Fluorination‐Enhanced Surface Stability of Disordered Rocksalt Cathodes

Li, Linze; Ahn, Juhyeon; Yue, Yuan; Tong, Wei; Chen, Guoying; Wang, Chongmin

doi:10.1002/adma.202106256

Title: Fluorination‐Enhanced Surface Stability of Disordered Rocksalt Cathodes

Journal Article · Tue Feb 08 00:00:00 EST 2022 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202106256· OSTI ID:1843999

^[1]; Ahn, Juhyeon ^[2]; Yue, Yuan ^[2]; Tong, Wei ^[2]; Chen, Guoying ^[2]; Wang, Chongmin ^[1]

Environmental Molecular Sciences Laboratory Pacific Northwest National Laboratory 902 Battelle Boulevard Richland WA 99354 USA
Energy Storage and Distributed Resources Division Lawrence Berkeley National Laboratory 1 Cyclotron Road Berkeley CA 94720 USA

Abstract Cation‐disordered rocksalt (DRX) oxides are a promising new class of high‐energy‐density cathode materials for next‐generation Li‐ion batteries. However, their capacity fade presents a major challenge. Partial fluorine (F) substitution into the oxygen (O) lattice appears to be an effective strategy for improving the cycling stability, but the underlying atomistic mechanism remains elusive. Here, using a combination of advanced transmission electron microscopy based imaging and spectroscopy techniques, the structural and chemical evolution upon cycling of Mn‐based DRX cathodes with an increasing F content (Li–Mn–Nb–O–F _x , x = 0, 0.05, 0.2) are probed. The atomic origin behind the beneficial effect of high‐level fluorination for enhancing the surface stability of the DRX is revealed. It is discovered that, due to the reduced O redox activity while with increasing F concentration, F in the DRX lattice mitigates the formation of an O‐deficient surface layer upon cycling. For low F‐substituted DRX, the O loss near the surface results in the formation of an amorphous cathode–electrolyte interphase layer and nanoscale voids after extended cycling. Increased F concentration in the DRX lattice minimizes both O loss and the interfacial reactions between DRX and the liquid electrolyte, enhancing the surface stability of DRX. These results provide guidance on the development of next‐generation cathode materials through anion substitution.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: DEAC02‐05CH11231; DE‐LC‐000L053

OSTI ID:: 1843999

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Vol. 34 Journal Issue: 12; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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