Scholar

[11] Yu N, Guo K, Zhang W, et al. Flexible high-energy asymmetric supercapacitors based on MnO@C composite nanosheet electrodes. J Mater Chem A, 2017, 5: 804-813 CrossRef Google Scholar

[12] Guo K, Wan Y, Yu N, et al. Hand-drawing patterned ultra-thin integrated electrodes for flexible microsupercapacitors. Energy Storage Mater, 2018, 11: 144-151 CrossRef Google Scholar

[13] Guo K, Ma Y, Li H, et al. Flexible wire-shaped supercapacitors in parallel double helix configuration with stable electrochemical properties under static/dynamic bending. Small, 2016, 12: 1024-1033 CrossRef PubMed Google Scholar

[14] Sun H, Xie S, Li Y, et al. Large-area supercapacitor textiles with novel hierarchical conducting structures. Adv Mater, 2016, 28: 8431-8438 CrossRef PubMed Google Scholar

[15] Zhang Y, Bai W, Cheng X, et al. Flexible and stretchable lithium-ion batteries and supercapacitors based on electrically conducting carbon nanotube fiber springs. Angew Chem Int Ed, 2014, 53: 14564-14568 CrossRef PubMed Google Scholar

[16] Zhai T, Lu X, Wang H, et al. An electrochemical capacitor with applicable energy density of 7.4 Wh/kg at average power density of 3000 W/kg. Nano Lett, 2015, 15: 3189-3194 CrossRef PubMed ADS Google Scholar

[17] Xia X, Zhang Y, Chao D, et al. Tubular TiC fibre nanostructures as supercapacitor electrode materials with stable cycling life and wide-temperature performance. Energy Environ Sci, 2015, 8: 1559-1568 CrossRef Google Scholar

[18] Zhu W, Li R, Xu P, et al. Vanadium trioxide@carbon nanosheet array-based ultrathin flexible symmetric hydrogel supercapacitors with 2 V voltage and high volumetric energy density. J Mater Chem A, 2017, 5: 22216-22223 CrossRef Google Scholar

[19] Li Q, Lu C, Chen C, et al. Layered NiCo2O4/reduced graphene oxide composite as an advanced electrode for supercapacitor. Energy Storage Mater, 2017, 8: 59-67 CrossRef Google Scholar

[20] Yang J, Xiong P, Zheng C, et al. Metal-organic frameworks: A new promising class of materials for a high performance supercapacitor electrode. J Mater Chem A, 2014, 2: 16640-16644 CrossRef Google Scholar

[21] Wang Y, Yang X, Pandolfo AG, et al. High-rate and high-volumetric capacitance of compact graphene-polyaniline hydrogel electrodes. Adv Energy Mater, 2016, 6: 1600185-1600190 CrossRef Google Scholar

[22] Yang X, Cheng C, Wang Y, et al. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science, 2013, 341: 534-537 CrossRef PubMed ADS Google Scholar

[23] Yan J, Ren CE, Maleski K, et al. Flexible MXene/graphene films for ultrafast supercapacitors with outstanding volumetric capacitance. Adv Funct Mater, 2017, 27: 1701264-1701273 CrossRef Google Scholar

[24] Li H, Tao Y, Zheng X, et al. Ultra-thick graphene bulk supercapacitor electrodes for compact energy storage. Energy Environ Sci, 2016, 9: 3135-3142 CrossRef Google Scholar

[25] 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, 61: 233-242 CrossRef Google Scholar

[26] Wu S, Zhu Y. Highly densified carbon electrode materials towards practical supercapacitor devices. Sci China Mater, 2016, 60: 25-38 CrossRef Google Scholar

[27] Ghidiu M, Lukatskaya MR, Zhao MQ, et al. Conductive two-dimensional titanium carbide ‘clay’ with high volumetric capacitance. Nature, 2014, 3: 78-81 CrossRef PubMed ADS Google Scholar

[28] Acerce M, Voiry D, Chhowalla M. Metallic 1T phase MoS2 nanosheets as supercapacitor electrode materials. Nat Nanotechnol, 2015, 10: 313-318 CrossRef PubMed ADS Google Scholar

[29] Liu Y, Wang W, Huang H, et al. The highly enhanced performance of lamellar WS2 nanosheet electrodes upon intercalation of single-walled carbon nanotubes for supercapacitors and lithium ions batteries. Chem Commun, 2014, 50: 4485-4488 CrossRef PubMed Google Scholar

[30] Liu Y, Wang W, Wang Y, et al. Homogeneously assembling like-charged WS2 and GO nanosheets lamellar composite films by filtration for highly efficient lithium ion batteries. Nano Energy, 2014, 7: 25-32 CrossRef Google Scholar

