釩液流電池大多選用大面積、高導電和多孔結構的碳材作為電
極，而石墨氈為符合此需求的材料之一。然而，石墨氈材料面臨電化
學活性不足及可逆性較差等問題，嚴重影響全電池效率的表現。因此
本研究將以二氧化鈰奈米線修飾電極為出發，利用奈米線形貌與氫
氣處理增加電極之電化學活性，期能藉由奈米線形貌之高比表面積
提升反應面積再透過氫氣還原作用處理，製造氧空缺做為反應之活
性點，催化釩離子反應。
本研究將利用二氧化鈰之奈米線混合於石墨氈上，並在高溫爐
管中利用氫氣處理，製造氧空缺，增加二氧化鈰之電化學活性。透過
多種材料分析技術與電化學量測，分析氫氣處理後之性質變化與應
用在釩液流電池中表現出效能之關聯性。
關鍵詞：儲能系統、釩液流電池、金屬氧

Carbon-based materials with large surface area, high conductivity,
and porous structure are used as the electrode in vanadium redox flow
battery (VRFB). However, the graphite felt has a low energy efficiency
problem due to its insufficient electrochemical activity and poor
reversibility. In order to solve this problem, we decorated electrode by
cerium oxide nanowires and treated it with hydrogen to increase the
electrochemical activity of the electrode. The high specific surface area of
the nanowires morphology was used to increase the reaction
area .Moreover, a part of the oxygen from cerium oxide was reduced byhydrogen treatment to produce oxygen vacancies.
In this study, the nanowires of cerium oxide were mixed with carbon
felts and treated with hydrogen in high temperature to increase the
electrochemical activity of cerium oxide. Through variety of material
analysis techniques and electrochemical measurements, we analyzed the
relation between the hydrogen treatment and the performance in vanadium
flow batteries.

1] H. Zhang, S. Liang, B. Sun, X. Yang, X. Wu, T. Yang, A hybrid redox flow
battery with high energy efficiency using a low cost sandwiched membrane as a
separator and LiMn2O4 as a cathode. Journal of Materials Chemistry A, 1 (2013)
14476.
[2] T.U. Daim, X. Li, J. Kim, S. Simms, Evaluation of energy storage technologies for
integration with renewable electricity: Quantifying expert opinions. Environmental
Innovation and Societal Transitions, 3 (2012) 29-49.
[3] C.J. Rydh, Environmental assessment of vanadium redox and lead-acid batteries
for stationary energy storage. J. Power Sources, 80 (1999) 21-29.
[4] S. Rubenwolf, O. Strohmeier, A. Kloke, S. Kerzenmacher, R. Zengerle, F. von
Stetten, Carbon electrodes for direct electron transfer type laccase cathodes
investigated by current density-cathode potential behavior. Biosens Bioelectron, 26
(2010) 841-845.
[5] N.A.a.S.A.W. DC, Flow Cell Development and Demonstration. NASA TM-
97067, (1979).
[6] E. Sum, M. Rychcik, M. Skyllas-kazacos, Investigation of the V(V)/V(IV) system
for use in the positive half-cell of a redox battery. Journal of Power Sources, 16
(1985) 85-95.
[7] E. Sum, M. Skyllas-Kazacos, A study of the V(II)/V(III) redox couple for redox
flow cell applications. J. Power Sources, 15 (1985) 179-190.
[8] P. Alotto, M. Guarnieri, F. Moro, Redox flow batteries for the storage of
renewable energy: A review. Renewable and Sustainable Energy Reviews, 29 (2014)
325-335.
[9] C. Jizhong, X. Ziqiang, L. Bei, Research on the characteristics of the vanadium
redox-flow battery in power systems applications. Journal of Power Sources, 241
(2013) 396-399.
[10] C. Fabjan, J. Garche, B. Harrer, L. Jörissen, C. Kolbeck, F. Philippi, G. Tomazic,
F. Wagner, The vanadium redox-battery: an efficient storage unit for photovoltaic
systems. Electrochim. Acta, 47 (2001) 825-831.
[11] M. Vijayakumar, S.D. Burton, C. Huang, L. Li, Z. Yang, G.L. Graff, J. Liu, J.
Hu, M. Skyllas-Kazacos, Nuclear magnetic resonance studies on vanadium(IV)
electrolyte solutions for vanadium redox flow battery. Journal of Power Sources, 195
(2010) 7709-7717.
