Skip to main content
SpringerLink
Log in

Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO2 and reduced graphene oxide via electrochemical deposition

电沉积制备氧化石墨烯/二氧化锰包裹镍纤维电极用于柔性固态超级电容器

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Flexible and micro-sized energy conversion/ storage components are extremely demanding in portable and multifunctional electronic devices, especially those small, flexible, roll-up and even wearable ones. Here in this paper, a two-step electrochemical deposition method has been developed to coat Ni fibers with reduced graphene oxide and MnO2 subsequently, giving rise to Ni@reduced-graphene-oxide@MnO2 sheath-core flexible electrode with a high areal specific capacitance of 119.4 mF cm−2 at a current density of 0.5 mA cm−2 in 1 mol L−1 Na2SO4 electrolyte. Using polyvinyl alcohol (PVA)- LiCl as a solid state electrolyte, two Ni@reduced-grapheneoxide@ MnO2 flexible electrodes were assembled into a freestanding, lightweight, symmetrical fiber-shaped micro-supercapacitor device with a maximum areal capacitance of 26.9 mF cm−2. A high power density of 0.1W cm−3 could be obtained when the energy density was as high as 0.27 mW h cm−3. Moreover, the resulting micro-supercapacitor device also demonstrated good flexibility and high cyclic stability. The present work provides a simple, facile and low-cost method for the fabrication of flexible, lightweight and wearable energy conversion/storage micro-devices with a high-performance.

摘要

便携式及多功能电子设备的不断进步要求为其提供动力能量的存储与转换器件向尺寸小、柔性、能够卷曲甚至可穿戴方向发展. 本文采用两步电化学沉积法依次将还原氧化石墨烯(rGO)和MnO2沉积到镍纤维上得到Ni@rGO@MnO2壳核结构的柔性电极. 该电极在 1 mol L−1 Na2SO4 电解液中电流密度为0.5 mA cm−2时面积比电容为119.4 mF cm−2. 以PVA-LiCl为固态电解液, 将两根Ni@rGO@MnO2电 极组装成自支撑、质轻、对称的纤维状微型超级电容器, 最大面积比电容为26.9 mF cm−2, 能量密度高达0.1 W cm−3 (0.27 mW h cm−3). 此 外, 该微型超级电容器还展现了良好的柔性和循环性能. 这项研究工作主要提供了一种简单、易操作、低成本的制备柔性、质轻、可穿 戴的高性能能量存储设备的方法.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Cheng JP, Zhang J, Liu F. Recent development of metal hydroxides as electrode material of electrochemical capacitors. RSC Adv, 2014, 4: 38893–38917

    Article  Google Scholar 

  2. Liu S, Sun S, You XZ. Inorganic nanostructured materials for high performance electrochemical supercapacitors. Nanoscale, 2014, 6: 2037–2045

    Article  Google Scholar 

  3. Wang G, Zhang L, Zhang J. A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev, 2012, 41: 797–828

    Article  Google Scholar 

  4. Yu L, Zhang G, Yuan C, et al. Hierarchical NiCO2O4@MnO2 coreshell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes. Chem Commun, 2013, 49: 137–139

    Article  Google Scholar 

  5. 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

    Article  Google Scholar 

  6. Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon, 2001, 39: 937–950

    Article  Google Scholar 

  7. Futaba DN, Hata K, Yamada T, et al. Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nat Mater, 2006, 5: 987–994

    Article  Google Scholar 

  8. Stoller MD, Park S, Zhu Y, et al. Graphene-based ultracapacitors. Nano Lett, 2008, 8: 3498–3502

    Article  Google Scholar 

  9. Wang DW, Li F, Zhao J, et al. Fabrication of graphene/polyaniline composite paper via in situ anodic electropolymerization for highperformance flexible electrode. ACS Nano, 2009, 3: 1745–1752

    Article  Google Scholar 

  10. Hu CC, Chang KH, Lin MC, et al. Design and tailoring of the nanotubular arrayed architecture of hydrous RuO2 for next generation supercapacitors. Nano Lett, 2006, 6: 2690–2695

