Solid and Quasi-Solid Electrolytes for Zinc Batteries: Balancing Water Activity, Ion Transport, and Interfaces

Abstract

Zinc batteries offer a compelling route to safe and low-cost energy storage, yet their reliance on aqueous electrolytes promotes hydrogen evolution, corrosion, cathode dissolution, and non-uniform zinc deposition. Replacing the liquid with a solid or quasi-solid electrolyte can suppress these processes, but it also removes the medium that enables rapid Zn2+ transport and conformal electrode contact. This tension, the price of removing water, has been obscured by inconsistent use of the term solid state and by comparisons based largely on bulk ionic conductivity. Here we critically examine zinc electrolytes across a continuum from water-rich hydrogels to dry polymers, solvated crystals, and inorganic conductors. We distinguish water content from thermodynamic water activity and classify these materials according to phase state, mobile-solvent fraction, and dominant transport mechanism. We show that neither high conductivity nor nominally water-free composition reliably predicts cell performance: electrolyte thickness, Zn2+ transference, interfacial resistance, and evolving contact often determine the practical outcome. Controlled-solvation and hybrid electrolytes therefore provide the most credible near-term path, whereas genuinely solvent-free Zn2+ conductors remain a longer-term scientific target. Progress will require transparent reporting of solvent state and validation using thin electrolytes, realistic electrode loadings, limited zinc excess, and calendar-life testing.