[12] M. Gattrell, J. Qian, C. Stewart, P. Graham, B. MacDougall, The electrochemical
reduction of VO2+ in acidic solution at high overpotentials. Electrochimica Acta, 51
(2005) 395-407
[13] M. Park, Y.-J. Jung, J. Kim, H.I. Lee, J. Cho, Synergistic effect of carbon
nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance
all-vanadium redox flow battery. Nano Lett., 13 (2013) 4833-4839.
[14] J. Jin, X. Fu, Q. Liu, Y. Liu, Z. Wei, K. Niu, J. Zhang, Identifying the Active Site
in Nitrogen-Doped Graphene for the VO2+/VO2
+ Redox Reaction. ACS Nano, 7
(2013) 4764-4773.
[15] D. Chen, M.A. Hickner, S. Wang, J. Pan, M. Xiao, Y. Meng, Directly fluorinated
polyaromatic composite membranes for vanadium redox flow batteries. Journal of
Membrane Science, 415-416 (2012) 139-144.
[16] H. Chen, T.N. Cong, W. Yang, C. Tan, Y. Li, Y. Ding, Progress in electrical
energy storage system: A critical review. Progress in Natural Science, 19 (2009) 291-
312.
[17] C. Ding, H. Zhang, X. Li, T. Liu, F. Xing, Vanadium Flow Battery for Energy
Storage: Prospects and Challenges. The Journal of Physical Chemistry Letters, 4
(2013) 1281-1294.
[18] M. Skyllas‐Kazacos, C. Menictas, M. Kazacos, Thermal Stability of
Concentrated V(V) Electrolytes in the Vanadium Redox Cell. J. Electrochem. Soc.,
143 (1996) L86-L88.
[19] F. Rahman, M. Skyllas-Kazacos, Solubility of vanadyl sulfate in concentrated
sulfuric acid solutions. J. Power Sources, 72 (1998) 105-110.
[20] G. Oriji, Y. Katayama, T. Miura, Investigation on V(IV)/V(V) species in a
vanadium redox flow battery. Electrochimica Acta, 49 (2004) 3091-3095.
[21] B. Dunn, H. Kamath, J.-M. Tarascon, Electrical Energy Storage for the Grid: A
Battery of Choices. Science, 334 (2011) 928-935.
[22] H. Zhou, J. Xi, Z. Li, Z. Zhang, L. Yu, L. Liu, X. Qiu, L. Chen, CeO2 decorated
graphite felt as a high-performance electrode for vanadium redox flow batteries. RSC
Adv., 4 (2014) 61912-61918.
[23] S. Cong, Y. Yuan, Z. Chen, J. Hou, M. Yang, Y. Su, Y. Zhang, L. Li, Q. Li, F.
Geng, Z. Zhao, Noble metal-comparable SERS enhancement from semiconducting
metal oxides by making oxygen vacancies. Nat Commun, 6 (2015) 7800.
[24] H.-M. Tsai, S.-Y. Yang, C.-C.M. Ma, X. Xie, Preparation and Electrochemical
Properties of Graphene-Modified Electrodes for All-Vanadium Redox Flow Batteries.
Electroanalysis, 23 (2011) 2139-2143.
[25] H.-M. Tsai, S.-J. Yang, C.-C.M. Ma, X. Xie, Preparation and electrochemical
activities of iridium-decorated graphene as the electrode for all-vanadium redox flow
batteries. Electrochimica Acta, 77 (2012) 232-236.
[26] T.M. Tseng, R.H. Huang, C.Y. Huang, C.C. Liu, K.L. Hsueh, F.S. Shieu, CarbonFelt Coated with Titanium Dioxide/Carbon Black Composite as Negative Electrode
for Vanadium Redox Flow Battery. Journal of the Electrochemical Society, 161
(2014) A1132-A1138.
[27] T.-C. Chang, J.-P. Zhang, Y.-K. Fuh, Electrical, mechanical and morphological
properties of compressed carbon felt electrodes in vanadium redox flow battery. J.
Power Sources, 245 (2014) 66-75.
[28] J.-Z. Chen, W.-Y. Liao, W.-Y. Hsieh, C.-C. Hsu, Y.-S. Chen, All-vanadium
redox flow batteries with graphite felt electrodes treated by atmospheric pressure
plasma jets. Journal of Power Sources, 274 (2015) 894-898.
[29] D. Chen, M.A. Hickner, E. Agar, E.C. Kumbur, Optimized Anion Exchange
Membranes for Vanadium Redox Flow Batteries. ACS Applied Materials &
Interfaces, 5 (2013) 7559-7566.
