SCIENCE CHINA Materials, Volume 61, Issue 2: 273-284(2018) https://doi.org/10.1007/s40843-017-9064-6

Facile synthesis of T-Nb2O5 nanosheets/nitrogen and sulfur co-doped graphene for high performance lithium-ion hybrid supercapacitors

More info
  • ReceivedMay 22, 2017
  • AcceptedJun 16, 2017
  • PublishedAug 8, 2017


Li-ion hybrid supercapacitors (Li-HSCs) have attracted increasing attention as a promising energy storage device with both high power and energy densities. We report a facile two-step hydrothermal method to prepare the orthorhombic niobium oxide (T-Nb2O5) nanosheets supported on nitrogen and sulfur co-doped graphene (T-Nb2O5/NS-G) as anode for Li-HSCs. X-ray diffraction and morphological analysis show that the T-Nb2O5 nanosheets successfully and uniformly distributed on the NS-G sheets. The T-Nb2O5/NS-G hybrid exhibits great rate capability (capacity retention of 63.1% from 0.05 to 5 A g−1) and superior cycling stability (a low capacity fading of ~6.4% after 1000 cycles at 0.5 A g−1). The full-cell consisting of T-Nb2O5/NS-G and active carbon (AC) results in high energy density (69.2 W h kg−1 at 0.1 A g−1), high power density (9.17 kW kg−1) and excellent cycling stability (95% of the initial energy after 3000 cycles). This excellent performance is mainly attributed to the highly conductive NS-G sheets, the uniformly distributed T-Nb2O5 nanosheets and the synergetic effects between them. These encouraging performances confirm that the obtained T-Nb2O5/NS-G has promising prospect as the anode for Li-HSCs.

Funded by

 the National Natural Science Foundation of China(21576138,51572127)

China-Israel Cooperative Program(2016YFE0129900)

Program for NCET-12-0629

Ph.D. Program Foundation of Ministry of Education of China(20133219110018)

Natural Science Foundation of Jiangsu Province(BK20160828)

Post-Doctoral Foundation(1501016B)

Six Major Talent Summit(XNY-011)

and PAPD of Jiangsu Province

and the program for Science and Technology Innovative Research Team in Universities of Jiangsu Province



This work was supported by the National Natural Science Foundation of China (21576138 and 51572127), China-Israel Cooperative Program (2016YFE0129900), Program for NCET-12-0629, PhD Program Foundation of Ministry of Education of China (20133219110018), the Natural Science Foundation of Jiangsu Province (BK20160828), Post-Doctoral Foundation (1501016B), Six Major Talent Summit (XNY-011), and PAPD of Jiangsu Province, and the program for Science and Technology Innovative Research Team in Universities of Jiangsu Province, China. We also thank Dr. Huaping Bai and Dr. Wanying Tang at the Analysis and Test Center, Nanjing University of Science and Technology for the XRD and Raman data collection.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Hao Q designed and engineered the experiments, and guided the whole process of writing and submission of the current paper; Jiao X performed the experiments, analyzed the data and wrote the paper with support from Liu P, Xia X, Lei W and Liu X. All authors contributed to the general discussion.

Author information

Xinyan Jiao received her BE degree in materials chemistry from Nanjing University of Science and Technology in 2010. Now she is a PhD candidate at the College of School of Chemical Engineering, Nanjing University of Science and Technology. Her recent research focuses on metal oxide/carbon nanocomposites for electrochemical energy storage systems.

Qingli Hao is a professor in materials chemistry at Nanjing University of Science and Technology. She received her PhD degree in chemistry from the University of Regensburg in 2003. Her research interest focuses on functional nanomaterials and their application in energy storage and conversion systems and chemical sensors.


Supplementary information

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


[1] Lim E, Jo C, Kim H, et al. Facile synthesis of Nb2O5@carbon core-shell nanocrystals with controlled crystalline structure for high-power anodes in hybrid supercapacitors. ACS Nano, 2015, 9: 7497-7505 CrossRef Google Scholar

[2] Lim E, Kim H, Jo C, et al. Advanced hybrid supercapacitor based on a mesoporous niobium pentoxide/carbon as high-performance anode. ACS Nano, 2014, 8: 8968-8978 CrossRef PubMed Google Scholar

[3] Kang K, Meng YS, Bréger J, et al. Electrodes with high power and high capacity for rechargeable lithium batteries. Science, 2006, 311: 977-980 CrossRef PubMed ADS Google Scholar

[4] Wang Q, Wen ZH, Li JH. A hybrid supercapacitor fabricated with a carbon nanotube cathode and a TiO2-B nanowire anode. Adv Funct Mater, 2006, 16: 2141-2146 CrossRef Google Scholar

