Mixed-Anion Contact Ion-Pair Formation Enabling Improved Performance of Halide-Free Mg-Ion Electrolytes

Ilic, Stefan; Lavan, Sydney N.; Leon, Noel J.; Liu, Haoyu; Jain, Akash; Key, Baris; Assary, Rajeev S.; Liao, Chen; Connell, Justin G.

doi:10.1021/acsami.3c11293

Title: Mixed-Anion Contact Ion-Pair Formation Enabling Improved Performance of Halide-Free Mg-Ion Electrolytes

Journal Article · 25 December 2023 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.3c11293 · OSTI ID:2477735

^[1]; Lavan, Sydney N. ^[1]; Leon, Noel J. ^[1]; Liu, Haoyu ^[1]; Jain, Akash ^[1];

^[1];

^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States)

In this article, discovery of stable and efficient electrolytes that are compatible with magnesium metal anodes and high-voltage cathodes is crucial to enabling energy storage technologies that can move beyond existing Li-ion systems. Many promising electrolytes for magnesium anodes have been proposed with chloride-based systems at the forefront; however, Cl-containing electrolytes lack the oxidative stability required by high-voltage cathodes. In this work, we report magnesium trifluoromethanesulfonate (triflate) as a viable coanion for Cl-free, mixed-anion magnesium electrolytes. The addition of triflate to electrolytes containing bis(trifluoromethane sulfonyl) imide (TFSI^–) anions yields significantly improved Coulombic efficiency, up to a 100 mV decrease in the plating/stripping overpotential, improved tolerance to trace H₂O, and improved oxidative stability (0.35 V improvement compared to that of hybrid TFSI-Cl electrolytes). Based on ¹⁹F nuclear magnetic resonance and Raman spectroscopy measurements, we propose that these improvements in performance are driven by the formation of mixed-anion contact ion pairs, where both triflate and TFSI^– are coordinated to Mg²⁺ in the electrolyte bulk. The formation of this mixed-anion magnesium complex is further predicted by the density functional theory to be thermodynamically driven. Collectively, this work outlines the guiding principles for the improved design of next-generation electrolytes for magnesium batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2477735

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 1 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Mixed-Anion Contact Ion-Pair Formation Enabling Improved Performance of Halide-Free Mg-Ion Electrolytes

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