Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries
Abstract
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-Fe0.9Co0.1OF 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 Fe0.9Co0.1OF 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.
- Authors:
-
[1];
[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
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN) and National Synchrotron Light Source II (NSLS-II)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); Chinese Academy of Sciences (CAS)
- OSTI Identifier:
- 1638818
- Report Number(s):
- BNL-216168-2020-JAAM
Journal ID: ISSN 1936-0851
- Grant/Contract Number:
- SC0012704; XDB07030200
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 14; Journal Issue: 8; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; in situ/ex situ multimodal analysis; lithium ion batteries; iron fluoride; cathode, reaction mechanism
Citation Formats
Hwang, Sooyeon, Ji, Xiao, Bak, Seong-Min, Sun, Ke, Bai, Jianming, Fan, Xiulin, Gan, Hong, Wang, Chunsheng, and Su, Dong. Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries. United States: N. p., 2020.
Web. doi:10.1021/acsnano.0c03714.
Hwang, Sooyeon, Ji, Xiao, Bak, Seong-Min, Sun, Ke, Bai, Jianming, Fan, Xiulin, Gan, Hong, Wang, Chunsheng, & Su, Dong. Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries. United States. https://doi.org/10.1021/acsnano.0c03714
Hwang, Sooyeon, Ji, Xiao, Bak, Seong-Min, Sun, Ke, Bai, Jianming, Fan, Xiulin, Gan, Hong, Wang, Chunsheng, and Su, Dong. Wed .
"Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries". United States. https://doi.org/10.1021/acsnano.0c03714. https://www.osti.gov/servlets/purl/1638818.
@article{osti_1638818,
title = {Revealing Reaction Pathways of Collective Substituted Iron Fluoride Electrode for Lithium Ion Batteries},
author = {Hwang, Sooyeon and Ji, Xiao and Bak, Seong-Min and Sun, Ke and Bai, Jianming and Fan, Xiulin and Gan, Hong and Wang, Chunsheng and Su, Dong},
abstractNote = {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-Fe0.9Co0.1OF 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 Fe0.9Co0.1OF 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.},
doi = {10.1021/acsnano.0c03714},
journal = {ACS Nano},
number = 8,
volume = 14,
place = {United States},
year = {Wed Jul 08 00:00:00 EDT 2020},
month = {Wed Jul 08 00:00:00 EDT 2020}
}
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