Understanding cation-disordered rocksalt oxyfluoride cathodes

Chen, Dongchang; Ahn, Juhyeon; Self, Ethan; Nanda, Jagjit; Chen, Guoying

doi:10.1039/d0ta12179g

Understanding cation-disordered rocksalt oxyfluoride cathodes

Journal Article · Sun Feb 28 23:00:00 EST 2021 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d0ta12179g· OSTI ID:1786286

Chen, Dongchang ^[1]; Ahn, Juhyeon ^[1]; ^[2]; ^[2]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Partial fluorine (F) substitution into the oxygen (O) sublattice has been shown to improve cycling stability of cation-disordered Li-excess rocksalt oxide (DRX) cathodes. Detailed understanding on failure mechanisms and key optimization knowledge of fluorinated-DRX (F-DRX), however, are lacking. In the present study, we incorporate different amounts of F into a baseline DRX system, Li_1.2Ti_0.4Mn_0.4O₂ (LTMO3.0, 3.0 denotes nominal Li/Mn ratio), and synthesize two oxyfluoride compounds, Li-rich Li_1.3Ti_0.3Mn_0.4O_1.7F_0.3 (LTMOF3.25) and Mn-rich Li_1.2Ti_0.2Mn_0.6O_1.8F_0.2 (LTMOF2.0) with an increased and reduced Li/Mn ratio of 3.25 and 2.0, respectively. Through careful monitoring of chemical and structural evolution, we show that cycling-induced changes are manifested not only by Mn reduction and degradation of its local coordination environment, but also by F enrichment and formation of LiF-type of domains on the surface. A “concerted-densification” based failure mechanism, involving atomic-level changes in both transition-metal cationic sublattice and oxygen/fluorine anionic sublattice, is proposed for the degradation in F-DRX cathode materials. The study reveals that increasing F content accompanied by reduced Li/Mn ratio mitigates the degradation process, offering key design strategies in achieving balanced cathode capacity and stability.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725; AC02-76SF00515; AC02-05CH11231

OSTI ID:: 1786286

Alternate ID(s):: OSTI ID: 1769458

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 12 Vol. 9; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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