    Article  Google Scholar 

  11. Wang H, Casalongue HS, Liang Y, et al. Ni(OH)2 nanoplates grown on graphene as advanced electrochemical pseudocapacitor materials. J Am Chem Soc, 2010, 132: 7472–7477

    Article  Google Scholar 

  12. Feng X, Yan Z, Chen N, et al. The synthesis of shape-controlled MnO2/graphene composites via a facile one-step hydrothermal method and their application in supercapacitors. J Mater Chem A, 2013, 1: 12818–12825

    Article  Google Scholar 

  13. Wang H, Deng J, Chen Y, et al. Hydrothermal synthesis of manganese oxide encapsulated multiporous carbon nanofibers for supercapacitors. Nano Res, 2016, 9: 2672–2680

    Article  Google Scholar 

  14. Rakhi RB, Chen W, Hedhili MN, et al. Enhanced rate performance of mesoporous Co3O4 nanosheet supercapacitor electrodes by hydrous RuO2 nanoparticle decoration. ACS Appl Mater Interfaces, 2014, 6: 4196–4206

    Article  Google Scholar 

  15. Wang H, Xu Z, Li Z, et al. Hybrid device employing three-dimensional arrays of MnO in carbon nanosheets bridges batterysupercapacitor divide. Nano Lett, 2014, 14: 1987–1994

    Article  Google Scholar 

  16. Chang HW, Lu YR, Chen JL, et al. Nanoflaky MnO2/functionalized carbon nanotubes for supercapacitors: an in situ X-ray absorption spectroscopic investigation. Nanoscale, 2015, 7: 1725–1735

    Article  Google Scholar 

  17. Zhang Z, Chi K, Xiao F, et al. Advanced solid-state asymmetric supercapacitors based on 3D graphene/MnO2 and graphene/polypyrrole hybrid architectures. J Mater Chem A, 2015, 3: 12828–12835

    Article  Google Scholar 

  18. Zhong J, Zhang Y, Zhong Q, et al. Fiber-based generator for wearable electronics and mobile medication. ACS Nano, 2014, 8: 6273–6280

    Article  Google Scholar 

  19. Xie B, Yang C, Zhang Z, et al. Shape-tailorable graphene-based ultra-high-rate supercapacitor for wearable electronics. ACS Nano, 2015, 9: 5636–5645

    Article  Google Scholar 

  20. Huang Y, Hu H, Huang Y, et al. From industrially weavable and knittable highly conductive yarns to large wearable energy storage textiles. ACS Nano, 2015, 9: 4766–4775

    Article  Google Scholar 

  21. 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

    Article  Google Scholar 

  22. Yu M, Cheng X, Zeng Y, et al. Dual-doped molybdenum trioxide nanowires: a bifunctional anode for fiber-shaped asymmetric supercapacitors and microbial fuel cells. Angew Chem Int Ed, 2016, 55: 6762–6766

    Article  Google Scholar 

  23. Yu M, Zhao S, Feng H, et al. Engineering thin MoS2 nanosheets on TiN nanorods: advanced electrochemical capacitor electrode and hydrogen evolution electrocatalyst. ACS Energy Lett, 2017, 2: 1862–1868

    Article  Google Scholar 

  24. Dong X, Chen L, Su X, et al. Flexible aqueous lithium-ion battery with high safety and large volumetric energy density. Angew Chem Int Ed, 2016, 55: 7474–7477

    Article  Google Scholar 

  25. Zeng Y, Zhang X, Meng Y, et al. Achieving ultrahigh energy density and long durability in a flexible rechargeable quasi-solidstate Zn-MnO2 battery. Adv Mater, 2017, 29: 1700274–1700281

    Article  Google Scholar 

  26. Wang Z, Carlsson DO, Tammela P, et al. Surface modified nanocellulose fibers yield conducting polymer-based flexible supercapacitors with enhanced capacitances. ACS Nano, 2015, 9: 7563–7571

    Article  Google Scholar 

  27. Dong L, Xu C, Yang Q, et al. High-performance compressible supercapacitors based on functionally synergic multiscale carbon composite textiles. J Mater Chem A, 2015, 3: 4729–4737

    Article  Google Scholar 

  28. Wang X, Liu B, Liu R, et al. Fiber-based flexible all-solid-state asymmetric supercapacitors for integrated photodetecting system. Angew Chem Int Ed, 2014, 53: 1849–1853

