Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published April 8, 2020 | Supplemental Material
Journal Article Open

Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes

Abstract

Conventional Li-ion cathodes store charge by reversible intercalation of Li coupled to metal cation redox. There has been increasing interest in new materials capable of accommodating more than one Li per transition-metal center, thereby yielding higher charge storage capacities. We demonstrate here that the lithium-rich layered iron sulfide Li₂FeS₂ as well as a new structural analogue, LiNaFeS₂, reversibly store ≥1.5 electrons per formula unit and support extended cycling. Ex situ and operando structural and spectroscopic data indicate that delithiation results in reversible oxidation of Fe²⁺ concurrent with an increase in the covalency of the Fe–S interactions, followed by reversible anion redox: 2 S²⁻/(S₂)²⁻. S K-edge spectroscopy unequivocally proves the contribution of the anions to the redox processes. The structural response to the oxidation processes is found to be different in Li₂FeS₂ in contrast to that in LiNaFeS₂, which we suggest is the cause for capacity fade in the early cycles of LiNaFeS₂. The materials presented here have the added benefit of avoiding resource-sensitive transition metals such as Co and Ni. In contrast to Li-rich oxide materials that have been the subject of so much recent study and that suffer capacity fade and electrolyte degradation issues, the materials presented here operate within the stable potential window of the electrolyte, permitting a clearer understanding of the underlying processes.

Additional Information

© 2020 American Chemical Society. Received: January 23, 2020; Published: March 30, 2020. This work was supported as part of the Center for Synthetic Control Across Length-scales for Advancing Rechargeables (SCALAR), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0019381. C.J.H. was supported by a Beckman-Gray Graduate Student Fellowship made possible by the Arnold and Mabel Beckman Foundation. J.J.Z. acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1745301. A.J.M. acknowledges a postdoctoral fellowship from the Resnick Sustainability Institute at Caltech. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. The authors thank Prof. Ryan G. Hadt and Sarah C. Bevilacqua for useful discussions.

Attached Files

Supplemental Material - ja0c00909_si_001.pdf

Files

ja0c00909_si_001.pdf
Files (6.7 MB)
Name Size Download all
md5:2d53d90907ce14c34dbc82e6a046efc5
6.7 MB Preview Download

Additional details

Created:
August 19, 2023
Modified:
October 19, 2023