Water or Anion? Uncovering the Zn²⁺ Solvation Environment in Mixed Zn(TFSI)₂ and LiTFSI Water-in-Salt Electrolytes

Abstract

Applications of aqueous zinc batteries for grid-scale energy storage are limited by their poor reversibility and the competing water splitting reaction. The recent invention of a water-in-salt (WIS) electrolyte concept provides a new route enabling a stable and highly reversible aqueous zinc battery chemistry. In the present work, a mixed zinc bis(trifluoromethane sulfonyl)imide (Zn(TFSI)2) and LiTFSI WIS electrolyte was studied using X-ray total scattering, X-ray absorption, and Fourier transform infrared spectroscopy in conjunction with classical molecular dynamics simulations. It was found that, in the highly concentrated WIS electrolyte consisting of 1 m Zn(TFSI)2 and 20 m LiTFSI, Zn2+ cations are mainly solvated by six waters in their first solvation shell, while the TFSI– anions are completely excluded. This ion solvation picture is fundamentally different from the previous understandings. The results suggest that additional studies are needed to fully understand the unusual stability and reversibility of zinc-WIS electrolyte-based batteries.