[5] Aravindan V, Gnanaraj J, Lee YS, et al. Insertion-type electrodes for nonaqueous Li-ion capacitors. Chem Rev, 2014, 114: 11619-11635 CrossRef PubMed Google Scholar

[6] Wu XL, Wen T, Guo HL, et al. Biomass-derived sponge-like carbonaceous hydrogels and aerogels for supercapacitors. ACS Nano, 2013, 7: 3589-3597 CrossRef PubMed Google Scholar

[7] Ma Y, Chang H, Zhang M, et al. Graphene-based materials for lithium-ion hybrid supercapacitors. Adv Mater, 2015, 27: 5296-5308 CrossRef PubMed Google Scholar

[8] Zhao G, Huang X, Wang X, et al. Synthesis and lithium-storage properties of MnO/reduced graphene oxide composites derived from graphene oxide plus the transformation of Mn(VI) to Mn(II) by the reducing power of graphene oxide. J Mater Chem A, 2015, 3: 297-303 CrossRef Google Scholar

[9] An C, Liu X, Gao Z, et al. Filling and unfilling carbon capsules with transition metal oxide nanoparticles for Li-ion hybrid supercapacitors: towards hundred grade energy density. Sci China Mater, 2017, 60: 217-227 CrossRef Google Scholar

[10] Dubal DP, Ayyad O, Ruiz V, et al. Hybrid energy storage: the merging of battery and supercapacitor chemistries. Chem Soc Rev, 2015, 44: 1777-1790 CrossRef PubMed Google Scholar

[11] Naoi K, Ishimoto S, Miyamoto J, et al. Second generation ‘nanohybrid supercapacitor’: evolution of capacitive energy storage devices. Energ Environ Sci, 2012, 5: 9363 CrossRef Google Scholar

[12] Wang Y, Hong Z, Wei M, et al. Layered H2Ti6O13-nanowires: a new promising pseudocapacitive material in non-aqueous electrolyte. Adv Funct Mater, 2012, 22: 5185-5193 CrossRef Google Scholar

[13] Kim H, Cho MY, Kim MH, et al. A novel high-energy hybrid supercapacitor with an anatase TiO2-reduced graphene oxide anode and an activated carbon cathode. Adv Energ Mater, 2013, 3: 1500-1506 CrossRef Google Scholar

[14] Kim JW, Augustyn V, Dunn B. The effect of crystallinity on the rapid pseudocapacitive response of Nb2O5. Adv Energ Mater, 2012, 2: 141-148 CrossRef Google Scholar

[15] Come J, Augustyn V, Kim JW, et al. Electrochemical kinetics of nanostructured Nb2O5 electrodes. J Electrochemical Soc, 2014, 161: A718-A725 CrossRef Google Scholar

[16] Wei M, Wei K, Ichihara M, et al. Nb2O5 nanobelts: a lithium intercalation host with large capacity and high rate capability. Electrochem Commun, 2008, 10: 980-983 CrossRef Google Scholar

[17] Cava RJ, Batlogg B, Krajewski JJ, et al. Electrical and magnetic properties of Nb2O5−δ crystallographic shear structures. Phys Rev B, 1991, 44: 6973-6981 CrossRef ADS Google Scholar

[18] Liu M, Yan C, Zhang Y. Fabrication of Nb2O5 nanosheets for high-rate lithium ion storage applications. Sci Rep, 2015, 5: 8326 CrossRef PubMed ADS Google Scholar

[19] Novoselov KS, Geim AK, Morozov SV, et al. Electric field effect in atomically thin carbon films. Science, 2004, 306: 666-669 CrossRef PubMed ADS Google Scholar

[20] Sun H, Mei L, Liang J, et al. Three-dimensional holey-graphene/niobia composite architectures for ultrahigh-rate energy storage. Science, 2017, 356: 599-604 CrossRef PubMed Google Scholar

[21] Kong L, Zhang C, Zhang S, et al. High-power and high-energy asymmetric supercapacitors based on Li+-intercalation into a T-Nb2O5/graphene pseudocapacitive electrode. J Mater Chem A, 2014, 2: 17962-17970 CrossRef Google Scholar

[22] Kong L, Zhang C, Wang J, et al. Free-standing T-Nb2O5 /graphene composite papers with ultrahigh gravimetric/volumetric capacitance for Li-ion intercalation pseudocapacitor. ACS Nano, 2015, 9: 11200-11208 CrossRef Google Scholar

