Emergent solvation phenomena in non-aqueous electrolytes with multiple anions

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

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)1955-1971
Number of pages17
JournalChem
Volume9
Issue number7
DOIs
StatePublished - Jul 13 2023
Externally publishedYes

Keywords

  • SDG7: Affordable and clean energy
  • anion association
  • electrodeposition
  • electrolyte design
  • multivalent battery
  • solvation structure

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