Bridging Transition Metal and Anion Redox Processes in Li-Rich Sulfide Cathodes

Patheria, Eshaan S.; Soldner, Leah S.; Ramakrishnan, Nayantara; Morrell, Colin T.; Qian, Michelle D.; Davis, Victoria K.; See, Kimberly A.

doi:10.1021/acs.chemmater.6c00047

Title: Bridging Transition Metal and Anion Redox Processes in Li-Rich Sulfide Cathodes

Journal Article · Wed May 27 00:00:00 UTC 2026 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.6c00047 · OSTI ID:3376158

^[1]; Soldner, Leah S. ^[1]; Ramakrishnan, Nayantara ^[2];

^[1];

^[1]; Davis, Victoria K. ^[1];

^[1]

California Institute of Technology, Pasadena, CA (United States)
Indian Institute of Technology Bombay, Maharashtra (India)

Li-ion batteries are essential for decarbonizing global transport and energy, but their scalability is constrained by limited supplies of critical cathode elements, such as Ni, Mn, Co, and P. To address this, we previously introduced high-energydensity Li-ion cathodes composed of Al, Fe, and S, which are elements already produced globally at industrial scale and batterygrade purity. These cathodes leverage sulfide anion redox, involving nonbonding S 3p states and localized distortions that form and break S−S bonds, enabling high capacity. Here, we expand this chemical space by incorporating Cu into cathodes Li_2.2d−zCu_zAl_0.2Fe_0.6S₂ (0 ≤ z ≤ 0.4), where highly covalent Cu−S interactions stabilize holes on Cu as Cu^>1+. This Cu redox extends charge compensation that was previously restricted to localized, electronically isolated S−S bonds. Cu also limits capacity, which we attribute to structural destabilization of the delithiated phase, despite the thermodynamic stability of Cu^>1+. By describing the effects of Cu on charge compensation and phase stability, we present a sulfide anion redox mechanism for next-generation multielectron redox Li-ion cathodes, where highly covalent transition metal states participate in otherwise electronically isolated redox processes involving anion nonbonding states.

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Research Organization:: Stanford University, Redwood City, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-76SF00515; SC0012704

OSTI ID:: 3376158

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 38; ISSN 1520-5002; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Bridging Transition Metal and Anion Redox Processes in Li-Rich Sulfide Cathodes

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