Superconcentrated Electrolytes Widens Insertion Electrochemistry to Soluble Layered Halides

Insertion compounds provide the fundamental basis of today’s commercialized Li-ion batteries. Throughout history, intense research has focus on the design of stellar electrodes mainly relying on layered oxides or sulfides, and leaving aside the corresponding halides because of solubility issues. This is no longer true. In this work, we show for the first time the feasibility to reversibly intercalate electrochemically Li⁺ into VX₃ compounds (X = Cl, Br, I) via the use of superconcentrated electrolytes, (5 M LiFSI in dimethyl carbonate), hence opening access to a novel family of Li_xVX₃ phases. Moreover, through an electrolyte engineering approach we unambiguously prove that the positive attribute of superconcentrated electrolytes against solubility of inorganic compounds is rooted in a thermodynamic rather than a kinetic effect. The mechanism and corresponding impact of our findings enrich the fundamental understanding of superconcentrated electrolytes and constitute a crucial step in the design of novel insertion compounds with tunable properties for a wide range of applications beyond Li-ion batteries.