[31] Sheng L, Jiang L, Wei T, et al. High volumetric energy density asymmetric supercapacitors based on well-balanced graphene and graphene-MnO2 electrodes with densely stacked architectures. Small, 2016, 12: 5217-5227 CrossRef PubMed Google Scholar

[32] Li H, Tao Y, Zheng X, et al. Compressed porous graphene particles for use as supercapacitor electrodes with excellent volumetric performance. Nanoscale, 2015, 7: 18459-18463 CrossRef PubMed ADS Google Scholar

[33] 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

[34] Gu L, Wang Y, Lu R, et al. Anodic electrodeposition of a porous nickel oxide-hydroxide film on passivated nickel foam for supercapacitors. J Mater Chem A, 2014, 2: 7161-7164 CrossRef Google Scholar

[35] 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

[36] Wu Y, Gao G, Wu G. Self-assembled three-dimensional hierarchical porous V2O5/graphene hybrid aerogels for supercapacitors with high energy density and long cycle life. J Mater Chem A, 2015, 3: 1828-1832 CrossRef Google Scholar

[37] Wang X, Lv L, Cheng Z, et al. High-density monolith of n-doped holey graphene for ultrahigh volumetric capacity of Li-ion batteries. Adv Energy Mater, 2016, 6: 1502100 CrossRef Google Scholar

[38] Feng J, Sun X, Wu C, et al. Metallic few-layered VS2 ultrathin nanosheets: high two-dimensional conductivity for in-plane supercapacitors. J Am Chem Soc, 2011, 133: 17832-17838 CrossRef PubMed Google Scholar

[39] Peng L, Peng X, Liu B, et al. Ultrathin two-dimensional MnO2/graphene hybrid nanostructures for high-performance, flexible planar supercapacitors. Nano Lett, 2013, 13: 2151-2157 CrossRef PubMed ADS Google Scholar

[40] Gao S, Sun Y, Lei F, et al. Ultrahigh energy density realized by a single-layer β-Co(OH)2 all-solid-state asymmetric supercapacitor. Angew Chem Int Ed, 2014, 53: 12789-12793 CrossRef PubMed Google Scholar

[41] Zhu Y, Murali S, Cai W, et al. Graphene and graphene oxide: synthesis, properties, and applications. Adv Mater, 2010, 22: 3906-3924 CrossRef PubMed Google Scholar

[42] Li L, Peng S, Wu HB, et al. A flexible quasi-solid-state asymmetric electrochemical capacitor based on hierarchical porous V2O5 nanosheets on carbon nanofibers. Adv Energy Mater, 2015, 5: 1500753-1500760 CrossRef Google Scholar

[43] Kong D, Li X, Zhang Y, et al. Encapsulating V2O5 into carbon nanotubes enables the synthesis of flexible high-performance lithium ion batteries. Energy Environ Sci, 2016, 9: 906-911 CrossRef Google Scholar

[44] Wu J, Gao X, Yu H, et al. A scalable free-standing V2O5/CNT film electrode for supercapacitors with a wide operation voltage (1.6 V) in an aqueous electrolyte. Adv Funct Mater, 2016, 26: 6114-6120 CrossRef Google Scholar

[45] Kim D, Yun J, Lee G, et al. Fabrication of high performance flexible micro-supercapacitor arrays with hybrid electrodes of MWNT/V2O5 nanowires integrated with a SnO2 nanowire UV sensor. Nanoscale, 2014, 6: 12034-12041 CrossRef PubMed ADS Google Scholar

[46] Wei Q, Liu J, Feng W, et al. Hydrated vanadium pentoxide with superior sodium storage capacity. J Mater Chem A, 2015, 3: 8070-8075 CrossRef Google Scholar

[47] Moretti A, Passerini S. Bilayered nanostructured V2O5·nH2O for metal batteries. Adv Energy Mater, 2016, 6: 1600868 CrossRef Google Scholar

[48] Song Y, Zhao W, Kong L, et al. Synchronous immobilization and conversion of polysulfides on a VO2–VN binary host targeting high sulfur load Li–S batteries. Energy Environ Sci, 2018, 11: 2620-2630 CrossRef Google Scholar

[49] Chen K, Xue D. High energy density hybrid supercapacitor: in-situ functionalization of vanadium-based colloidal cathode. ACS Appl Mater Interfaces, 2016, 8: 29522-29528 CrossRef Google Scholar

[50] Watanabe T. Characterization of vanadium oxide sol as a starting material for high rate intercalation cathodes. Solid State Ion, 2002, 151: 313-320 CrossRef Google Scholar

