Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes

Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes

TitleRole of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes
Publication TypeJournal Article
Year of Publication2020
AuthorsDongchang Chen, Jinpeng Wu, Joseph K Papp, Bryan D McCloskey, Wanli Yang, Guoying Chen
JournalSmall
Volume16
Issue22
Pagination2000656
Date Published05/2020
ISSN1613-6810
Abstract

Owing to the capacity boost from oxygen redox activities, Li‐rich cation‐disordered rocksalts (LRCDRS) represent a new class of promising high‐energy Li‐ion battery cathode materials. Redox‐inactive transition‐metal (TM) cations, typically d0 TM, are essential in the formation of rocksalt phases, however, their role in electrochemical performance and cathode stability is largely unknown. In the present study, the effect of two d0 TM (Nb5+ and Ti4+) is systematically compared on the redox chemistry of Mn‐based model LRCDRS cathodes, namely Li1.3Nb0.3Mn0.4O2 (LNMO), Li1.25Nb0.15Ti0.2Mn0.4O2 (LNTMO), and Li1.2Ti0.4Mn0.4O2 (LTMO). Although electrochemically inactive, d0 TM serves as a modulator for oxygen redox, with Nb5+ significantly enhancing initial charge storage contribution from oxygen redox. Further studies using differential electrochemical mass spectroscopy and resonant inelastic X‐ray scattering reveal that Ti4+ is better in stabilizing the oxidized oxygen anions (On, 0 < n < 2), leading to a more reversible O redox process with less oxygen gas release. As a result, much improved chemical, structural and cycling stabilities are achieved on LTMO. Detailed evaluation on the effect of d0 TM on degradation mechanism further suggests that proper design of redox‐inactive TM cations provides an important avenue to balanced capacity and stability in this newer class of cathode materials.

DOI10.1002/smll.202000656
Short TitleSmall
Refereed DesignationRefereed