Science China Materials

, Volume 59, Issue 12, pp 1037–1050 | Cite as

Properties of mesoporous carbon modified carbon felt for anode of all-vanadium redox flow battery

  • Charles N. Schmidt
  • Guozhong Cao


A novel anode material for all-vanadium redox flow battery was synthesized by dispersion coating of sol-gel processed (resorcinol-furaldehyde) mesoporous carbon (MPC) onto the surface of polyacrylonitrile carbon felt (CF). The coated samples were then annealed at 900°C and 1100°C and the subsequent morphology, surface chemistry, and electrochemical properties of the MPC coated CF were characterized and compared with an uncoated CF. Addition of the MPC coating is shown to dramatically increase surface area while also increasing the number of active surface oxygen groups particularly for samples annealed at 1100°C. MPC coating shows a mixed effect on electrochemical properties. Characterization with cyclic voltammetry reveals the introduction of MPC coating provides roughly 30% increase in peak current density for the oxidation and reduction reactions of the V(IV)/V(V) redox couple, which is attributed to the significantly increased number of active reaction sites. However, MPC coating seems to be accompanied by a reduction in conductivity as demonstrated by increased redox peak separation and charge transfer resistance. This negative effect on conductivity can be mitigated by heat treatment (at or above 1100°C) which improves surface graphitization reducing redox peak separation and charge transfer resistance such that it is comparable with uncoated samples.


vanadium redox flow battery carbon felt mesoporous carbon catalyst surface area 



The authors acknowledge the support of UniEnergy Technologies and the University of Washington Clean Energy Institute.


