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Unravel crystallization kinetics of V(V) electrolytes for all-vanadium redox flow battery by in situ Raman spectroscopy

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Abstract

Redox flow battery technology has received much attention as a unique approach for possible use in grid-scale energy storage. The all-vanadium redox flow battery is currently one of the most advanced battery systems because of the symmetric design of its positive and negative electrolyte solution. However, the thermal and chemical instabilities of V(V) species as well as the permeation problem have caused incompatibility issues among the flow battery system, especially the membrane separator and electrode. It is essential to understand the underlying fundamentals of vanadium stability in order to provide guidelines for the development of advanced composite membrane and electrode and eventually address the incompatibility issue. In this study, we illustrate the kinetics parameters of V(V) crystallization via an in situ Raman study. Our results show that a 1.5-M V(V) solution with 2.625-M H2SO4 has a three times higher rate constant of crystallization and lower effective activation energy (44.67 kJ·mol−1) than a 2-M V(V) solution with 3.5-M H2SO4 (52.10 kJ·mol−1) during heat treatment at 60 °C, 65 °C, and 70 °C. In addition, the 2-M V(V) solution with 2.125-M H2SO4 had a much higher rate constant and much lower effective activation energy (25.13 kJ·mol−1) than the previously described two solutions, which indicates the paramount effect of the H2SO4 concentration on V(V) crystallization. We attribute the improved stability of the 2-M V(V) solution with 3.5 M H2SO4 to the formation of V–O-V-H2SO4 complexes under the high H2SO4 concentration.

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Acknowledgements

The authors would like to acknowledge financial support primarily from the U.S. Department of Energy (DOE) Office of Electricity through its Energy Storage Program at Pacific Northwest National Laboratory (PNNL) under Contract No. 57558. The Raman, XRD, and SEM measurements were performed at the William R. Wiley Environmental and Molecular Sciences Laboratory, a national scientific user facility at PNNL sponsored by the DOE Office of Biological and Environmental Research. PNNL is operated by Battelle Memorial Institute under contract no. DE-AC05-76RL01830 for the DOE.

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Authors and Affiliations

  1. Physical and Computational Science Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA

    Zaoyan Wan, Site Li, Ping Chen, Frank Yeung, Yilin Wang, Zheming Wang & Xin Zhang

  2. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA

    Zimin Nie, Yangang Liang, Ruozhu Feng & Wei Wang

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  1. Zaoyan Wan
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Wan, Z., Li, S., Chen, P. et al. Unravel crystallization kinetics of V(V) electrolytes for all-vanadium redox flow battery by in situ Raman spectroscopy. Adv Compos Hybrid Mater 6, 119 (2023). https://doi.org/10.1007/s42114-023-00635-2

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