[30] A. Parasuraman, T.M. Lim, C. Menictas, M. Skyllas-Kazacos, Review of
material research and development for vanadium redox flow battery applicat ions.
Electrochimica Acta, 101 (2013) 27-40.
[31] C. Yao, H. Zhang, T. Liu, X. Li, Z. Liu, Carbon paper coated with supported
tungsten trioxide as novel electrode for all-vanadium flow battery. Journal of Power
Sources, 218 (2012) 455-461.
[32] Y. Shen, H. Xu, P. Xu, X. Wu, Y. Dong, L. Lu, Electrochemical catalytic activity
of tungsten trioxide- modified graphite felt toward VO2+/VO2
+ redox reaction.
Electrochimica Acta, 132 (2014) 37-41.
[33] X. Wu, H. Xu, L. Lu, H. Zhao, J. Fu, Y. Shen, P. Xu, Y. Dong, PbO2-modified
graphite felt as the positive electrode for an all-vanadium redox flow battery. Journal
of Power Sources, 250 (2014) 274-278.
[34] Z. González, A. Sánchez, C. Blanco, M. Granda, R. Menéndez, R. Santamaría,
Enhanced performance of a Bi-modified graphite felt as the positive electrode of a
vanadium redox flow battery. Electrochemistry Communications, 13 (2011) 1379-
1382.
[35] B. Sun, M. Skyllas-Kazakos, Chemical modification and electrochemical
behaviour of graphite fibre in acidic vanadium solution. Electrochim. Acta, 36 (1991)
513-517.
[36] W.H. Wang, X.D. Wang, Investigation of Ir-modified carbon felt as the positive
electrode of an all-vanadium redox flow battery. Electrochimica Acta, 52 (2007)
6755-6762.
[37] M. Rychcik, M. Skyllas-Kazacos, EVALUATION OF ELECTRODE
MATERIALS FOR VANADIUM REDOX CELL. J. Power Sources, 19 (1987) 45-
54.
[38] J. Han, H. Yoo, M. Kim, G. Lee, J. Choi, High-performance bipolar plate of thin
IrOx-coated TiO2nanotubes in vanadium redox flow batteries. Catal. Today, 295
(2017) 132-139.
[39] K.J. Kim, M.-S. Park, J.-H. Kim, U. Hwang, N.J. Lee, G. Jeong, Y.-J. Kim,
Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries. Chem.
Commun., 48 (2012) 5455-5457.
[40] Z. He, L. Dai, S. Liu, L. Wang, C. Li, Mn3O4 anchored on carbon nanotubes as
an electrode reaction catalyst of V(IV)/V(V) couple for vanadium redox flow
batteries. Electrochimica Acta, 176 (2015) 1434-1440.
[41] A. Di Blasi, C. Busaccaa, O. Di Blasia, N. Briguglio, G. Squadrito, V.
Antonuccia, Synthesis of flexible electrodes based on electrospun carbon nanofibers
with Mn3O4nanoparticles for vanadium redox flow battery application. Applied
Energy, 190 (2017) 165-171.
[42] B. Li, M. Gu, Z. Nie, X. Wei, C. Wang, V. Sprenkle, W. Wang, Nanorod
niobium oxide as powerful catalysts for an all vanadium redox flow battery. Nano
Lett., 14 (2014) 158-165.
[43] J. Winsberg, T. Hagemann, T. Janoschka, M.D. Hager, U.S. Schubert, Redox-
Flow Batteries: From Metals to Organic Redox-Active Materials. Angew Chem Int
Ed Engl, 56 (2017) 686-711.
[44] H.T. Thu Pham, C. Jo, J. Lee, Y. Kwon, MoO2 nanocrystals interconnected on
mesocellular carbon foam as a powerful catalyst for vanadium redox flow battery.
RSC Adv., 6 (2016) 17574-17582.
[45] J. Maruyama, T. Hasegawa, S. Iwasaki, T. Fukuhara, Y. Orikasa, Y. Uchimoto,
Carbonaceous thin film coating with Fe–N4 site for enhancement of dioxovanadium
ion reduction. Journal of Power Sources, 324 (2016) 521-527.
[46] A. Di Blasi, O. Di Blasi, N. Briguglio, A.S. Aricò, D. Sebastián, M.J. Lázaro, G.
Monforte, V. Antonucci, Investigation of several graphite-based electrodes for
vanadium redox flow cell. Journal of Power Sources, 227 (2013) 15-23.