  1. 1.
    Dunn B, Kamath H, Tarascon JM. Electrical energy storage for the grid: a battery of choices. Science, 2011, 334: 928–935CrossRefGoogle Scholar
  2. 2.
    Yang Z, Zhang J, Kintner-Meyer MCW, et al. Electrochemical energy storage for green grid. Chem Rev, 2011, 111: 3577–3613CrossRefGoogle Scholar
  3. 3.
    Council NR. The NationalAcademies Summit onAmerica’s Energy Future: Summary of a Meeting. Washington: National Academies Press, 2008Google Scholar
  4. 4.
    Weber AZ, Mench MM, Meyers JP, et al. Redox flow batteries: a review. J Appl Electrochem, 2011, 41: 1137–1164CrossRefGoogle Scholar
  5. 5.
    Wang W, Luo Q, Li B, et al. Recent progress in redox flow battery research and development. Adv Funct Mater, 2013, 23: 970–986CrossRefGoogle Scholar
  6. 6.
    Ponce de León C, Frías-Ferrer A, González-García J, et al. Redox flow cells for energy conversion. J Power Sources, 2006, 160: 716–732CrossRefGoogle Scholar
  7. 7.
    Skyllas-Kazacos M. New all-vanadium redox flow cell. J Electrochem Soc, 1986, 133: 1057CrossRefGoogle Scholar
  8. 8.
    Sum E, Rychcik M, Skyllas-kazacos M. Investigation of the V(V)/V(IV) system for use in the positive half-cell of a redox battery. J Power Sources, 1985, 16: 85–95CrossRefGoogle Scholar
  9. 9.
    Sum E, Skyllas-Kazacos M. Astudy of the V(II)/V(III) redox couple for redox flowcell applications. J Power Sources, 1985, 15: 179–190CrossRefGoogle Scholar
  10. 10.
    Skyllas-Kazacos M, Rychick M, Robins R. All-vanadium redox battery. US Patent, US4786567A, 1988-11-22Google Scholar
  11. 11.
    Rahman F, Skyllas-Kazacos M. Vanadium redox battery: positive half-cell electrolyte studies. J Power Sources, 2009, 189: 1212–1219CrossRefGoogle Scholar
  12. 12.
    Parasuraman A, Lim TM, Menictas C, et al. Review of material research and development for vanadium redox flow battery applications. Electrochim Acta, 2013, 101: 27–40CrossRefGoogle Scholar
  13. 13.
    Park S, Kim H. Fabrication of nitrogen-doped graphite felts as positive electrodes using polypyrrole as a coating agent in vanadium redox flow batteries. J Mater Chem A, 2015, 3: 12276–12283CrossRefGoogle Scholar
  14. 14.
    Di Blasi A, Di Blasi O, Briguglio N, et al. Investigation of several graphite-based electrodes for vanadium redox flow cell. J Power Sources, 2013, 227: 15–23CrossRefGoogle Scholar
  15. 15.
    Wu X, Xu H, Shen Y, et al. Treatment of graphite felt by modified Hummers method for the positive electrode of vanadium redox flow battery. Electrochim Acta, 2014, 138: 264–269CrossRefGoogle Scholar
  16. 16.
    Kim KJ, Kim YJ, Kim JH, et al. The effects of surface modification on carbon felt electrodes for use in vanadium redox flow batteries. Mater Chem Phys, 2011, 131: 547–553CrossRefGoogle Scholar
  17. 17.
    Liu T, Li X, Nie H, et al. Investigation on the effect of catalyst on the electrochemical performance of carbon felt and graphite felt for vanadium flow batteries. J Power Sources, 2015, 286: 73–81CrossRefGoogle Scholar
  18. 18.
    Mayrhuber I, Dennison CR, Kalra V, et al. Laser-perforated carbon paper electrodes for improved mass-transport in high power density vanadium redox flow batteries. J Power Sources, 2014, 260: 251–258CrossRefGoogle Scholar
  19. 19.
    Jin J, Fu X, Liu Q, et al. Identifying the active site in nitrogen-doped graphene for the VO2+/VO2+ redox reaction. ACS Nano, 2013, 7: 4764–4773CrossRefGoogle Scholar
  20. 20.
    Fabjan C, Garche J, Harrer B, et al. The vanadiumredox-battery: an efficient storage unit for photovoltaic systems. Electrochim Acta, 2001, 47: 825–831CrossRefGoogle Scholar
  21. 21.
    Liu H, Yang L, Xu Q, et al. An electrochemically activated graphite electrode with excellent kinetics for electrode processes of V(II)/V(III) and V(IV)/V(V) couples in a vanadium redox flow battery. RSC Adv, 2014, 4: 55666–55670CrossRefGoogle Scholar
  22. 22.
    Kaneko H, Nozaki K, Wada Y, et al. Vanadium redox reactions and carbon electrodes for vanadium redox flow battery. Electrochim Acta, 1991, 36: 1191–1196CrossRefGoogle Scholar
