High-Energy Density Li-Ion Battery Cathode Using Only Industrial Elements

Abstract

Copyright and License

© 2025 The Authors. Published by American Chemical Society.  This publication is licensed under CC-BY-NC-ND 4.0.

Acknowledgement

This material is based upon work supported by the National Science Foundation (NSF) under Award No. DMR-2340864. K.A.S. acknowledges support from the Packard Fellowship for Science and Engineering, the Alfred P. Sloan Foundation, and the Camille and Henry Dreyfus Foundation. E.S.P. acknowledges support from the Robert and Patricia Switzer Foundation. E.S.P., M.D.Q., and C.T.M. acknowledge NSF Graduate Research Fellowship support under Award No. DGE-2139433. B.F. and P.G. acknowledge support from NSF Award No. DMR-1904714. Initial work on this material was partially supported by 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. This research used beamlines 2-2 and 4-3 at the Stanford Synchrotron Radiation Light Source (SSRL). Use of SSRL, 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. This research used beamlines 8-BM and 28-ID-1 of the National Synchrotron Light Source II (NSLS-II), a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Brookhaven National Laboratory (BNL) under Contract No. DE-SC0012704. The authors thank the Resnick Environmental Analysis Center at Caltech for ICP-MS and the Beckman Institute and Caltech X-ray Crystallography Facility for CuKα XRD. The authors also thank Dr. Yonghua Du and Dr. Sarah Nicholas at 8-BM(NSLS-II) for their assistance with S K-edge XAS, Dr. Gihan Kwon at 28-ID-1 (NSLS-II) for his help with sXRD, and Dr. Erik Nelson and Dr. Matthew Latimer at 2-2 and 4-3 (SSRL) for their help with Fe K-edge XAS. The authors last thank Dr. Joshua J. Zak and Dr. Zachery W. B. Iton for their feedback and insights.

Supplemental Material

Previous work on Li₂FeS₂; Rietveld refinement results; unfit reflections and superstructure in Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; elemental analysis of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; impurities ruled out in sXRD patterns; first cycle charge Fe, S, and total oxidation capacities; comparison of anion frameworks; first cycle replicates of Li₂FeS₂, Li_2.2Al_0.2Fe_0.6S₂, and Li_2.4Al_0.4Fe_0.2S₂; GITT of Li₂FeS₂, Li_2.2Al_0.2Fe_0.6S₂, and Li_2.4Al_0.4Fe_0.2S₂; first cycle performance metrics of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; C/10 cycling data of individual cells; representativeC/10 galvanostatic cycles; rate capability data of individual cells; representative galvanostatic cycles of rate capability tests; additional Fe K-edge XAS data and its limitations; additional Fe K-edge XAS; long-range structural changes in Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; ex situ XRD of (0 0 1) reflection of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; full ex situ XRD patterns of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; cation inventory and capacity limits of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; XRD of ‘Al_0.2Fe_0.6S₂’; S content before and after annealing; comparison of crystal structures of Li_2.2Al_0.2Fe_0.6S₂ and Al₂FeS₄; XRD and Rietveld analysis before and after annealing; weighted averages and weighted standard deviations of isomer shifts and quadrupole splittings; Mössbauer data and fits of Li₂FeS₂; Mössbauer data and fits of Li_2.2Al_0.2Fe_0.6S₂; all Mössbauer fit parameters; Fe K-edge EXAFS first and second shells; Li₂FeS₂ EXAFS k³χ(k) data and fits; Li_2.2Al_0.2Fe_0.6S₂ EXAFS k³χ(k) data and fits; Li₂FeS₂ EXAFS k³-weighted |χ(R)| data and fits; Li_2.2Al_0.2Fe_0.6S₂ EXAFS k³-weighted |χ(R)| data and fits; all EXAFS fit parameters; parameter-free Mössbauer centroids of Li₂FeS₂ and Li_2.2Al_0.2Fe_0.6S₂; relative covalency of (S₂)^2– and S^2– with Fe; volumetric vs gravimetric energy densities of commercial and emerging Li-ion battery cathodes; and relevant values and references for energy densities (PDF)

Conflict of Interest

The authors declare the following competing financial interest(s): A U.S. patent has been filed by the California Institute of Technology related to this work: E.S.P. and K.A.R. Lithium-Rich Aluminum Iron Sulfide Li-Ion Battery Cathodes U.S. Application No. 18/369,425, PCT Application No. PCT/US2023/033004, filed September 18, 2023.