[47] L. Yue, W. Li, F. Sun, L. Zhao, L. Xing, Highly hydroxylated carbon fibres as
electrode materials of all-vanadium redox flow battery. Carbon, 48 (2010) 3079-3090.
[48] W. Li, J. Liu, C. Yan, Graphite–graphite oxide composite electrode for vanadium
redox flow battery. Electrochimica Acta, 56 (2011) 5290-5294.
[49] X. Wu, H. Xu, P. Xu, Y. Shen, L. Lu, J. Shi, J. Fu, H. Zhao, Microwave-treated
graphite felt as the positive electrode for all-vanadium redox flow battery. Journal of
Power Sources, 263 (2014) 104-109.
[50] K.J. Kim, S.W. Lee, T. Yim, J.G. Kim, J.W. Choi, J.H. Kim, M.S. Park, Y.J.
Kim, A new strategy for integrating abundant oxygen functional groups into carbon
felt electrode for vanadium redox flow batteries. Sci Rep, 4 (2014) 6906.
[51] <Liu-2016-Electrochemical behavior of vanadium.pdf>.
[52] A. Di Blasi, O. Di Blasi, N. Briguglio, A.S. Arico, D. Sebastian, M.J. Lazaro, G.
Monforte, V. Antonucci, Investigation of several graphite-based electrodes for
vanadium redox flow cell. 227 (2012) 15-23.
[53] X. Wang, X. Li, L. Zhang, Y. Yoon, P.K. Weber, H. Wang, J. Guo, H. Dai, NDoping
of Graphene Through Electrothermal Reactions with Ammonia. Science, 324
(2009) 768-771.
[54] A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, P.M.
Ajayan, Synthesis Of Nitrogen-Doped Graphene Films For Lithium Battery
Application. ACS Nano, 4 (2010) 6337-6342.
[55] Y. Wang, Y. Shao, D.W. Matson, J. Li, Y. Lin, Nitrogen-Doped Graphene and
Its Application in Electrochemical Biosensing. ACS Nano, 4 (2010) 1790-1798.
[56] V. Nallathambi, J.-W. Lee, S.P. Kumaraguru, G. Wu, B.N. Popov, Development
of high performance carbon composite catalyst for oxygen reduction reaction in PEM
Proton Exchange Membrane fuel cells. J. Power Sources, 183 (2008) 34-42.
[57] S. Maldonado, K.J. Stevenson, Influence of Nitrogen Doping on Oxygen
Reduction Electrocatalysis at Carbon Nanofiber Electrodes. J. Phys. Chem. B, 109
(2005) 4707-4716.
[58] Y. Shao, J. Sui, G. Yin, Y. Gao, Nitrogen-doped carbon nanostructures and their
composites as catalytic materials for proton exchange membrane fuel cell. Appl.
Catal. B: Environ., 79 (2008) 89-99.
[59] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Nitrogen-Doped Carbon Nanotube
Arrays with High Electrocatalytic Activity for Oxygen Reduction. Science, 323
(2009) 760-764.
[60] R.A. Sidik, A.B. Anderson, N.P. Subramanian, S.P. Kumaraguru, B.N. Popov,
O2 Reduction on Graphite and Nitrogen-Doped Graphite: Experiment and Theory. J.
Phys. Chem. B, 110 (2006) 1787-1793.
[61] G. Wu, D. Li, C. Dai, D. Wang, N. Li, Well-Dispersed High-Loading Pt
Nanoparticles Supported by Shell−Core Nanostructured Carbon for Methanol
Electrooxidation. Langmuir, 24 (2008) 3566-3575.
[62] J.-i. Ozaki, S.-i. Tanifuji, A. Furuichi, K. Yabutsuka, Enhancement of oxygen
reduction activity of nanoshell carbons by introducing nitrogen atoms from metal
phthalocyanines. Electrochim. Acta, 55 (2010) 1864-1871.
[63] C. Médard, M. Lefèvre, J.P. Dodelet, F. Jaouen, G. Lindbergh, Oxygen reduction
by Fe-based catalysts in PEM fuel cell conditions: Activity and selectivity of the
catalysts obtained with two Fe precursors and various carbon supports. Electrochim.
Acta, 51 (2006) 3202-3213.
[64] C.-H. Wang, S.-T. Chang, H.-C. Hsu, H.-Y. Du, J.C.-S. Wu, L.-C. Chen, K.-H.
