Emergent solvation phenomena in non-aqueous electrolytes with multiple anions

Driscoll, Darren M.; Lavan, Sydney N.; Zorko, Milena; Redfern, Paul C.; Ilic, Stefan; Agarwal, Garvit; Fister, Timothy T.; Assary, Rajeev S.; Cheng, Lei; Strmcnik, Dusan; Balasubramanian, Mahalingam; Connell, Justin G.

doi:10.1016/j.chempr.2023.03.021

Title: Emergent solvation phenomena in non-aqueous electrolytes with multiple anions

Journal Article · Wed Apr 19 00:00:00 UTC 2023 · Chem

DOI: https://doi.org/10.1016/j.chempr.2023.03.021 · OSTI ID:2007636

Driscoll, Darren M. ^[1]; Lavan, Sydney N. ^[1]; Zorko, Milena ^[1]; Redfern, Paul C. ^[2]; Ilic, Stefan ^[1]; Agarwal, Garvit ^[1]; Fister, Timothy T. ^[1]; Assary, Rajeev S. ^[1]; Cheng, Lei ^[1]; Strmcnik, Dusan ^[1]; Balasubramanian, Mahalingam ^[1];

^[1]

Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)
Argonne National Laboratory (ANL), Argonne, IL (United States)

As the search for new battery chemistries with higher capacities and more stable supply chains expands, requiring increasingly complex electrolytes with multiple solvents and anions, it is becoming clear that understanding and controlling the working cation solvation structure is key to enabling improved stability and reversibility. In this work, we discover an emergent solvation behavior in multivalent electrolytes containing multiple anions, where bis(trifluoromethane sulfonyl) imide (TFSI⁻) anions that are fully dissociated in isolation form contact ion pairs with Zn²⁺ when combined with more strongly coordinating halides. This coordination modifies the electrochemical response, activating additional redox species as the halide association strength weakens (i.e., Cl⁻ > Br⁻ > I⁻) and systematically lowering overpotentials for metal deposition. This work suggests a completely new framework for electrolyte design in which anion chemistry can be used to tune both the bulk speciation and the interfacial solvation structure, enabling profound changes to the electrochemical behavior of the system.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2007636

Journal Information:: Chem, Journal Name: Chem Journal Issue: 7 Vol. 9; ISSN 2451-9294

Publisher:: Cell PressCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Emergent solvation phenomena in non-aqueous electrolytes with multiple anions

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