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

Patheria, Eshaan S.; Guzman, Pedro; Soldner, Leah S.; Qian, Michelle D.; Morrell, Colin T.; Kim, Seong Shik; Hunady, Kyle; Priesen Reis, Elena R.; Dulock, Nicholas V.; Neilson, James R.; Weker, Johanna Nelson; Fultz, Brent; See, Kimberly A.

doi:10.1021/jacs.4c18440

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

Journal Article · 04 March 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c18440 · OSTI ID:2527365

^[1]; Guzman, Pedro ^[1]; Soldner, Leah S. ^[1];

^[1];

^[1]; Hunady, Kyle ^[1]; Priesen Reis, Elena R. ^[1];

^[1];

^[2];

^[3]; Fultz, Brent ^[1];

^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States)
Colorado State University, Fort Collins, CO (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li₂FeS₂, composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al³⁺ for Fe²⁺ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g^–1) and energy density (≳1000 Wh·kg^–1). We show that Al³⁺ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; SC0012704; SC0019381

OSTI ID:: 2527365

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 147; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (49)

Some defect structures of iron sulfide Fasiska, E. J. Physica Status Solidi (a), Vol. 10, Issue 1 https://doi.org/10.1002/pssa.2210100119	journal	March 1972
Mössbauer study of the magnetic structure of Fe7S8 Levinson, Lionel M.; Treves, D. Journal of Physics and Chemistry of Solids, Vol. 29, Issue 12 https://doi.org/10.1016/0022-3697(68)90019-X	journal	December 1968
Mössbauer 57Fe isomer shift as a measure of valence in mixed-valence iron sulfides Goodenough, John B.; Fatseas, G. A. Journal of Solid State Chemistry, Vol. 41, Issue 1 https://doi.org/10.1016/0022-4596(82)90028-7	journal	January 1982
Mössbauer investigation of synthetic single crystal monoclinic Fe7S8 Gosselin, J. R.; Townsend, M. G.; Tremblay, R. J. Materials Research Bulletin, Vol. 10, Issue 1 https://doi.org/10.1016/0025-5408(75)90145-2	journal	January 1975
New electrolyte compositions stable over the 0 to 5 V voltage range and compatible with the Li1+xMn2O4/carbon Li-ion cells Tarascon, J.; Guyomard, D. Solid State Ionics, Vol. 69, Issue 3-4 https://doi.org/10.1016/0167-2738(94)90418-9	journal	August 1994
K- and L-edge X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) determination of differential orbital covalency (DOC) of transition metal sites Baker, Michael L.; Mara, Michael W.; Yan, James J. Coordination Chemistry Reviews, Vol. 345 https://doi.org/10.1016/j.ccr.2017.02.004	journal	August 2017
Synthesis and electrochemical properties of pure LiFeSO4F in the triplite structure Ati, M.; Melot, B. C.; Chotard, J. -N. Electrochemistry Communications, Vol. 13, Issue 11 https://doi.org/10.1016/j.elecom.2011.08.023	journal	November 2011
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries Manthiram, Arumugam; Song, Bohang; Li, Wangda Energy Storage Materials, Vol. 6 https://doi.org/10.1016/j.ensm.2016.10.007	journal	January 2017
Metal-ligand redox in layered oxide cathodes for Li-ion batteries Ogley, Matthew J. W.; Menon, Ashok S.; Pandey, Gaurav C. Joule, Vol. 9, Issue 1 https://doi.org/10.1016/j.joule.2024.10.007	journal	January 2025
Structure of Li5AlS4 and comparison with other lithium-containing metal sulfides Lim, Hanjin; Kim, Sung-Chul; Kim, Jaegyeom Journal of Solid State Chemistry, Vol. 257 https://doi.org/10.1016/j.jssc.2017.09.018	journal	January 2018
Li _4.3 AlS _3.3 Cl _0.7 : A Sulfide–Chloride Lithium Ion Conductor with Highly Disordered Structure and Increased Conductivity Gamon, Jacinthe; Dyer, Matthew S.; Duff, Benjamin B. Chemistry of Materials, Vol. 33, Issue 22 https://doi.org/10.1021/acs.chemmater.1c02751	journal	November 2021
Effect of Metal d Band Position on Anion Redox in Alkali-Rich Sulfides Kim, Seong Shik; Agyeman-Budu, David N.; Zak, Joshua J. Chemistry of Materials, Vol. 36, Issue 13 https://doi.org/10.1021/acs.chemmater.4c00490	journal	June 2024
