Design Principles and Routes for Calcium Alkoxyaluminate Electrolytes

Multivalent-ion battery technologies are increasingly attractive options for meeting diverse energy storage needs. Calcium ion batteries (CIB) are particularly appealing candidates for their earthly abundance, high theoretical volumetric energy density, and relative safety advantages. At present, only a few Ca-ion electrolyte systems are reported to reversibly plate at room temperature: for example, aluminates and borates, including Ca[TPFA]₂, where [TPFA]^- = [Al(OC(CF₃)₃)₄]^- and Ca[B(hfip)₄]₂, [B(hfip)₄]₂^- = [B(OCH(CF₃)₂)₄]^-. Analyzing the structure of these salts reveals a common theme: the prevalent use of a weakly coordinating anion (WCA) consisting of a tetracoordinate aluminum/boron (Al/B) center with fluorinated alkoxides. Leveraging the concept of theory-aided design, we report an innovative, one-pot synthesis of two new calcium-ion electrolyte salts (Ca[Al(tftb)₄]₂, Ca[Al(hftb)₄]₂) and two reported salts (Ca[Al(hfip)₄]₂ and Ca[TPFA]₂) where hfip = (-OCH(CF₃)₂), tftb = (-OC(CF₃)(Me)₂), hftb = (-OC(CF₃)₂(Me)), [TPFA]^- = [Al(OC(CF₃)₃)₄]^-. We also reveal the dependence of Coulombic efficiency on their inherent propensity for cation-anion coordination.