[23] Song H, Fu J, Ding K, et al. Flexible Nb2O5 nanowires/graphene film electrode for high-performance hybrid Li-ion supercapacitors. J Power Sources, 2016, 328: 599-606 CrossRef ADS Google Scholar

[24] Liu Q, Wu Z, Ma Z, et al. One-pot synthesis of nitrogen and sulfur co-doped graphene supported MoS2 as high performance anode materials for lithium-ion batteries. Electrochim Acta, 2015, 177: 298-303 CrossRef Google Scholar

[25] Ren X, Ren X, Pang L, et al. MoS2/sulfur and nitrogen co-doped reduced graphene oxide nanocomposite for enhanced electrocatalytic hydrogen evolution. Int J Hydrogen Energ, 2016, 41: 916-923 CrossRef Google Scholar

[26] Zhang X, Yan P, Zhang R, et al. A novel approach of binary doping sulfur and nitrogen into graphene layers for enhancing electrochemical performances of supercapacitors. J Mater Chem A, 2016, 4: 19053-19059 CrossRef Google Scholar

[27] Yun YS, Le VD, Kim H, et al. Effects of sulfur doping on graphene-based nanosheets for use as anode materials in lithium-ion batteries. J Power Sources, 2014, 262: 79-85 CrossRef ADS Google Scholar

[28] Wang H, Hao Q, Yang X, et al. Effect of graphene oxide on the properties of its composite with polyaniline. ACS Appl Mater Interfaces, 2010, 2: 821-828 CrossRef PubMed Google Scholar

[29] Zhang J, Shi Z, Wang C. Effect of pre-lithiation degrees of mesocarbon microbeads anode on the electrochemical performance of lithium-ion capacitors. Electrochim Acta, 2014, 125: 22-28 CrossRef Google Scholar

[30] Augustyn V, Come J, Lowe MA, et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat Mater, 2013, 12: 518-522 CrossRef PubMed ADS Google Scholar

[31] Yang W, Chen L, Liu X, et al. N,S-codoped microporous carbon nanobelts with blooming nanoflowers for oxygen reduction. J Mater Chem A, 2016, 4: 5834-5838 CrossRef Google Scholar

[32] Yu W, Wang H, Liu S, et al. N, O-codoped hierarchical porous carbons derived from algae for high-capacity supercapacitors and battery anodes. J Mater Chem A, 2016, 4: 5973-5983 CrossRef Google Scholar

[33] Liang J, Jiao Y, Jaroniec M, et al. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. Angew Chem Int Ed, 2012, 51: 11496-11500 CrossRef PubMed Google Scholar

[34] Palatnikov M, Shcherbina O, Sidorov N, et al. The structure of niobium and tantalum oxides processed by concentrated light flux. Ukr J Phys Opt, 2012, 13: 207 CrossRef Google Scholar

[35] Xu J, Su D, Zhang W, et al. A nitrogen-sulfur co-doped porous graphene matrix as a sulfur immobilizer for high performance lithium-sulfur batteries. J Mater Chem A, 2016, 4: 17381-17393 CrossRef Google Scholar

[36] Wen T, Wu X, Tan X, et al. One-pot synthesis of water-swellable Mg-Al layered double hydroxides and graphene oxide nanocomposites for efficient removal of As(V) from aqueous solutions. ACS Appl Mater Interfaces, 2013, 5: 3304-3311 CrossRef PubMed Google Scholar

[37] Dong Y, Pang H, Yang HB, et al. Carbon-based dots co-doped with nitrogen and sulfur for high quantum yield and excitation-independent emission. Angew Chem Int Ed, 2013, 52: 7800-7804 CrossRef PubMed Google Scholar

[38] Niu S, Lv W, Zhou G, et al. N and S co-doped porous carbon spheres prepared using L-cysteine as a dual functional agent for high-performance lithium-sulfur batteries. Chem Commun, 2015, 51: 17720-17723 CrossRef PubMed Google Scholar

[39] Sun F, Wang J, Chen H, et al. High efficiency immobilization of sulfur on nitrogen-enriched mesoporous carbons for Li-S batteries. ACS Appl Mater Interfaces, 2013, 5: 5630-5638 CrossRef PubMed Google Scholar

[40] Wang T, Wang LX, Wu DL, et al. Interaction between nitrogen and sulfur in co-doped graphene and synergetic effect in supercapacitor. Sci Rep, 2015, 5: 9591 CrossRef PubMed ADS Google Scholar

[41] Li Y, Wang G, Wei T, et al. Nitrogen and sulfur co-doped porous carbon nanosheets derived from willow catkin for supercapacitors. Nano Energ, 2016, 19: 165-175 CrossRef Google Scholar