[51] Perera SD, Patel B, Nijem N, et al. Vanadium oxide nanowire-carbon nanotube binder-free flexible electrodes for supercapacitors. Adv Energy Mater, 2011, 1: 936-945 CrossRef Google Scholar

[52] Bauhofer W, Kovacs JZ. A review and analysis of electrical percolation in carbon nanotube polymer composites. Compos Sci Tech, 2009, 69: 1486-1498 CrossRef Google Scholar

[53] Lv G, Wu D, Fu R, et al. Electrochemical properties of conductive filler/carbon aerogel composites as electrodes of supercapacitors. J Non-Crystalline Solids, 2008, 354: 4567-4571 CrossRef ADS Google Scholar

[54] Wu NL, Wang SY. Conductivity percolation in carbon-carbon supercapacitor electrodes. J Power Sources, 2002, 110: 233-236 CrossRef ADS Google Scholar

[55] 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

[56] Yan J, Wang Q, Wei T, et al. Template-assisted low temperature synthesis of functionalized graphene for ultrahigh volumetric performance supercapacitors. ACS Nano, 2014, 8: 4720-4729 CrossRef PubMed Google Scholar

[57] Lukatskaya MR, Mashtalir O, Ren CE, et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science, 2013, 341: 1502-1505 CrossRef PubMed ADS Google Scholar

[58] Yan J, Wang Q, Lin C, et al. Interconnected frameworks with a sandwiched porous carbon layer/graphene hybrids for supercapacitors with high gravimetric and volumetric performances. Adv Energy Mater, 2014, 4: 1400500-1400509 CrossRef Google Scholar

[59] 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

[60] Yu ZY, Chen LF, Song LT, et al. Free-standing boron and oxygen co-doped carbon nanofiber films for large volumetric capacitance and high rate capability supercapacitors. Nano Energy, 2015, 15: 235-243 CrossRef Google Scholar

[61] Long C, Chen X, Jiang L, et al. Porous layer-stacking carbon derived from in-built template in biomass for high volumetric performance supercapacitors. Nano Energy, 2015, 12: 141-151 CrossRef Google Scholar

[62] Jiang L, Sheng L, Long C, et al. Densely packed graphene nanomesh-carbon nanotube hybrid film for ultra-high volumetric performance supercapacitors. Nano Energy, 2015, 11: 471-480 CrossRef Google Scholar

[63] Jung N, Kwon S, Lee D, et al. Synthesis of chemically bonded graphene/carbon nanotube composites and their application in large volumetric capacitance supercapacitors. Adv Mater, 2013, 25: 6854-6858 CrossRef PubMed Google Scholar

  • Figure 1

    Schematic fabrication process of V2O5·nH2O/CNTs composite films.

  • Figure 2

    Characterization of V2O5·nH2O aerogel: (a) XRD, (b) V 2p XPS spectrum, (c) SEM image and (d) TEM image.

  • Figure 3

    Top-view SEM images of (a) CNT, (b) V2O5·nH2O, and (c) VC-5% films. Inset in (a) and (b): the cross-section SEM image of the CNT and V2O5·nH2O film, respectively. The cross-section SEM image of the (d) VC-5%, (e) VC-10%, and (f) VC-15% films. (g) Cross-section SEM image and the elemental mapping image of (h) C, (i) O, and (j) V elements in the composite film.

  • Figure 4

    The effects of CNTs mass ratio on (a) the square resistance, (b) the density and thickness of different film samples. Schematic cross-section microstructure, ion diffusion, and electron transfer in composite films with (c) a small (5 wt%) and large amount (≥10 wt%) of CNTs. Schemes in (a): the microstructure of layered composite films with different ratio of CNTs (black lines) and V2O5·nH2O nanosheets (yellow planes), in which the contact points of crossed CNTs are marked with red semi-spheres.

  • Figure 5

    Electrochemical performances of different film samples. (a) CV curves, (b) gravimetric capacitance, (c) volumetric capacitance, and (d) EIS plots of different film samples. (e) CV and (f) GCD curves of the VC-10% film electrode. (g) The volumetric capacitance of different flexible film electrodes.

  • Figure 6

    Electrochemical performance of symmetric SCs based on VC-10% film: (a) CV curves, (b) GCD curves, (c) volumetric capacitance, (d) gravimetric Ragone plot and (e) cycling performance.

  • Figure 7

    Flexibility characterization of flexible SCs. (a) Scheme of a bent flexible SC. (b) The CV curves, (c) GCD curves, and (d) capacitance retention of a flexible SC bent to different degrees.


Contact and support