(Keynote) Pro and Con of Bi-Decorated Carbon Felts in Vanadium Redox Flow Batteries

Abstract

Carbon felts are commonly utilized electrodes in vanadium flow batteries due to their low cost, light weight, good electronic conductivity, and chemical inertness. In contrast, their activity in catalyzing the vanadium redox reactions is less remarkable. In particular at the negative side, where V3+ reduction competes with the parasitic hydrogen evolution reaction (HER) at low potentials. In the literature, the addition of Bi3+ into the electrolyte [1] or its deposition on the felts has been suggested as a remedy. However, it is not clear yet, whether the Bi decoration remains stable with time and cycling and which mechanisms are responsible for the observed performance increase.The aim of this work is therefore to unravel more details about the catalyzing effect of Bi and its stability on the cell level. To this effect, the electrode kinetics with and without Bi decoration were studied comparing results obtained using Friedl’s method [2] with cyclic voltammetry (CV) data analyzed by the Polarographica curve fitting routine [3]. This approach can also be generalized to obtain precise kinetic information with other decorating metals.We furthermore applied negative dynamic hydrogen bubble templating (DHBT) deposition as an interesting way to coat commercially available carbon felts with a structured metallic layer of high surface area. Using this strategy, a significant positive effect was observed. However, the drying parameters and post-processing of the felts are important parameters which severely affect the final performance.In order to study the stability of Bi deposits in realistic battery experiments, in-situ synchrotron radiography has been used to monitor the Bi-decorated felts during charge-discharge cycles [4]. The figure demonstrates the effect of different flow rates on the Bi deposition patterns. Dark spots show metal-decorated areas within the felts at flow rates of 5 mlmin-1 (left), 15 mlmin-1 (middle) and 25 mlmin-1 (right). It can be easily seen that the operation conditions influence the felt decoration significantly, while Bi deposits dissolve and deposit during the charge-discharge routine. Further studies will be necessary to find out a) whether different deposit positions affect the performance enhancement and b) if DHBT-Bi remains more stable under operating conditions.In our presentation, we will not only focus on the materials, but also highlight techniques especially suitable for the stuctural and electrochemical analysis of felt electrodes.[1] B. Li, M. Gu, Z. Nie, Y. Shao, Q. Luo, X. Wei, X. Li, J. Xiao, C. Wang, V. Sprenkle, W. Wang, Bismuth Nanoparticle Decorating Graphite Felt as a High-Performance Electrode for an All-Vanadium Redox Flow Battery, Nano Letters 13(3) (2013) 1330-1335.[2] J. Friedl and U. Stimming, Determining Electron Transfer Kinetics at Porous Electrodes, Electrochim. Acta 227 (2017) 235–245.[3] T. Tichter, J. Schneider, D. Andrae, M. Gebhard, and C. Roth, Universal algorithm for simulating and evaluating cyclic voltammetry atmacroporous electrodes by considering random arrays of microelectrodes, ChemPhysChem 21 (2019) 428 –441.[4] M. Gebhard, T. Tichter, J. Schneider, J. Mayer, A. Hilger, M. Osenberg, M. Rahn, I. Manke, C. Roth J. Power Sources 478 (2020) 228695. Figure 1