Anion-derived contact ion pairing as a unifying principle for electrolyte design

Abstract

Enabling new electrochemical technologies requires systems that can operate under ever-more demanding conditions, and progress in energy storage applications reveals tantalizing opportunities to reimagine electrolyte design for performance at extreme potentials. A common thread among these innovations is the formation of significant populations of contact ion pairs (CIPs) in the electrolyte, regardless of the specific cation chemistry or solvent system. The examples summarized in this review suggest that a set of general electrolyte design rules likely exists, where the purposeful selection of anion chemistry can yield CIP structures with tunable control over reaction thermodynamics, kinetics, and interphase chemistry. Identifying the relevant descriptors for high-performance, anion-derived CIP structures can be achieved utilizing a combined experimental and computational approach, aided by machine learning and artificial intelligence, to more rapidly survey the vast combinatorial space available and to enable a new generation of electrolytes for decarbonized electrochemical processes at scale.