  23. 23.
    Oriji G, Katayama Y, Miura T. Investigation on V(IV)/V(V) species in a vanadium redox flow battery. Electrochim Acta, 2004, 49: 3091–3095CrossRefGoogle Scholar
  24. 24.
    Liu HJ, Xu Q, Yan CW, et al. The effect of temperature on the electrochemical behavior of the V(IV)/V(V) couple on a graphite electrode. Int J Electrochem Sci, 2011, 6: 3483–3496Google Scholar
  25. 25.
    Huang KL, Li X, Liu S, et al. Research progress of vanadium redox flow battery for energy storage in China. Renewable Energy, 2008, 33: 186–192CrossRefGoogle Scholar
  26. 26.
    Vijayakumar M, Li L, Graff G, et al. Towards understanding the poor thermal stability of V5+ electrolyte solution in vanadium redox flow batteries. J Power Sources, 2011, 196: 3669–3672CrossRefGoogle Scholar
  27. 27.
    Sun B, Skyllas-Kazacos M. Modification of graphite electrode materials for vanadium redox flow battery application—I. Thermal treatment. Electrochim Acta, 1992, 37: 1253–1260CrossRefGoogle Scholar
  28. 28.
    Sun B, Skyllas-Kazacos M. Chemicalmodification of graphite electrode materials for vanadium redox flow battery application—part II. Acid treatments. Electrochim Acta, 1992, 37: 2459–2465CrossRefGoogle Scholar
  29. 29.
    Vijayakumar M, Burton SD, Huang C, et al. Nuclearmagnetic resonance studies on vanadium (IV) electrolyte solutions for vanadium redox flow battery. J Power Sources, 2010, 195: 7709–7717CrossRefGoogle Scholar
  30. 30.
    Lübke M, Ding N, Powell MJ, et al. VO2 nano-sheet negative electrodes for lithium-ion batteries. Electrochemistry Commun, 2016, 64: 56–60CrossRefGoogle Scholar
  31. 31.
    Wu X, Xu H, Lu L, et al. PbO2-modified graphite felt as the positive electrode for an all-vanadium redox flow battery. J Power Sources, 2014, 250: 274–278CrossRefGoogle Scholar
  32. 32.
    He Z, Dai L, Liu S, et al. Mn3O4 anchored on carbon nanotubes as an electrode reaction catalyst of V(IV)/V(V) couple for vanadium redox flow batteries. Electrochim Acta, 2015, 176: 1434–1440CrossRefGoogle Scholar
  33. 33.
    Park M, Jung Y, Kim J, et al. Synergistic effect of carbon nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance all-vanadium redox flow battery. Nano Lett, 2013, 13: 4833–4839CrossRefGoogle Scholar
  34. 34.
    Wei G, Fan X, Liu J, et al. Electrospun carbon nanofibers/electrocatalyst hybrids as asymmetric electrodes for vanadium redox flow battery. J Power Sources, 2015, 281: 1–6CrossRefGoogle Scholar
  35. 35.
    Han P, Wang X, Zhang L, et al. RuSe/reduced graphene oxide: an efficient electrocatalyst for VO2+/V2 + redox couples in vanadium redox flow batteries. RSC Adv, 2014, 4: 20379CrossRefGoogle Scholar
  36. 36.
    Candelaria SL, Shao Y, Zhou W, et al. Nanostructured carbon for energy storage and conversion. Nano Energy, 2012, 1: 195–220CrossRefGoogle Scholar
  37. 37.
    Garcia BB, Candelaria SL, Liu D, et al. High performance high-purity sol-gel derived carbon supercapacitors from renewable sources. Renewable Energy, 2011, 36: 1788–1794CrossRefGoogle Scholar
  38. 38.
    Candelaria SL, Uchaker E, Cao G. Comparison of surface and bulk nitrogenmodification in highly porous carbon for enhanced supercapacitors. Sci China Mater, 2015, 58: 521–533CrossRefGoogle Scholar
  39. 39.
    Massé RC, Uchaker E, Cao G. Beyond Li-ion: electrode materials for sodium- and magnesium-ion batteries. Sci China Mater, 2015, 58: 715–766CrossRefGoogle Scholar
  40. 40.
    Candelaria SL, Garcia BB, Liu D, et al. Nitrogen modification of highly porous carbon for improved supercapacitor performance. J Mater Chem, 2012, 22: 9884CrossRefGoogle Scholar
  41. 41.
    Guo H, Gao Q. Boron and nitrogen co-doped porous carbon and its enhanced properties as supercapacitor. J Power Sources, 2009, 186: 551–556CrossRefGoogle Scholar
  42. 42.
    Kim W, Joo JB, Kim N, et al. Preparation of nitrogen-doped mesoporous carbon nanopipes for the electrochemical double layer capacitor. Carbon, 2009, 47: 1407–1411CrossRefGoogle Scholar
  43. 43.
