Current Understanding of Nonaqueous Electrolytes for Calcium-Based Batteries

Calcium metal batteries are receiving growing research attention due to significant breakthroughs in recent years that have indicated reversible Ca plating/stripping with attractive Coulombic efficiencies (90-95%), once thought to be out of reach. While the Ca anode is often described as being surface film-controlled, the ability to access reversible Ca electrochemistry is highly electrolyte-dependent in general, which affects both interfacial chemistry on plated Ca along with more fundamental Ca²⁺/Ca redox properties. This mini-review describes recent progress towards a reversible Ca anode from the point of view of the most successful electrolyte chemistries identified to date. This includes, centrally, what is currently known about the Ca²⁺ solvation environment in these systems. Experimental (physico-chemical and spectroscopy) and computational results are summarized for the two major solvent classes - carbonates and ethers - that have yielded promising results so far. Current knowledge gaps and opportunities to improve fundamental understanding of Ca²⁺/Ca redox are also identified.