    Article  Google Scholar 

  29. Wang Q, Wang X, Xu J, et al. Flexible coaxial-type fiber supercapacitor based on NiCO2O4 nanosheets electrodes. Nano Energy, 2014, 8: 44–51

    Article  Google Scholar 

  30. Yu D, Qian Q, Wei L, et al. Emergence of fiber supercapacitors. Chem Soc Rev, 2015, 44: 647–662

    Article  Google Scholar 

  31. Xu H, Hu X, Sun Y, et al. Flexible fiber-shaped supercapacitors based on hierarchically nanostructured composite electrodes. Nano Res, 2014, 8: 1148–1158

    Article  Google Scholar 

  32. 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

    Article  Google Scholar 

  33. Shao Y, El-Kady MF, Wang LJ, et al. Graphene-based materials for flexible supercapacitors. Chem Soc Rev, 2015, 44: 3639–3665

    Article  Google Scholar 

  34. Zhao C, Shu K, Wang C, et al. Reduced graphene oxide and polypyrrole/reduced graphene oxide composite coated stretchable fabric electrodes for supercapacitor application. Electrochim Acta, 2015, 172: 12–19

    Article  Google Scholar 

  35. He Y, Chen W, Li X, et al. Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. ACS Nano, 2013, 7: 174–182

    Article  Google Scholar 

  36. Zhang Z, Xiao F, Wang S. Hierarchically structured MnO2/graphene/carbon fiber and porous graphene hydrogel wrapped copper wire for fiber-based flexible all-solid-state asymmetric supercapacitors. J Mater Chem A, 2015, 3: 11215–11223

    Article  Google Scholar 

  37. Zhu J, He J. Facile synthesis of graphene-wrapped honeycomb MnO2 nanospheres and their application in supercapacitors. ACS Appl Mater Interfaces, 2012, 4: 1770–1776

    Article  Google Scholar 

  38. Lai L, Yang H, Wang L, et al. Preparation of supercapacitor electrodes through selection of graphene surface functionalities. ACS Nano, 2012, 6: 5941–5951

    Article  Google Scholar 

  39. Feng X, Zhou J, Wang L, et al. Synthesis of shape-controlled NiOgraphene nanocomposites with enhanced supercapacitive properties. New J Chem, 2015, 39: 4026–4034

    Article  Google Scholar 

  40. Lai F, Miao YE, Huang Y, et al. Flexible hybrid membranes of NiCO2O4-doped carbon nanofiber@MnO2 core-sheath nanostructures for high-performance supercapacitors. J Phys Chem C, 2015, 119: 13442–13450

    Article  Google Scholar 

  41. Xie Y, Xia C, Du H, et al. Enhanced electrochemical performance of polyaniline/carbon/titanium nitride nanowire array for flexible supercapacitor. J Power Sources, 2015, 286: 561–570

    Article  Google Scholar 

  42. Buller S, Karden E, Kok D, et al. Modeling the dynamic behavior of supercapacitors using impedance spectroscopy. In: Thirty-Sixth IAS Annual Meeting. Conference Record of the 2001 IEEE, 2001, 4: 2500–2504

    Google Scholar 

  43. Barcellona S, Piegari L. A lithium-ion capacitor model working on a wide temperature range. J Power Sources, 2017, 342: 241–251

    Article  Google Scholar 

  44. Kaempgen M, Chan CK, Ma J, et al. Printable thin film supercapacitors using single-walled carbon nanotubes. Nano Lett, 2009, 9: 1872–1876

    Article  Google Scholar 

  45. 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: 065401

    Article  Google Scholar 

  46. Bae J, Song MK, Park YJ, et al. Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage. Angew Chem Int Ed, 2011, 50: 1683–1687

    Article  Google Scholar 

  47. Ren J, Bai W, Guan G, et al. Flexible and weaveable capacitor wire based on a carbon nanocomposite fiber. Adv Mater, 2013, 25: 5965–5970

    Article  Google Scholar 

  48. Yuan L, Lu XH, Xiao X, et al. Flexible solid-state supercapacitors based on carbon nanoparticles/MnO2 nanorods hybrid structure. ACS Nano, 2011, 6: 656–661