    Vinu A, Anandan S, Anand C, et al. Fabrication of partially graphitic three-dimensional nitrogen-doped mesoporous carbon using polyaniline nanocomposite through nanotemplating method. Microporous Mesoporous Mater, 2008, 109: 398–404CrossRefGoogle Scholar
  44. 44.
    Shao Y, Wang X, Engelhard M, et al. Nitrogen-doped mesoporous carbon for energy storage in vanadium redox flow batteries. J Power Sources, 2010, 195: 4375–4379CrossRefGoogle Scholar
  45. 45.
    Vijayakumar M, Nie Z, Walter E, et al. Understanding aqueous electrolyte stability through combined computational and magnetic resonance spectroscopy: a case study on vanadium redox flow battery electrolytes. Chem Plus Chem, 2015, 80: 428–437Google Scholar
  46. 46.
    Qiu G, Dennison CR, Knehr KW, et al. Pore-scale analysis of effects of electrode morphology and electrolyte flow conditions on performance of vanadium redox flow batteries. J Power Sources, 2012, 219: 223–234CrossRefGoogle Scholar
  47. 47.
    Park M, Ryu J, Kim Y, et al. Corn protein-derived nitrogen-doped carbonmaterials with oxygen-rich functional groups: a highly efficient electrocatalyst for all-vanadium redox flow batteries. Energy Environ Sci, 2014, 7: 3727–3735CrossRefGoogle Scholar
  48. 48.
    Ryu J, Park M, Cho J. Catalytic effects of B/N-co-doped porous carbon incorporated with ketjenblack nanoparticles for all-vanadium redox flow batteries. J Electrochem Soc, 2016, 163: A5144–A5149CrossRefGoogle Scholar
  49. 49.
    Liu J, Wang ZA, Wu XW, et al. Porous carbon derived from disposable shaddock peel as an excellent catalyst toward V2+/V2 + couple for vanadium redox battery. J Power Sources, 2015, 299: 301–308CrossRefGoogle Scholar
  50. 50.
    García BB, Liu D, Sepehri S, et al. Hexamethylenetetramine multiple catalysis as a porosity and pore sizemodifier in carbon cryogels. J Non-Crystalline Solids, 2010, 356: 1620–1625CrossRefGoogle Scholar
  51. 51.
    Tuinstra F, Koenig JL. Raman spectrum of graphite. J Chem Phys, 1970, 53: 1126–1130CrossRefGoogle Scholar
  52. 52.
    Wei G, Jia C, Liu J, et al. Carbon felt supported carbon nanotubes catalysts composite electrode for vanadium redox flow battery application. J Power Sources, 2012, 220: 185–192CrossRefGoogle Scholar
  53. 53.
    Li X, Huang K, Liu S, et al. Characteristics of graphite felt electrode electrochemically oxidized for vanadium redox battery application. Trans Nonferrous Met Soc China, 2007, 17: 195–199CrossRefGoogle Scholar
  54. 54.
    Liu F, Wang H, Xue L, et al. Effect of microstructure on the mechanical properties of PAN-based carbon fibers during high-temperature graphitization. J Mater Sci, 2008, 43: 4316–4322CrossRefGoogle Scholar
  55. 55.
    Sadezky A, Muckenhuber H, Grothe H, et al. Raman microspectroscopy of soot and related carbonaceousmaterials: spectral analysis and structural information. Carbon, 2005, 43: 1731–1742CrossRefGoogle Scholar
  56. 56.
    Wang Y, Alsmeyer DC, McCreery RL. Raman spectroscopy of carbon materials: structural basis of observed spectra. Chem Mater, 1990, 2: 557–563CrossRefGoogle Scholar
  57. 57.
    Ko TH. Raman spectrum of modified PAN-based carbon fibers during graphitization. J Appl Polym Sci, 1996, 59: 577–580CrossRefGoogle Scholar
  58. 58.
    Schweiss R. Influence of bulk fibre properties of PAN-based carbon felts on their performance in vanadium redox flow batteries. J Power Sources, 2015, 278: 308–313CrossRefGoogle Scholar
  59. 59.
    González Z, Botas C, Blanco C, et al. Graphite oxide-based graphene materials as positive electrodes in vanadium redox flow batteries. J Power Sources, 2013, 241: 349–354CrossRefGoogle Scholar
  60. 60.
    Jeong S, An S, Jeong J, et al. Effect of mesocelluar carbon foam electrodematerial on performance of vanadium redox flow battery. J Power Sources, 2015, 278: 245–254CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  1. 1.Department of Materials Science and EngineeringUniversity of WashingtonSeattleUSA

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