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In situ monitoring redox processes in energy storage using UV–Vis spectroscopy

Nature Energy volume 8, pages 567–576 (2023)Cite this article

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Abstract

Understanding energy storage mechanisms in electrochemical energy storage devices lays the foundations for improving their energy and power density. Here we introduce in situ ultraviolet–visible (UV–Vis) spectroscopy method to distinguish battery-type, pseudocapacitive and electrical double-layer charge storage processes. On the basis of Ti3C2Tx MXene in aqueous acidic and neutral electrolytes, and lithium titanium oxide in an organic electrolyte, we found a correlation between the evolution of UV–Vis spectra and the charge storage mechanism. The electron transfer number for Ti3C2Tx in an acidic electrolyte was calculated using quantitative analysis, which was close to previous measurements using X-ray absorption spectroscopy. Further, we tested the methodology to distinguish the non-Faradaic process in Ti3C2Tx MXene in a water-in-salt electrolyte, despite well-defined peaks in cyclic voltammograms. In situ UV–Vis spectroscopy is a fast and cost-effective technique that effectively supplements electrochemical characterization to track changes in oxidation state and materials chemistry and determine the charge storage mechanism.

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Fig. 1: The setup for in situ electrochemical UV–Vis spectroscopy.
Fig. 2: Electrochemical CV curves, reconstructed CV curves and in situ electrochemical UV–Vis spectra.
Fig. 3: Correlation between in situ UV–Vis spectra and electrochemical results.
Fig. 4: Comparison of electrochemical and UV–Vis CV curves of selected electrochemical systems collected using the CV method.
Fig. 5: EDL and surface redox contributions to the total charge for Ti3C2Tx in different electrolytes.
Fig. 6: Schematic illustrating the difference of mechanisms of charge storage by Ti3C2Tx in different electrolytes.

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All relevant data are available within the paper and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Fluid Interface Reactions, Structures, and Transport (FIRST) Center, an Energy Frontier Research Center (EFRC) funded by the US Department of Energy, Office of Science and Office of Basic Energy Sciences. D.Z. and Y.G. also acknowledge funding for MXene synthesis from NSF Grant DMR-2041050.

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  1. These authors contributed equally: Danzhen Zhang, Ruocun (John) Wang.

Authors and Affiliations

  1. A. J. Drexel Nanomaterials Institute, and Department of Materials Science and Engineering, Drexel University, Philadelphia, PA, USA

    Danzhen Zhang, Ruocun (John) Wang, Xuehang Wang & Yury Gogotsi

  2. Storage of Electrochemical Energy (SEE), Department of Radiation Science and Technology, Delft University of Technology, Delft, The Netherlands

    Xuehang Wang

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  1. Danzhen Zhang
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Contributions

D.Z., X.W. and Y.G. planned the research. D.Z. R.W. and X.W. designed the experiments. D.Z. synthesized and characterized all materials, performed in situ experiments and analysed data. R.W. developed in situ data anaylsis tools and protocols. D.Z. wrote the paper and R.W., X.W. and Y.G. edited and reviewed the paper.

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Correspondence to Xuehang Wang or Yury Gogotsi.

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Nature Energy thanks Obaidallah Munteshari, Jean-Marie Tarascon and Wei Wang for their contribution to the peer review of this work.

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Zhang, D., Wang, R.(., Wang, X. et al. In situ monitoring redox processes in energy storage using UV–Vis spectroscopy. Nat Energy 8, 567–576 (2023). https://doi.org/10.1038/s41560-023-01240-9

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