[42] Wang R, Lang J, Zhang P, et al. Fast and large lithium storage in 3D porous VN nanowires-graphene composite as a superior anode toward high-performance hybrid supercapacitors. Adv Funct Mater, 2015, 25: 2270-2278 CrossRef Google Scholar

[43] Kim H, Hong J, Park YU, et al. Sodium storage behavior in natural graphite using ether-based electrolyte systems. Adv Funct Mater, 2015, 25: 534-541 CrossRef Google Scholar

[44] Kim G, Jo C, Kim W, et al. TiO2 nanodisks designed for Li-ion batteries: a novel strategy for obtaining an ultrathin and high surface area anode material at the ice interface. Energ Environ Sci, 2013, 6: 2932 CrossRef Google Scholar

[45] Wang X, Yan C, Yan J, et al. Orthorhombic niobium oxide nanowires for next generation hybrid supercapacitor device. Nano Energ, 2015, 11: 765-772 CrossRef Google Scholar

[46] Yang H, Xu H, Wang L, et al. Microwave-assisted rapid synthesis of self-assembled T-Nb2O5 nanowires for high-energy hybrid supercapacitors. Chem Eur J, 2017, 23: 4203-4209 CrossRef PubMed Google Scholar

[47] Yan L, Chen G, Sarker S, et al. Ultrafine Nb2O5 nanocrystal coating on reduced graphene oxide as anode material for high performance sodium ion battery. ACS Appl Mater Interfaces, 2016, 8: 22213-22219 CrossRef Google Scholar

[48] Liu W, Li J, Feng K, et al. Advanced Li-ion hybrid supercapacitors based on 3D graphene-foam composites. ACS Appl Mater Interfaces, 2016, 8: 25941-25953 CrossRef Google Scholar

[49] Wang X, Li G, Chen Z, et al. High-performance supercapacitors based on nanocomposites of Nb2O5 nanocrystals and carbon nanotubes. Adv Energ Mater, 2011, 1: 1089-1093 CrossRef Google Scholar

[50] Wang X, Li G, Tjandra R, et al. Fast lithium-ion storage of Nb2O5 nanocrystals in situ grown on carbon nanotubes for high-performance asymmetric supercapacitors. RSC Adv, 2015, 5: 41179-41185 CrossRef Google Scholar

  • Figure 1

    Schematic diagram of the synthesis of T-Nb2O5/NS-G hybrid.

  • Figure 2

    (a) XRD patterns of the Nb2O5 precursor/NS-G and T-Nb2O5/NS-G hybrid. TEM images of the NS-G (b), Nb2O5 precursor/NS-G (c) and T-Nb2O5/NS-G hybrid (d, e). (f) HRTEM image and SAED pattern of the T-Nb2O5/NS-G hybrid.

  • Figure 3

    (a) Raman spectra of the GO, NS-G and T-Nb2O5/NS-G hybrid. (b) TGA curve of the T-Nb2O5/NS-G hybrid.

  • Figure 4

    (a) Overview XPS spectrum of the T-Nb2O5/NS-G hybrid. (b–e) High-resolution spectra of C 1s (b), N 1s (c) , S 2p (d) and Nb 3d (e) of the T-Nb2O5/NS-G hybrid.

  • Figure 5

    (a) CV curves and (b) specific peak currents of T-Nb2O5/NS-G hybrid at sweep rates from 0.1 to 0.7 mV s−1. (c) CV curves of T-Nb2O5/NS-G with separation between total currents and capacitive currents at 0.1 mV s−1. (d) Capacitive contributions of T-Nb2O5/NS-G at various sweep rates.

  • Figure 6

    (a) Galvanostatic charge/discharge profiles of T-Nb2O5/NS-G hybrid at 0.05 A g−1. (b) Rate capacity of the T-Nb2O5, T-Nb2O5/rGO and T-Nb2O5/NS-G hybrid at current densities ranging from 0.05 to 5 A g−1. (c) Cycling performance of the T-Nb2O5, T-Nb2O5/rGO and T-Nb2O5/NS-G hybrid at 0.1 A g−1. (d) Cycling performance of the T-Nb2O5/NS-G hybrid and the corresponding Coulombic efficiency at 0.4 A g−1.

  • Figure 7

    (a) CV curves of T-Nb2O5/NS-G//AC at various scan rates. (b, c) Galvanostatic charge/discharge curves of T-Nb2O5/NS-G//AC at different current densities. (d) Cycling performance of T-Nb2O5/NS-G//AC.

  • Figure 8

    Ragone plots of T-Nb2O5/NS-G//AC.

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