Lithium Transport in Li _4.4 M _0.4 M ′ _0.6 S ₄ (M = Al ³⁺ , Ga ³⁺ , and M ′ = Ge ⁴⁺ , Sn ⁴⁺ ): Combined Crystallographic, Conductivity, Solid State NMR, and Computational Studies Leube, Bernhard T.; Inglis, Kenneth K.; Carrington, Elliot J. Chemistry of Materials, Vol. 30, Issue 20 https://doi.org/10.1021/acs.chemmater.8b03175	journal	September 2018
Computationally Guided Discovery of the Sulfide Li₃AlS₃ in the Li–Al–S Phase Field: Structure and Lithium Conductivity Gamon, Jacinthe; Duff, Benjamin B.; Dyer, Matthew S. Chemistry of Materials, Vol. 31, Issue 23 https://doi.org/10.1021/acs.chemmater.9b03230	journal	October 2019
Irreversible Anion Oxidation Leads to Dynamic Charge Compensation in the Ru-Poor, Li-Rich Cathode Li₂Ru_0.3Mn_0.7O₃ Zak, Joshua J.; Zuba, Mateusz; Lebens-Higgins, Zachary W. ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02537	journal	December 2022
Chemical and Structural Indicators for Large Redox Potentials in Fe-Based Positive Electrode Materials Melot, Brent C.; Scanlon, David O.; Reynaud, Marine ACS Applied Materials & Interfaces, Vol. 6, Issue 14 https://doi.org/10.1021/am405579h	journal	March 2014
Ligand K-Edge X-ray Absorption Spectroscopy: A Direct Probe of Ligand−Metal Covalency Glaser, Thorsten; Hedman, Britt; Hodgson, Keith O. Accounts of Chemical Research, Vol. 33, Issue 12 https://doi.org/10.1021/ar990125c	journal	December 2000
High-Resolution Synchrotron Studies and Magnetic Properties of Frustrated Antiferromagnets MAl₂S₄ (M = Mn²⁺, Fe²⁺, Co²⁺) Menard, Melissa C.; Ishii, Rieko; Higo, Tomoya Chemistry of Materials, Vol. 23, Issue 12 https://doi.org/10.1021/cm200561p	journal	May 2011
Sulfate-Based Polyanionic Compounds for Li-Ion Batteries: Synthesis, Crystal Chemistry, and Electrochemistry Aspects Rousse, G.; Tarascon, J. M. Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm4022358	journal	September 2013
Multielectron, Cation and Anion Redox in Lithium-Rich Iron Sulfide Cathodes Hansen, Charles J.; Zak, Joshua J.; Martinolich, Andrew J. Journal of the American Chemical Society, Vol. 142, Issue 14 https://doi.org/10.1021/jacs.0c00909	journal	March 2020
Evidence for Low-Valent Electronic Configurations in Iron–Sulfur Clusters Brown, Alexandra C.; Thompson, Niklas B.; Suess, Daniel L. M. Journal of the American Chemical Society, Vol. 144, Issue 20 https://doi.org/10.1021/jacs.2c01872	journal	May 2022
An Exploration of Sulfur Redox in Lithium Battery Cathodes Zak, Joshua J.; Kim, Seong Shik; Laskowski, Forrest A. L. Journal of the American Chemical Society, Vol. 144, Issue 23 https://doi.org/10.1021/jacs.2c02668	journal	June 2022
Cation Vacancies Enable Anion Redox in Li Cathodes Kim, Seong Shik; Kitchaev, Daniil A.; Patheria, Eshaan S. Journal of the American Chemical Society, Vol. 146, Issue 30 https://doi.org/10.1021/jacs.4c05769	journal	July 2024
Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li ₄ FeSbO ₆ McCalla, Eric; Sougrati, Moulay Tahar; Rousse, Gwenaelle Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/jacs.5b01424	journal	April 2015
A non-academic perspective on the future of lithium-based batteries Frith, James T.; Lacey, Matthew J.; Ulissi, Ulderico Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-35933-2	journal	January 2023
Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox Li, Biao; Sougrati, Moulay Tahar; Rousse, Gwenaëlle Nature Chemistry, Vol. 13, Issue 11 https://doi.org/10.1038/s41557-021-00775-2	journal	September 2021
Exploring the bottlenecks of anionic redox in Li-rich layered sulfides Saha, Sujoy; Assat, Gaurav; Sougrati, Moulay Tahar Nature Energy, Vol. 4, Issue 11 https://doi.org/10.1038/s41560-019-0493-0	journal	November 2019
Post-lithium-ion battery cell production and its compatibility with lithium-ion cell production infrastructure Duffner, Fabian; Kronemeyer, Niklas; Tübke, Jens Nature Energy, Vol. 6, Issue 2 https://doi.org/10.1038/s41560-020-00748-8	journal	January 2021
The role of O2 in O-redox cathodes for Li-ion batteries House, Robert A.; Marie, John-Joseph; Pérez-Osorio, Miguel A. Nature Energy, Vol. 6, Issue 8 https://doi.org/10.1038/s41560-021-00780-2	journal	March 2021
