Carbon Paper Electrodes Modified with Bismuth for Enhancing the Performance of Vanadium Redox Flow Batteries

Redox flow batteries (RFBs) are a promising technology for grid scale stationary energy storage to complement renewable energy systems. Although RFBs have a relatively low energy density, they offer important benefits such as long lifetime, decoupled energy and power, high round-trip efficiency, scalability and design flexibility, fast response and low environmental impacts. These benefits make them superior to many other stationary energy storage technologies [1-3]. The vanadium RFB (VRFB) is the most widely used RFB in industry for grid scale energy storage and for integration of renewable energy generation systems [4]. However, due to their slow redox reaction rates, their performance and stability are limited and VRFBs would thus benefit from enhancement of the electrode kinetics [5]. Various catalysts have been employed to improve the redox reaction rates [5-6]. Bismuth is considered a suitable candidate due to its good reactivity with oxygen, low toxicity, relatively low cost and comparable catalytic properties to other metal competitors [5, 7-8]. In this study, we present a novel modified VRFB electrode composed of carbonized bismuth-polyaniline (Bi-PANI) on a thermally-treated carbon paper substrate. The battery performance was evaluated in a 5 cm2 flow cell using a ‘zero-gap’ design with a 1.6 M VOSO4 in 3 M H2SO4 electrolyte. Charge-discharge of the VRFB was performed at a constant current density (ranging from 10 to 80 mA cm−2) with upper and lower voltage cut-offs of 1.65 and 0.8 V, respectively. Thermally treated carbon paper electrodes were tested as a comparison, and it was found that the VRFB efficiency was significantly enhanced, from 51% to 68% at a current density of 80 mA cm− 2, due to the modification of the electrodes with Bi-PANI. The charge-discharge capacity was also improved by around 17.2%. In addition, the stability of the battery using the modified electrodes was evaluated for over 200 cycles. The improved battery performance was attributed to the catalytic effect of the Bi particles on the VO2+/VO2 + and V2+/V3+ redox reactions leading to a significant increase in capacity, voltage, and energy efficiency. References: [1] M. Skyllas-Kazacos, L. Cao, M. Kazacos, N. Kausar, A. Mousa, ChemSusChem. 9 (2016) 1521–1543. [2] A.K. Singh, M. Pahlevaninezhad, N. Yasri, E. Roberts, ChemSusChem. (2021). [3] M. Pahlevaninezhad, P. Leung, M. Pahlevani, F. C. Walsh, C. Ponce de Leon, and E. P. L. Roberts, Experimental and Computational Studies of Disperse Blue-1 in Organic Non-Aqueous Redox Flow Batteries, J. Power Sources, Volume 500, 15 July 2021, 229942. [4] X.Z. Yuan, C. Song, A. Platt, N. Zhao, H. Wang, H. Li, K. Fatih, D. Jang, Int. J. Energy Res. (2019). [5] S. Moon, B.W. Kwon, Y. Chung, Y. Kwon, Journal of The Electrochemical Society, 166 (12) A2602-A2609 (2019) [6] W. Lee, C. Jo, S. Youk, H. Y. Shin, J. Lee, Y. Chung, and Y. Kwon, Appl. Surf. Sci., 429, 187 (2018) [7] Z González, A. Sánchez, C. Blanco, M. Granda, R. Menéndez, and R. Santamaria, Electrochem. Commun., 13, 1379 (2011). [8] B. Li, M. Gu, Z. Nie, Y. Shao, Q. Luo, X. wei, X. Li, J. Xiao, C. Wang, V. Sprenkle, and W. Wang, Nano Lett., 13, 1330 (2013).