Triarylmethyl cation redox mediators enhance Li–O2 battery discharge capacities

Askins, Erik J.; Zoric, Marija R.; Li, Matthew; Amine, Rachid; Amine, Khalil; Curtiss, Larry A.; Glusac, Ksenija D.

doi:10.1038/s41557-023-01268-0

Triarylmethyl cation redox mediators enhance Li–O₂ battery discharge capacities

Journal Article · Thu Jul 06 00:00:00 EDT 2023 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-023-01268-0· OSTI ID:1996583

^[1]; ^[2]; ^[3]; Amine, Rachid ^[3]; ^[3]; Curtiss, Larry A. ^[3]; ^[4]

Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. of Illinois, Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

A major impediment to Li–O₂ battery commercialization is the low discharge capacities resulting from electronically insulating Li₂O₂ film growth on carbon electrodes. Redox mediation offers an effective strategy to drive oxygen chemistry into solution, avoiding surface-mediated Li₂O₂ film growth and extending discharge lifetimes. As such, the exploration of diverse redox mediator classes can aid the development of molecular design criteria. Here, in this work, we report a class of triarylmethyl cations that are effective at enhancing discharge capacities up to 35-fold. Surprisingly, we observe that redox mediators with more positive reduction potentials lead to larger discharge capacities because of their improved ability to suppress the surface-mediated reduction pathway. This result provides important structure–property relationships for future improvements in redox-mediated O₂/Li₂O₂ discharge capacities. Furthermore, we applied a chronopotentiometry model to investigate the zones of redox mediator standard reduction potentials and the concentrations needed to achieve efficient redox mediation at a given current density. We expect this analysis to guide future redox mediator exploration.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515

OSTI ID:: 1996583

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 9 Vol. 15; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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