Amorphous iron fluorosulfate as a high-capacity cathode utilizing combined intercalation and conversion reactions with unexpectedly high reversibility Heo, Jaehoon; Jung, Sung-Kyun; Hwang, Insang Nature Energy, Vol. 8, Issue 1 https://doi.org/10.1038/s41560-022-01148-w	journal	November 2022
Energy consumption of current and future production of lithium-ion and post lithium-ion battery cells Degen, F.; Winter, M.; Bendig, D. Nature Energy, Vol. 8, Issue 11 https://doi.org/10.1038/s41560-023-01355-z	journal	September 2023
Integrated rocksalt–polyanion cathodes with excess lithium and stabilized cycling Huang, Yimeng; Dong, Yanhao; Yang, Yang Nature Energy, Vol. 9, Issue 12 https://doi.org/10.1038/s41560-024-01615-6	journal	August 2024
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides Hong, Jihyun; Gent, William E.; Xiao, Penghao Nature Materials, Vol. 18, Issue 3 https://doi.org/10.1038/s41563-018-0276-1	journal	February 2019
Capturing dynamic ligand-to-metal charge transfer with a long-lived cationic intermediate for anionic redox Li, Biao; Kumar, Khagesh; Roy, Indrani Nature Materials, Vol. 21, Issue 10 https://doi.org/10.1038/s41563-022-01278-2	journal	June 2022
Pushing the limit of 3d transition metal-based layered oxides that use both cation and anion redox for energy storage Zhang, Minghao; Kitchaev, Daniil A.; Lebens-Higgins, Zachary Nature Reviews Materials, Vol. 7, Issue 7 https://doi.org/10.1038/s41578-022-00416-1	journal	February 2022
Ferromagnetic correlations in the layered van der Waals sulfide FeAl₂S₄ Verchenko, Valeriy Yu.; Kanibolotskiy, Alexander V.; Bogach, Alexey V. Dalton Transactions, Vol. 51, Issue 21 https://doi.org/10.1039/D2DT00671E	journal	January 2022
Magnetic Anisotropy in Pyrrhotite Bin, M.; Pauthenet, R. Journal of Applied Physics, Vol. 34, Issue 4 https://doi.org/10.1063/1.1729413	journal	April 1963
Transition-metal dichalcogenides from disintercalation processes. Crystal structure determination and Mossbauer study of Li ₂ FeS ₂ and its disintercalates Li _x FeS ₂ (0.2⩽x⩽2) Blandeau, L.; Ouvrard, G.; Calage, Y. Journal of Physics C: Solid State Physics, Vol. 20, Issue 27 https://doi.org/10.1088/0022-3719/20/27/007	journal	September 1987
Crystal structure of Li 2 FeS 2 Batchelor, R. J.; Einstein, F. W. B.; Jones, C. H. W. Physical Review B, Vol. 37, Issue 7 https://doi.org/10.1103/PhysRevB.37.3699	journal	March 1988
Spin-integrated and spin-resolved photoemission study of Fe chalcogenides Shimada, K.; Mizokawa, T.; Mamiya, K. Physical Review B, Vol. 57, Issue 15 https://doi.org/10.1103/PhysRevB.57.8845	journal	April 1998
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
MossA : a program for analyzing energy-domain Mössbauer spectra from conventional and synchrotron sources Prescher, Clemens; McCammon, Catherine; Dubrovinsky, Leonid Journal of Applied Crystallography, Vol. 45, Issue 2 https://doi.org/10.1107/S0021889812004979	journal	March 2012
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
The crystal structure of a pyrrhotite (Fe7S8) Fleet, M. E. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 10 https://doi.org/10.1107/S0567740871004990	journal	October 1971
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Optimized LiFePO[sub 4] for Lithium Battery Cathodes Yamada, A.; Chung, S. C.; Hinokuma, K. Journal of The Electrochemical Society, Vol. 148, Issue 3 https://doi.org/10.1149/1.1348257	journal	January 2001
Crystal structure refinement of MnTe₂, MnSe₂, and MnS₂: cation-anion and anion–anion bonding distances in pyrite-type structures Tokuda, Makoto; Yoshiasa, Akira; Mashimo, Tsutomu Zeitschrift für Kristallographie - Crystalline Materials, Vol. 234, Issue 6 https://doi.org/10.1515/zkri-2018-2134	journal	February 2019
Fundamentals of XAFS Newville, M. Reviews in Mineralogy and Geochemistry, Vol. 78, Issue 1 https://doi.org/10.2138/rmg.2014.78.2	journal	January 2014
A framework for integrating supply chain, environmental, and social justice factors during early stationary battery research Putsche, Victoria L.; Pattany, Jasmine; Ghosh, Tapajyoti Frontiers in Sustainability, Vol. 4 https://doi.org/10.3389/frsus.2023.1287423	journal	November 2023

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