Methodologies for operando ATR-IR spectroscopy of magnesium battery electrolytes

Samajdar, Rudra N. and Brown, Scott A. and Kairy, Shravan K. and Robertson, Stuart D. and Wain, Andrew J. (2022) Methodologies for operando ATR-IR spectroscopy of magnesium battery electrolytes. Analytical Chemistry, 94 (43). pp. 14985-14993. ISSN 0003-2700 (https://doi.org/10.1021/acs.analchem.2c02843)

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Abstract

We explore the suitability of operando attenuated total reflection infrared (ATR-IR) spectroscopy methodologies for the study of organoaluminate electrolytes for Mg battery applications. The "all-phenyl complex" in tetrahydrofuran (THF), with the molecular structure [Mg Cl ·6THF] [AlPh ] , is used as an exemplar electrolyte to compare two different spectroelectrochemical cell configurations. In one case, a Pt gauze is used as a working electrode, while in the second case, a thin (∼10 nm) Pt film working electrode is deposited directly on the surface of the ATR crystal. Spectroscopic measurements indicate substantial differences in the ATR-IR response for the two configurations, reflecting the different spatial arrangements of the working electrode with respect to the ATR sampling volume. The relative merits and potential pitfalls associated with the two approaches are discussed.