Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution

Yu, Mingliang; Wang, Jing; Lei, Ming; Jung, Min Soo; Zhuo, Zengqing; Yang, Yufei; Zheng, Xueli; Sandstrom, Sean; Wang, Chunsheng; Yang, Wanli; Jiang, De-en; Liu, Tongchao; Ji, Xiulei

doi:10.1126/sciadv.adn4441

Title: Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution

Journal Article · 22 May 2024 · Science Advances

DOI: https://doi.org/10.1126/sciadv.adn4441 · OSTI ID:2340919

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Oregon State University, Corvallis, OR (United States); Oregon State University
Argonne National Laboratory (ANL), Argonne, IL (United States)
Vanderbilt University, Nashville, TN (United States)
Oregon State University, Corvallis, OR (United States); Seoul National University (Korea, Republic of)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Stanford University, CA (United States)
Stanford University, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Oregon State University, Corvallis, OR (United States)
University of Maryland, College Park, MD (United States)

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F^– and PO₄^3– facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li₃PO₄ into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF₃. Our results show that Fe-cations and anions of F^– and PO₄^3– act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

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Research Organization:: Oregon State University, Corvallis, OR (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; SC0012704; SC0023408

OSTI ID:: 2340919

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 21 Vol. 10; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Ultrahigh Conductive Graphene Paper Based on Ball-Milling Exfoliated Graphene Teng, Chao; Xie, Dan; Wang, Jianfeng Advanced Functional Materials, Vol. 27, Issue 20 https://doi.org/10.1002/adfm.201700240	journal	March 2017
High‐Nickel NMA: A Cobalt‐Free Alternative to NMC and NCA Cathodes for Lithium‐Ion Batteries Li, Wangda; Lee, Steven; Manthiram, Arumugam Advanced Materials, Vol. 32, Issue 33 https://doi.org/10.1002/adma.202002718	journal	July 2020
Bulk and Short‐Circuit Anion Diffusion in Epitaxial Fe ₂ O ₃ Films Quantified Using Buried Isotopic Tracer Layers Kaspar, Tiffany C.; Taylor, Sandra D.; Yano, Kayla H. Advanced Materials Interfaces, Vol. 8, Issue 9 https://doi.org/10.1002/admi.202001768	journal	March 2021
Commercialization of Lithium Battery Technologies for Electric Vehicles Zeng, Xiaoqiao; Li, Matthew; Abd El‐Hady, Deia Advanced Energy Materials, Vol. 9, Issue 27 https://doi.org/10.1002/aenm.201900161	journal	June 2019
From Copper to Basic Copper Carbonate: A Reversible Conversion Cathode in Aqueous Anion Batteries Gallagher, Trenton C.; Wu, Che‐Yu; Lucero, Marcos Angewandte Chemie, Vol. 134, Issue 31 https://doi.org/10.1002/ange.202203837	journal	June 2022
Reversible Copper Cathode for Nonaqueous Dual‐Ion Batteries Yu, Mingliang; Sui, Yiming; Sandstrom, Sean K. Angewandte Chemie, Vol. 134, Issue 47 https://doi.org/10.1002/ange.202212191	journal	October 2022
The Electrochemistry of Black Carbons Besenhard, J�rgen O.; Fritz, Heinz P. Angewandte Chemie International Edition in English, Vol. 22, Issue 12 https://doi.org/10.1002/anie.198309501	journal	December 1983
Scalable Synthesis of Tavorite LiFeSO4F and NaFeSO4F Cathode Materials Tripathi, Rajesh; Ramesh, T. N.; Ellis, Brian L. Angewandte Chemie International Edition, Vol. 49, Issue 46 https://doi.org/10.1002/anie.201003743	journal	October 2010
An XPS investigation on the thermal stability of the insulating surface layer of soft magnetic composite powder Oikonomou, C.; Hryha, E.; Nyborg, L. Surface and Interface Analysis, Vol. 48, Issue 7 https://doi.org/10.1002/sia.5993	journal	April 2016
Fading Mechanisms and Voltage Hysteresis in FeF ₂ -NiF ₂ Solid Solution Cathodes for Lithium and Lithium-Ion Batteries Huang, Qiao; Pollard, Travis P.; Ren, Xiaolei Small, Vol. 15, Issue 6 https://doi.org/10.1002/smll.201804670	journal	January 2019
Effect of aluminium doping on cathodic behaviour of LiNi0.7Co0.3O2 Madhavi, S.; Subba Rao, G. V.; Chowdari, B. V. R. Journal of Power Sources, Vol. 93, Issue 1-2 https://doi.org/10.1016/S0378-7753(00)00559-0	journal	February 2001
Influence of the Discretization Methods on the Distribution of Relaxation Times Deconvolution: Implementing Radial Basis Functions with DRTtools Wan, Ting Hei; Saccoccio, Mattia; Chen, Chi Electrochimica Acta, Vol. 184 https://doi.org/10.1016/j.electacta.2015.09.097	journal	December 2015
Synthesis of [Co/LiF/C] nanocomposite and its application as cathode in lithium-ion batteries Wall, Clemens; Prakash, Raju; Kübel, Christian Journal of Alloys and Compounds, Vol. 530 https://doi.org/10.1016/j.jallcom.2012.03.080	journal	July 2012
Perspective on Performance, Cost, and Technical Challenges for Practical Dual-Ion Batteries Placke, Tobias; Heckmann, Andreas; Schmuch, Richard Joule, Vol. 2, Issue 12 https://doi.org/10.1016/j.joule.2018.09.003	journal	December 2018
Modified synthesis of [Fe/LiF/C] nanocomposite, and its application as conversion cathode material in lithium batteries Prakash, Raju; Wall, Clemens; Mishra, Ajay Kumar Journal of Power Sources, Vol. 196, Issue 14 https://doi.org/10.1016/j.jpowsour.2011.03.007	journal	July 2011
LiF/Fe nanocomposite as a lithium-rich and high capacity conversion cathode material for Li-ion batteries Li, Ting; Chen, Zhong X.; Ai, Xin P. Journal of Power Sources, Vol. 217 https://doi.org/10.1016/j.jpowsour.2012.05.111	journal	November 2012
Battery materials for low-cost electric transportation Turcheniuk, Kostiantyn; Bondarev, Dmitry; Amatucci, Glenn G. Materials Today, Vol. 42 https://doi.org/10.1016/j.mattod.2020.09.027	journal	January 2021
Catalysis of nickel nanodomains on Li-F dissociation for high-capacity fluoride cathodes with prior delithiation ability Wu, Tao; Cui, Yanhua; Wei, Kaiyuan Nano Energy, Vol. 103 https://doi.org/10.1016/j.nanoen.2022.107843	journal	December 2022
Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries Kim, Sung-Wook; Pereira, Nathalie; Chernova, Natasha A. ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b03643	journal	September 2015
Pomegranate-Structured Conversion-Reaction Cathode with a Built-in Li Source for High-Energy Li-Ion Batteries Fan, Xiulin; Zhu, Yujie; Luo, Chao ACS Nano, Vol. 10, Issue 5 https://doi.org/10.1021/acsnano.6b02309	journal	May 2016
Sputter-Deposited Amorphous Li₃PO₄ Solid Electrolyte Films Ohnishi, Tsuyoshi; Takada, Kazunori ACS Omega, Vol. 7, Issue 24 https://doi.org/10.1021/acsomega.2c02104	journal	June 2022
Fabrication of LiF/Fe/Graphene Nanocomposites As Cathode Material for Lithium-Ion Batteries Ma, Ruguang; Dong, Yucheng; Xi, Liujiang ACS Applied Materials & Interfaces, Vol. 5, Issue 3 https://doi.org/10.1021/am302558w	journal	January 2013
Pushing Nanoionics to the Limits: Charge Carrier Chemistry in Extremely Small Systems Maier, Joachim Chemistry of Materials, Vol. 26, Issue 1 https://doi.org/10.1021/cm4021657	journal	September 2013
Combinatorially Prepared [LiF] _{1− x} Fe _x Nanocomposites for Positive Electrode Materials in Li-Ion Batteries Liao, Peng; MacDonald, Bretton L.; Dunlap, R. A. Chemistry of Materials, Vol. 20, Issue 2 https://doi.org/10.1021/cm702656k	journal	December 2007
Structural and Electronic Properties of Li-Ion Battery Cathode Material FeF₃ Li, R. F.; Wu, S. Q.; Yang, Y. The Journal of Physical Chemistry C, Vol. 114, Issue 39 https://doi.org/10.1021/jp1050518	journal	September 2010
Lithium-free transition metal monoxides for positive electrodes in lithium-ion batteries Jung, Sung-Kyun; Kim, Hyunchul; Cho, Min Gee Nature Energy, Vol. 2, Issue 2 https://doi.org/10.1038/nenergy.2016.208	journal	January 2017
Computational understanding of Li-ion batteries Urban, Alexander; Seo, Dong-Hwa; Ceder, Gerbrand npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2016.2	journal	March 2016
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
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Revisiting metal fluorides as lithium-ion battery cathodes Hua, Xiao; Eggeman, Alexander S.; Castillo-Martínez, Elizabeth Nature Materials, Vol. 20, Issue 6 https://doi.org/10.1038/s41563-020-00893-1	journal	January 2021
Inhibiting collective cation migration in Li-rich cathode materials as a strategy to mitigate voltage hysteresis Huang, Jianping; Ouyang, Bin; Zhang, Yaqian Nature Materials, Vol. 22, Issue 3, p. 353-361 https://doi.org/10.1038/s41563-022-01467-z	journal	January 2023
Aqueous Li-ion battery enabled by halogen conversion–intercalation chemistry in graphite Yang, Chongyin; Chen, Ji; Ji, Xiao Nature, Vol. 569, Issue 7755 https://doi.org/10.1038/s41586-019-1175-6	journal	May 2019
