Electrochemical Cycling of Redox-Active Boron Cluster-Based Materials in the Solid State.

This work demonstrates the first successful electrochemical cycling of a redox-active boron cluster-based material in the solid state. Specifically, we designed and synthesized an ether-functionalized dodecaborate cluster, B 12 (OCH 3 ) 12 , which is the smallest redox-active building block in the B 12 (OR) 12 family. This species can reversibly access four oxidation states in solution, ranging from a dianion to a radical cation. We show that a chemically isolated and characterized neutral [B 12 (OCH 3 ) 12 ] 0 cluster can be utilized as a cathode active material in a PEO-based rechargeable all-solid-state cell with a lithium metal anode. The cell exhibits an impressive active material utilization close to 95% at C/20 rate, a high Coulombic efficiency of 96%, and reversibility, with only 4% capacity fade after 16 days of cycling. This work represents a conceptual departure in the development of redox-active components for electrochemical storage and serves as an entry point to a broader class of borane-based materials.