Revisiting metal fluorides as lithium-ion battery cathodes

Hua, Xiao; Eggeman, Alexander S.; Castillo-Martínez, Elizabeth; Robert, Rosa; Geddes, Harry S.; Lu, Ziheng; Pickard, Chris J.; Meng, Wei; Wiaderek, Kamila M.; Pereira, Nathalie; Amatucci, Glenn G.; Midgley, Paul A.; Chapman, Karena W.; Steiner, Ullrich; Goodwin, Andrew L.; Grey, Clare P.

doi:10.1038/s41563-020-00893-1

Revisiting metal fluorides as lithium-ion battery cathodes

Journal Article · Thu Jan 21 00:00:00 EST 2021 · Nature Materials

DOI:https://doi.org/10.1038/s41563-020-00893-1· OSTI ID:1818446

^[1]; ^[2]; Castillo-Martínez, Elizabeth ^[3]; Robert, Rosa ^[4]; Geddes, Harry S. ^[5]; Lu, Ziheng ^[4]; ^[6]; Meng, Wei ^[4]; Wiaderek, Kamila M. ^[7]; Pereira, Nathalie ^[8]; Amatucci, Glenn G. ^[8]; Midgley, Paul A. ^[4]; ^[9]; ^[10]; ^[5]; ^[4]

Univ. of Cambridge (United Kingdom); Adolphe Merkle Inst., Fribourg (Switzerland); Univ. of Oxford (United Kingdom). Inorganic Chemistry Lab.
Univ. of Cambridge (United Kingdom); Univ. of Manchester (United Kingdom)
Univ. of Cambridge (United Kingdom); Univ. Complutense de Madrid (Spain)
Univ. of Cambridge (United Kingdom)
Univ. of Oxford (United Kingdom). Inorganic Chemistry Lab.
Univ. of Cambridge (United Kingdom); Tohoku Univ., Sendai (Japan). Advanced Inst. for Materials Research
Argonne National Lab. (ANL), Argonne, IL (United States)
Rutgers Univ., New Brunswick, NJ (United States)
State Univ. of New York (SUNY), Stony Brook, NY (United States)
Adolphe Merkle Inst., Fribourg (Switzerland)

Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF₃ using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF₂ and CuF₂. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F- sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle's surface, along with a cation-ordered and stacking-disordered phase, A-Li_xFe_yF₃, which is structurally related to alpha-/beta-LiMn²⁺Fe³⁺F₆ and which topotactically transforms to B- and then C-Li_xFe_yF₃, before forming LiF and Fe. Lithiation of FeF₂ and CuF₂ results in a buffer phase between FeF₂/CuF₂ and LiF. Overall, the resulting principles will aid future developments of a wider range of isomorphic metal fluorides.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Engineering and Physical Sciences Research Council (EPSRC); European Commission - Marie Sklodowska-Curie Actions (MSCA); European Research Council (ERC); Royal Society United Kingdom; Swiss National Science Foundation (SNSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0001294

OSTI ID:: 1818446

Alternate ID(s):: OSTI ID: 1814984
OSTI ID: 1818337

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 6 Vol. 20; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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