Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides

Title
Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides
Authors
임기필홍지현William E. GentPenghao Xiao서동화Jinpeng WuPeter M. CsernicaChristopher J. TakacsDennis NordlundCheng-Jun Sun빈 스톤Donata PassarelloWanli YangDavid PrendergastGerbrand CederMichael F. ToneyWilliam C. Chueh
Keywords
Li-ion battery; Lithium Compounds; Materials Science; Anion Redox; Materials Chemistry; Synchrotron X-ray Ananlysis; Materials Characterization; Energy Materials
Issue Date
2019-03
Publisher
Nature materials
Citation
VOL 18-265
Abstract
Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4  V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2− xIr1− ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure– redox coupling arises from the local stabilization of short approximately 1.8  Å metal– oxygen π bonds and approximately 1.4  O– O dimers during oxygen redox, which occurs in Li2− ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.
URI
http://pubs.kist.re.kr/handle/201004/69138
ISSN
1476-1122
Appears in Collections:
KIST Publication > Article
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE