Alkoxy-functionalized ionic liquid electrolytes: understanding ionic coordination of calcium ion speciation for the rational design of calcium electrolytes

Abstract

There is growing interest in the rational design of electrolytes for multivalent-ion batteries by tuning the molecular-level interactions of solvate species present in the electrolytes. Herein, we report our effort to control Ca-ion speciation in ionic liquid (IL) based electrolytes through the design of alkoxy-functionalized cations. Quantitative analysis reveals that the alkoxy-functionalized ammonium cation (N₀₇⁺), bearing seven ether oxygen atoms, can effectively displace the bis(trifluoromethanesulfonyl)imide anion (TFSI⁻) from the Ca²⁺ ion coordination sphere, facilitating the reversible Ca deposition/stripping process. More importantly, post-analysis of Ca deposits surface chemistry and density functional theory calculations of Ca-ion speciation indicate the formation of an organic-rich, but inorganic-poor solid electrolyte interphase layer, which enables Ca²⁺ ion diffusion rather than passivating the Ca metal electrode. Finally, as a proof-of-concept, a prototype Ca/V₂O₅ cell using the optimized IL-based electrolyte ([Ca(BH₄)₂]_0.05[N₀₇TFSI]_0.95) is demonstrated for the first time, exhibiting a remarkable initial discharge capacity of 332 mA h g⁻¹ and reversible capacity of 244 mA h g⁻¹.