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WIREs Energy Environ.
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Recent progress on carbon and metal based electrocatalysts for vanadium redox flow battery

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Abstract Attractive features of vanadium redox flow battery (VRFB) such as long durability, easy scalability, and low levelized cost of energy have influenced its prominence in the sectors where renewable energy is to be stored at a large scale. However, viability of VRFB to be used for a wide‐range of applications such as household electrification, electric vehicle charging infrastructure, and so on has been limited by its low power density. In principle, the power density of VRFB is dependent upon rate of electrochemical reaction on the electrode. The electrochemical properties of the electrode can be improved either by pretreatment of the electrode or by depositing electrocatalyst on the electrode. The use of electrocatalyst helps to lower overpotential losses and reduces the charge‐transfer resistance, which results the VRFB to operate at higher current densities. This review discusses the development and progress of carbon and metal‐based electrocatalyst that have been used for VRFB applications. This article is categorized under: Fuel Cells and Hydrogen > Science and Materials Energy Efficiency > Science and Materials Energy and Development > Science and Materials
A typical vanadium redox flow battery
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CV curves at scan rate 2 mV s−1 for (a) V2+/V3+ redox couple, (b) VO2+/VO2+ redox couple, (c) Nyquist plots in the three kinds of electrodes recorded in 0.1 M VOSO4 + 2 M H2SO4, and (d) Charge–discharge curve of the VRFB single cell with different electrodes at a current density of 100 mA cm−2. (Reprinted with permission (through Copyright Clearance Central) from reference Wei et al. (2015). Copyright © 2015 Elsevier Ltd)
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(a) CVs recorded at a 5‐mm diameter bare GC electrode and a GC electrode modified with N‐rGO‐Mn3O4 at 30 mV s−1 in 1.0 M VOSO4 + 2.0 M H2SO4 between −0.7 V (initial potential) and 1.3 V for N‐rGO‐Mn3O4 and between −0.9 (initial potential) and 1.3 V for bare GC. The dashed line shows the response obtained at the modified GC electrode in blank H2SO4. (b) Cyclic voltammograms recorded in 1.0 M VOSO4 + 2.0 M H2SO4 at an N‐rGO/Mn3O4‐modified GC electrode at before and after 2000 cycles between 0.4 (initial potential) and 1.3 V at 500 mV s−1. (Reprinted with permission (through Copyright Clearance Central) from Ejigu et al. (2015). Copyright ©2015 American Chemical Society)
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Cyclic voltammograms with or without Nb2O5 nanorods onto glassy carbon as working electrodes in solutions of 2 M VOSO4 + 5 M HCl. (Reprinted with permission (through Copyright Clearance Central) from reference Li et al. (2014). Copyright © 2014 American Chemical Society)
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(a) The contact angles of GF and CeO2/GFs, (b) Cyclic voltammograms curves of GF and CeO2/GFs at a scan rate of 1 mV s−1 in a solution of 0.1 M VOSO4 + 2 M H2SO4.(Reprinted with permission (through Copyright Clearance Central) from Zhou et al. (2014). Copyright © The Royal Society of Chemistry 2014)
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(a) Illustration of the mechanism for VO2+/VO2+ redox reaction occurring in the presence of Ta2O5 nanoparticles on the surface of the GF electrode, (b) EIS curves of GF and various wt.% of Ta2O5 on GF with an excitation signal of 10 mV under an open‐circuit potential, and (c) CV curves of the electrodes at a scan rate of 3 mV s−1 in 0.05 M VOSO4 + 2 M H2SO4 solution.(Reprinted with permission (through Copyright Clearance Central) from Bayeh et al. (2018). Copyright © 2018 American Chemical Society)
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Illustration of fabrication process, and the designed structure of 3D graphene‐nanowall‐modified CF. (Reprinted with permission (through Creative Commons) from Li et al. (2016). Copyright © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
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Cyclic voltammetry curves for diverse electrodes (GCE‐Glassy carbon electrode, α,γ‐TiO2 represent anatase and rutile phase, respectively, AB‐Acetylene black) in (a) 1.6 M V3+ + 3.0 M H2SO4 electrolyte at 10 mV s−1, (b) 1.6 M VO2+ + 3.0 M H2SO4 electrolyte at 10 mV s−1 . (Reprinted with permission (through Copyright Clearance Central) from reference Cheng et al. (2019). Copyright © 2019 John Wiley & Sons, Ltd.)
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(a) Schematic of GO‐rGO/GF hybrid electrode in VRFBs, (b) Nyquist diagrams, and (c) CV curves of different electrodes at a scan rate of 5 mV s−1 in 0.1 M VO2+ + 2 M H2SO4.(Reprinted with permission (through Copyright Clearance Central) from reference (Hu, Jing, M., Wang, Sun, Xu, Ren, Cheng, Yan, Fan, & Li, 2018). Copyright © 2017 Elsevier
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(a) SEM image of CNF/CNT grown over CF surface prepared at 700°C, (b) Charge–discharge voltage profiles of untreated and as‐prepared electrode at 40 mA cm−2; Cyclic voltammograms with untreated CF and CNF/CNT deposited CF in different temperatures and in 0.1 M VO2+ + 2 M H2SO4 (c) V+2/V+3, (d) VO2+/VO2+ redox couple at 5 mV s−1. (Reprinted with permission (through Copyright Clearance Central) from Park et al. (2013). Copyright © 2013, American Chemical Society)
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Cyclic voltammograms of the pristine graphite, GONP‐50, GONP‐90, and GONP‐120 at scan rate of 10 mV s−1 in 2 M VOSO4 + 2 M H2SO4. (Reprinted with permission (through Copyright Clearance Centre) from Han et al. (2011), Copyright © 2010 Elsevier)
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Electrocatalysts for VRFB. C, carbon; GO, graphene oxide; GNW, graphene nanowall; MWCNT, multiwall carbon nanotube; NW, nanowire; N‐rGO, nitrogen doped reduced graphene oxide; PDA, polydopamine; rGO, reduced graphene oxide; X = F, Cl, and Br)
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SEM images of the mesoporous AC derived from (a) coconut shell (reprinted with permission (through Copyright Clearance Centre) from Ulaganathan et al. (2015). Copyright © 2014 Elsevier), (b) sugarcane bagasse (reprinted with permission (through Copyright Clearance Centre) from Mahanta et al. (2019), Copyright © 2019 Elsevier), (c) tire waste (reprinted with permission (through Copyright Clearance Centre) from Kumar et al. (2018), Copyright © 2018 American Chemical Society); and Cyclic voltammograms (CVs) of cell using AC electrocatalyst derived from (d) coconut shell at scan rate 5 mV s−1 in 0.85 M VO2+ + 0.85 M V3+ + 4 M H2SO4 (reprinted with permission (through Copyright Clearance Centre) from Ulaganathan et al. (2015), Copyright © 2014 Elsevier), (e) sugarcane bagasse at scan rate 10 mV s−1 in 0.1M VO2+ + 2.5 M H2SO4 (reprinted with permission (through Copyright Clearance Centre) from Mahanta et al. (2019), Copyright © 2019 Elsevier), (f) tire waste at scan rate 10 mV s−1 in 0.1 M VO2+ + 2 M H2SO4 (reprinted with permission (through Copyright Clearance Centre) from Kumar et al. (2018), Copyright © 2018 American Chemical Society)
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Energy Efficiency > Science and Materials
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