Journal
NATURE MATERIALS
Volume 18, Issue 3, Pages 256-+Publisher
NATURE PORTFOLIO
DOI: 10.1038/s41563-018-0276-1
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Funding
- Office of Vehicle Technologies, Battery Materials Research Program, US Department of Energy (DOE)
- Advanced Light Source Doctoral Fellowship
- Siebel Scholars programme
- Kwanjeong Education Foundation
- Office of Science, Office of Basic Energy Sciences, of the US DOE [DE-AC02-05CH11231, DE-AC02-76SF00515]
- National Science Foundation [ECCS-1542152]
- US DOE [DE-AC02-06CH11357]
- Canadian Light Source
- NorthEast Center for Chemical Energy Storage, an Energy Frontier Research Center - US DOE, Office of Science, Office of Basic Energy Sciences [DE-SC0012583]
- China Automotive Battery Research Institute
- General Research Institute for NonFerrous Metals
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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 angstrom metal-oxygen pi bonds and approximately 1.4 angstrom O-O dimers during oxygen redox, which occurs in Li2-xIr1-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.
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