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Transition Metal Migration Can Facilitate Ionic Diffusion in Defect Garnet-Based Intercalation Electrodes

Bashian, NH; Abdel-Latif, S; Zuba, M; Griffith, KJ; Ganose, AM; Stiles, JW; Zhou, S; ... Melot, BC; + view all (2020) Transition Metal Migration Can Facilitate Ionic Diffusion in Defect Garnet-Based Intercalation Electrodes. ACS Energy Letters , 5 (5) pp. 1448-1455. 10.1021/acsenergylett.0c00376. Green open access

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Abstract

The importance of metal migration during multielectron redox activity has been characterized, revealing a competing demand to satisfy bonding requirements and local strains in structures upon alkali intercalation. The local structural evolution required to accommodate intercalation in Y2(MoO4)3 and Al2(MoO4)3 has been contrasted by operando characterization methods, including X-ray absorption spectroscopy and diffraction, along with nuclear magnetic resonance measurements. Computational modeling further rationalized behavioral differences. The local structure of Y2(MoO4)3 was maintained upon lithiation, while the structure of Al2(MoO4)3 underwent substantial local atomic rearrangements as the more ionic character of the bonds in Al2(MoO4)3 allowed Al to mix off its starting octahedral position to accommodate strain during cycling. However, this mixing was prevented in the more covalent Y2(MoO4)3, which accommodated strain through rotational motion of polyhedral subunits. Knowing that an increased ionic character can facilitate the diffusion of redox-inactive metals when cycling multielectron electrodes offers a powerful design principle when identifying next-generation intercalation hosts.

Type: Article
Title: Transition Metal Migration Can Facilitate Ionic Diffusion in Defect Garnet-Based Intercalation Electrodes
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acsenergylett.0c00376
Publisher version: https://doi.org/10.1021/acsenergylett.0c00376
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
Keywords: Redox reactions, Lithiation, Ions, Chemical structure, Materials
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10096570
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