    Article  Google Scholar 

  49. Pandey GP, Rastogi AC, Westgate CR. All-solid-state supercapacitors with poly(3,4-ethylenedioxythiophene)-coated carbon fiber paper electrodes and ionic liquid gel polymer electrolyte. J Power Sources, 2014, 245: 857–865

    Article  Google Scholar 

  50. Yu P, Li Y, Zhao X, et al. Graphene-wrapped polyaniline nanowire arrays on nitrogen-doped carbon fabric as novel flexible hybrid electrode materials for high-performance supercapacitor. Langmuir, 2014, 30: 5306–5313

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Ministry of Education of China (IRT1148), the National Natural Science Foundation of China (51772157 and 21173116), Synergistic Innovation Center for Organic Electronics and Information Displays, Jiangsu Province “Six Talent Peak” (2015-JY-015), Jiangsu Provincial Natural Science Foundation (BK20141424), the Program of Nanjing University of Posts and Telecommunications (NY214088), and the Open Research Fund of State Key Laboratory of Bioelectronics of Southeast University (I2015010).

Author information

Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing, 210023, China

    Jinhua Zhou  (周锦华), You Ge  (葛优), Hongli Zhu  (朱红丽), Xiaomiao Feng  (冯晓苗), Ruiqing Liu  (刘瑞卿), Yanwen Ma  (马延文) & Lianhui Wang  (汪联辉)

  2. Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

    Jinhua Zhou  (周锦华), Ningna Chen  (陈宁娜) & Wenhua Hou  (侯文华)

Authors
  1. Jinhua Zhou  (周锦华)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ningna Chen  (陈宁娜)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. You Ge  (葛优)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hongli Zhu  (朱红丽)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Xiaomiao Feng  (冯晓苗)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ruiqing Liu  (刘瑞卿)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yanwen Ma  (马延文)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lianhui Wang  (汪联辉)
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Wenhua Hou  (侯文华)
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xiaomiao Feng  (冯晓苗) or Wenhua Hou  (侯文华).

Additional information

Jinhua Zhou received her MSc degree under the supervision of Prof. Xiaomiao Feng in the Department of Materials Chemistry at the Nanjing University of Posts and Telecommunications in 2016. She is currently a PhD under the supervision of Prof. Wenhua Hou at Nanjing University. Her research is mainly focused on the synthesis of 2D materials, and their application for energy conversion and storage devices.

Ningna Chen obtained her MSc degree from Nanjing University of Posts & Telecommunications in 2015. Currently, she is pursuing her PhD degree under the supervision of Prof. Wenhua Hou at Nanjing University. Her research is mainly focused on the synthesis of two-dimensional layered transition metal oxide nanomaterials, and their application for energy conversion and storage devices.

Xiaomiao Feng is a Professor in the Department of Materials Chemistry at the Nanjing University of Posts and Telecommunications. She received her PhD from Nanjing University, Nanjing (China) in 2007. Between July 2012 and July 2013 she joined the research group of Prof. J. Wang at the Department of Nanoengineering, University of California, San Diego as a visiting scholar. Her research interests include nanomaterials, naonomachines, biosensors and super capacitors.

Wenhua Hou is a professor in the School of Chemistry and Chemical Engineering at Nanjing University. He received his BS (1985) and PhD (1993) in chemistry from Nanjing University. He worked as visiting scholar at the State University of New York at Albany and University of California, San Diego. His research interests include the synthesis of 2D layer nanomaterials for potocatalysis and energy storage.

Electronic supplementary material

40843_2017_9168_MOESM1_ESM.pdf

Flexible All-solid-state Micro-supercapacitor based on Ni Fiber Electrode Coated with MnO2 and Reduced Graphene Oxide via Electrochemical Deposition

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhou, J., Chen, N., Ge, Y. et al. Flexible all-solid-state micro-supercapacitor based on Ni fiber electrode coated with MnO2 and reduced graphene oxide via electrochemical deposition. Sci. China Mater. 61, 243–253 (2018). https://doi.org/10.1007/s40843-017-9168-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-017-9168-9

Keywords

Search

Navigation