Data · dataset · 2026
Multi-Step Oxygen Redox Mechanism in the Polyanionic Lithium-Rich Cathode Li<sub>2</sub>FeSiO<sub>4</sub>
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Lithium-rich cathode materials offer significantly higher energy densities than conventional cathode materials, due to their ability to store charge beyond the formal transition-metal redox limit, via so-called “oxygen redox”.
Description
In lithium-rich oxides, oxygen redox is accompanied by molecular O<sub>2</sub> formation and transition-metal migration, associated with irreversible structural change and poor cycling stability.
Lithium-rich silicates provide an alternative lithium-rich chemistry, and have been proposed to be resilient to O<sub>2</sub> formation at the top of charge, due to their covalently bonded [SiO4]4− framework. We report a computational study of the top-of-charge behavior of the prototypical silicate cathode Li<sub>2</sub>FeSiO<sub>4</sub>. Using density functional theory, we predict that fully delithiated FeSiO<sub>4</sub> is thermodynamically unstable with respect to oxidation of oxide ions to form molecular O<sub>2</sub> within the bulk material.
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Ab initio molecular dynamics shows this decomposition occurs spontaneously, via a multistep mechanism involving Fe<sup>IV</sup> migration and disproportionation to Fe<sup>III</sup> and Fe<sup>V</sup>, and subsequent Fe<sup>V</sup> reduction alongside molecular O<sub>2</sub> formation. Our findings demonstrate that polyanionic frameworks do not inherently prevent O<sub>2</sub> formation in lithium-rich cathodes, and illustrate how different previously proposed oxygen redox mechanisms can function as steps within a compound process.
Links
Where it is published
- DOI doi.org/10.1021/jacs.6c02850.s001 ↗
DOI / persistent id · from zivahub uct ac za
Catalogue records · 1
- OAI-PMH record api.figshare.com/v2/oai?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Af… ↗
metadata API · from zivahub uct ac za
Topics
- From keywords
- Biochemistry and cell biology · Bioinformatics and computational biology · Cancer · Chemistry · Earth & Environmental Science · Ecology · Evolutionary biology · Life Sciences · Medicine & Health · Social Science · Sociology
- Inferred from text
- Density functional theory 75%
Provenance · 1 source records, 17 field assertions
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|---|---|---|---|
| ZivaHub | oai:figshare.com:article/34018417 | 12 d ago | JSON v1 |
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