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

Austin D Ready; Ahamed Irshad; Anna Kallistova; Moises Carrillo; Milan Gembicky; Ram Seshadri; Sri Narayan; Alexander M Spokoyny

doi:10.1021/jacs.3c03065

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

J Am Chem Soc. 2023 Jul 5;145(26):14345-14353. doi: 10.1021/jacs.3c03065. Epub 2023 Jun 23.

Authors

Austin D Ready¹, Ahamed Irshad², Anna Kallistova³, Moises Carrillo¹, Milan Gembicky⁴, Ram Seshadri^{3

5}, Sri Narayan², Alexander M Spokoyny^{1

6}

Affiliations

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States.
² Department of Chemistry and Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, California 90089, United States.
³ Materials Department and Materials Research Laboratory, University of California, Santa Barbara, Santa Barbara, California 93106, United States.
⁴ Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92521, United States.
⁵ Department of Chemistry and Biochemistry, University of California, Santa Barbara, Santa Barbara, California 93106, United States.
⁶ California NanoSystems Institute (CNSI), University of California, Los Angeles, Los Angeles, California 90095, United States.

PMID: 37351898
DOI: 10.1021/jacs.3c03065

Abstract

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, B₁₂(OCH₃)₁₂, which is the smallest redox-active building block in the B₁₂(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 [B₁₂(OCH₃)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.