Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries
Abstract
Abstract Cation‐disordered rocksalt (DRX) materials have emerged as a class of novel high‐capacity cathodes for Li‐ion batteries. However, the commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies show that fluorination of DRX cathodes can effectively reduce oxygen loss and improve cycling stability; however, the underlying atomic‐scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, the correlation between the electrochemical properties and structural evolution in Mn‐redox‐based DRX cathodes, Li 1.2 Ti 0.4– x Mn 0.4+ x O 2.0‐ x F x ( x = 0 and 0.2) is examined. It is found that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. A novel rocksalt‐to‐spinel‐like structural transformation in the DRX bulk is further revealed, which surprisingly contributes to a gradual capacity increase during cycling. The results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.
- Authors:
-
[1];
[1]
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE
- OSTI Identifier:
- 1813390
- Alternate Identifier(s):
- OSTI ID: 1785746
- Grant/Contract Number:
- AC02-05CH11231; LC-000L053; AC05-76RLO1830; DEAC02‐05CH11231; DE‐LC‐000L053
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Functional Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 25; Journal ID: ISSN 1616-301X
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; cation-disordered rocksalt; fluorination; Li-ion batteries; scanning transmission electron microscopy; structural transformation
Citation Formats
Li, Linze, Lun, Zhengyan, Chen, Dongchang, Yue, Yuan, Tong, Wei, Chen, Guoying, Ceder, Gerbrand, and Wang, Chongmin. Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries. United States: N. p., 2021.
Web. doi:10.1002/adfm.202101888.
Li, Linze, Lun, Zhengyan, Chen, Dongchang, Yue, Yuan, Tong, Wei, Chen, Guoying, Ceder, Gerbrand, & Wang, Chongmin. Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries. United States. https://doi.org/10.1002/adfm.202101888
Li, Linze, Lun, Zhengyan, Chen, Dongchang, Yue, Yuan, Tong, Wei, Chen, Guoying, Ceder, Gerbrand, and Wang, Chongmin. Sat .
"Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries". United States. https://doi.org/10.1002/adfm.202101888. https://www.osti.gov/servlets/purl/1813390.
@article{osti_1813390,
title = {Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries},
author = {Li, Linze and Lun, Zhengyan and Chen, Dongchang and Yue, Yuan and Tong, Wei and Chen, Guoying and Ceder, Gerbrand and Wang, Chongmin},
abstractNote = {Abstract Cation‐disordered rocksalt (DRX) materials have emerged as a class of novel high‐capacity cathodes for Li‐ion batteries. However, the commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies show that fluorination of DRX cathodes can effectively reduce oxygen loss and improve cycling stability; however, the underlying atomic‐scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, the correlation between the electrochemical properties and structural evolution in Mn‐redox‐based DRX cathodes, Li 1.2 Ti 0.4– x Mn 0.4+ x O 2.0‐ x F x ( x = 0 and 0.2) is examined. It is found that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. A novel rocksalt‐to‐spinel‐like structural transformation in the DRX bulk is further revealed, which surprisingly contributes to a gradual capacity increase during cycling. The results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.},
doi = {10.1002/adfm.202101888},
journal = {Advanced Functional Materials},
number = 25,
volume = 31,
place = {United States},
year = {Sat Apr 17 00:00:00 EDT 2021},
month = {Sat Apr 17 00:00:00 EDT 2021}
}
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