Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Li, Linze; Lun, Zhengyan; Chen, Dongchang; Yue, Yuan; Tong, Wei; Chen, Guoying; Ceder, Gerbrand; Wang, Chongmin

doi:10.1002/adfm.202101888

Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Journal Article · Wed Jun 16 04:00:00 EDT 2021 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202101888· OSTI ID:1798186

Li, Linze ^[1]; Lun, Zhengyan ^[2]; Chen, Dongchang ^[3]; Yue, Yuan ^[3]; Tong, Wei ^[3]; Chen, Guoying ^[3]; Ceder, Gerbrand ^[3]; ^[1]

BATTELLE (PACIFIC NW LAB)
University of California, Berkeley
Lawrence Berkeley National Laboratory

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies have shown that fluorination of DRX cathodes can effectively reduce the oxygen loss and improve the 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, we examine the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li1.2Ti0.4-xMn0.4+xO2.0-xFx (x = 0 and 0.2). We find that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. We further reveal a novel rocksalt-to-spinel-like structural transformation in the DRX bulk, which surprisingly contributes to a gradual capacity increase during cycling. Our results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1798186

Report Number(s):: PNNL-SA-159215

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 25 Vol. 31

Country of Publication:: United States

Language:: English

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