Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Hwang, Sooyeon; Ji, Xiao; Bak, Seong-Min; Sun, Ke; Bai, Jianming; Fan, Xiulin; Gan, Hong; Wang, Chunsheng; Su, Dong

doi:10.1021/acsnano.0c03714

Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries

Journal Article · Wed Jul 08 00:00:00 EDT 2020 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.0c03714· OSTI ID:1638818

^[1]; Ji, Xiao ^[2]; ^[3]; Sun, Ke ^[3]; ^[4]; ^[2]; ^[3]; ^[2]; ^[5]

Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Univ. of Maryland, College Park, MD (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics

Metal fluorides present a high redox potential among the conversion-type compounds, which make them specially work as cathode materials of lithium ion batteries. To mitigate the notorious cycling instability of conversion-type materials, substitutions of anion and cation have been proposed but the role of foreign elements in reaction pathway is not fully evaluated. In this work, we explored the lithiation pathway of a rutile-Fe_0.9Co_0.1OF cathode with multimodal analysis, including ex situ and in situ transmission electron microscopy and synchrotron X-ray techniques. Our work revealed a prolonged intercalation–extrusion–cation disordering process during phase transformations from the rutile phase to rocksalt phase, which microscopically corresponds to topotactic rearrangement of Fe/Co–O/F octahedra. During this process, the diffusion channels of lithium transformed from 3D to 2D while the corner-sharing octahedron changed to edge-sharing octahedron. DFT calculations indicate that the Co and O cosubstitution of the Fe_0.9Co_0.1OF cathode can improve its structural stability by stabilizing the thermodynamic semistable phases and reducing the thermodynamic potentials. We anticipate that our study will inspire further explorations on untraditional intercalation systems for secondary battery applications.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN) and National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: Chinese Academy of Sciences (CAS); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1638818

Report Number(s):: BNL--216168-2020-JAAM

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 8 Vol. 14; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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