Strain-retardant coherent perovskite phase stabilized Ni-rich cathode Wang, Liguang; Liu, Tongchao; Wu, Tianpin Nature, Vol. 611, Issue 7934 https://doi.org/10.1038/s41586-022-05238-3	journal	November 2022
Battery cost forecasting: a review of methods and results with an outlook to 2050 Mauler, Lukas; Duffner, Fabian; Zeier, Wolfgang G. Energy & Environmental Science, Vol. 14, Issue 9 https://doi.org/10.1039/D1EE01530C	journal	January 2021
Nanocrystallinity effects in lithium battery materials Jamnik, Janez; Maier, Joachim Physical Chemistry Chemical Physics, Vol. 5, Issue 23 https://doi.org/10.1039/b309130a	journal	January 2003
Reversible lithium storage in LiF/Ti nanocomposites Yu, X. Q.; Sun, J. P.; Tang, K. Physical Chemistry Chemical Physics, Vol. 11, Issue 41 https://doi.org/10.1039/b908149f	journal	January 2009
A ferrocene-based carbon–iron lithium fluoride nanocomposite as a stable electrode material in lithium batteries Prakash, Raju; Mishra, Ajay Kumar; Roth, Arne Journal of Materials Chemistry, Vol. 20, Issue 10 https://doi.org/10.1039/b919097j	journal	January 2010
Preparation of graphene by exfoliation of graphite using wet ball milling Zhao, Weifeng; Fang, Ming; Wu, Furong Journal of Materials Chemistry, Vol. 20, Issue 28 https://doi.org/10.1039/c0jm01354d	journal	January 2010
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
First-principles calculations of the atomic structure and electronic states of LixFeF3 Mori, Masahiro; Tanaka, Shingo; Senoh, Hiroshi Physical Review B, Vol. 100, Issue 3 https://doi.org/10.1103/PhysRevB.100.035128	journal	July 2019
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Enhanced lithium storage and chemical diffusion in metal-LiF nanocomposites: Experimental and theoretical results Zhukovskii, Yuri F.; Balaya, Palani; Dolle, Mickael Physical Review B, Vol. 76, Issue 23 https://doi.org/10.1103/PhysRevB.76.235414	journal	December 2007
Quantum and thermal effects in H 2 dissociative adsorption: Evaluation of free energy barriers in multidimensional quantum systems Mills, Greg; Jónsson, Hannes Physical Review Letters, Vol. 72, Issue 7 https://doi.org/10.1103/PhysRevLett.72.1124	journal	February 1994
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Self-Limiting Growth of Metal Fluoride Thin Films by Oxidation Reactions Employing Molecular Precursors Qiu, S. R.; Lai, H. -F.; Yarmoff, J. A. Physical Review Letters, Vol. 85, Issue 7 https://doi.org/10.1103/PhysRevLett.85.1492	journal	August 2000
Reversible planar gliding and microcracking in a single-crystalline Ni-rich cathode Bi, Yujing; Tao, Jinhui; Wu, Yuqin Science, Vol. 370, Issue 6522 https://doi.org/10.1126/science.abc3167	journal	December 2020
Electrochemical performance of LiVPO4F synthesized by ball-milling assisted sol-gel method Xiong, Zhongqiong; Zhang, Guoqing; Mo, Lijiang Russian Journal of Electrochemistry, Vol. 50, Issue 10 https://doi.org/10.1134/S102319351406007X	journal	June 2014
Study of the Electrochemical Intercalation of Different Anions from Non-Aqueous Electrolytes into a Graphite-Based Cathode Fromm, Olga; Meister, Paul; Qi, Xin ECS Transactions, Vol. 58, Issue 14 https://doi.org/10.1149/05814.0055ecst	journal	February 2014
Electrochemical Intercalation of PF ₆ into Graphite Seel, J. A.; Dahn, J. R. Journal of The Electrochemical Society, Vol. 147, Issue 3, p. 892-898 https://doi.org/10.1149/1.1393288	journal	January 2000
Energy and Capacity Projections for Practical Dual-Graphite Cells Dahn, J. R.; Seel, J. A. Journal of The Electrochemical Society, Vol. 147, Issue 3 https://doi.org/10.1149/1.1393289	journal	January 2000
Electrochemically Active Lithia/Metal and Lithium Sulfide/Metal Composites Obrovac, M. N.; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 5, Issue 4 https://doi.org/10.1149/1.1452482	journal	January 2002
Carbon-Metal Fluoride Nanocomposites: Structure and Electrochemistry of FeF₃ : C Badway, F.; Pereira, N.; Cosandey, F. Journal of The Electrochemical Society, Vol. 150, Issue 9, p. A1209-A1218 https://doi.org/10.1149/1.1596162	journal	January 2003
Carbon Metal Fluoride Nanocomposites: High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries Badway, F.; Cosandey, F.; Pereira, N. Journal of The Electrochemical Society, Vol. 150, Issue 10, p. A1318-A1327 https://doi.org/10.1149/1.1602454	journal	January 2003

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