Chen, Oxygen reducing activity of methanol-tolerant catalysts by high-temperature
pyrolysis. Diamond Relat. Mater., 20 (2011) 322-329.
[65] C.-H. Wang, H.-C. Hsu, S.-T. Chang, H.-Y. Du, C.-P. Chen, J.C.-S. Wu, H.-C.
Shih, L.-C. Chen, K.-H. Chen, Platinum nanoparticles embedded in pyrolyzed
nitrogen-containing cobalt complexes for high methanol-tolerant oxygen reduction
activity. J. Mater. Chem., 20 (2010) 7551.
[66] F. Jaouen, S. Marcotte, J.-P. Dodelet, G. Lindbergh, Oxygen Reduction Catalysts
for Polymer Electrolyte Fuel Cells from the Pyrolysis of Iron Acetate Adsorbed on
Various Carbon Supports. J. Phys. Chem. B, 107 (2003) 1376-1386.
[67] D. Villers, X. Jacques-Bedard, J.-P. Dodelet, Fe-based catalysts for oxygen
reduction in PEM fuel cells pretreatment of the carbon support. J. Electrochem. Soc.,
151 (2004) A1507-A1515.
[68] Y. Shao, X. Wang, M. Engelhard, C. Wang, S. Dai, J. Liu, Z. Yang, Y. Lin,
Nitrogen-doped mesoporous carbon for energy storage in vanadium redox flow
batteries. Journal of Power Sources, 195 (2010) 4375-4379.
[69] L.G. Cançado, A. Jorio, E.H .M . Ferreira, F. Stavale, C.A. A chete, R. B. Capaz,
M.V.O. Moutinho, A. Lombardo, T.S. Kulmala, A.C. Ferrari, Quantifying Defects in
Graphene via Raman Spectroscopy at Different Excitation Energies. Nano Lett., 11
(2011) 3190-3196.
[70] W.Y. Li, J.G. Liu, C.W. Yan, Multi-walled carbon nanotubes used as an
electrode reaction catalyst for VO2+/VO2
+ for a vanadium redox flow battery. Carbon,
49 (2011) 3463-3470.
[71] W.Y. Li, J.G. Liu, C.W. Yan, Modified multiwalled carbon nanotubes as an
electrode reaction catalyst for an all vanadium redox flow battery. J Solid State Electr,
17 (2013) 1369-1376.
[72] M. Park, Y.J. Jung, J. Kim, H. Lee, J. Cho, Synergistic effect of carbon
nanofiber/nanotube composite catalyst on carbon felt electrode for high-performance
all-vanadium redox flow battery. Nano Lett, 13 (2013) 4833-4839.
[73] O. Di Blasi, N. Briguglio, C. Busacca, M. Ferraro, V. Antonucci, A. Di Blasi,
Electrochemical investigation of thermically treated graphene oxides as electrode
materials for vanadium redox flow battery. Applied Energy, 147 (2015) 74-81.
[74] Z. Ji, X. Wang, H. Zhang, S. Lin, H. Meng, B. Sun, S. George, T. Xia, A.E. Nel,
J.I. Zink, Designed Synthesis of CeO2 Nanorods and Nanowires for Studying
Toxicological Effects of High Aspect Ratio Nanomaterials. ACS Nano, 6 (2012)
5366-5380.
[75] W. Gao, Z. Zhang, J. Li, Y. Ma, Y. Qu, Surface engineering on CeO2 nanorods
by chemical redox etching and their enhanced catalytic activity for CO oxidation.
Nanoscale, 7 (2015) 11686-11691.
[76] J. Vazquez-Galvan, C. Flox, C. Fabrega, E. Ventosa, A. Parra, T. Andreu, J.R.
Morante, Hydrogen-Treated Rutile TiO2 Shell in Graphite-Core Structure as a
Negative Electrode for High-Performance Vanadium Redox Flow Batteries.
ChemSusChem, 10 (2017) 2089-2098.
[77] Bard A. J. , Faulkner L.R. , Electrochemical Methods - Fundamentals and
Application. ISBN 0-471-04372-9.
[78] P. Han, Y. Yue, Z. Liu, W. Xu, L. Zhang, H. Xu, S. Dong, G. Cui, Graphene
oxide nanosheets/multi-walled carbon nanotubes hybrid as an excellent
electrocatalytic material towards VO2+/VO2+ redox couples for vanadium redox flow
batteries. Energy Eviron. Sci., 4 (2011) 4710.