학술논문
Accessing Mg-Ion Storage in V 2 PS 10 via Combined Cationic-Anionic Redox with Selective Bond Cleavage.
Document Type
Academic Journal
Author
Wright MA; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Stephenson Institute for Renewable Energy, University of Liverpool, L69 7ZF, Liverpool, UK.; Surta TW; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Evans JA; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Lim J; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Stephenson Institute for Renewable Energy, University of Liverpool, L69 7ZF, Liverpool, UK.; Jo H; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Hawkins CJ; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Bahri M; Albert Crewe Centre, University of Liverpool, Research Technology Building, Elisabeth Street, Pembroke Place, L69 3GE, Liverpool, UK.; Daniels LM; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Chen R; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Zanella M; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Chagas LG; Johnson Matthey Technology Centre, Sonning Common, RG4 9NH, Reading, UK.; Cookson J; Johnson Matthey Technology Centre, Sonning Common, RG4 9NH, Reading, UK.; Collier P; Johnson Matthey Technology Centre, Sonning Common, RG4 9NH, Reading, UK.; Cibin G; Diamond Light Source, Harwell Science and Innovation Campus, OX11 0DE, Didcot, UK.; Chadwick AV; School of Physical Sciences, University of Kent, CT2 7NH, Canterbury, UK.; Dyer MS; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Browning ND; Albert Crewe Centre, University of Liverpool, Research Technology Building, Elisabeth Street, Pembroke Place, L69 3GE, Liverpool, UK.; School of Engineering, Department of Mechanical, Materials and Aerospace Engineering, University of Liverpool, L69 3GH, Liverpool, UK.; Claridge JB; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Hardwick LJ; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.; Stephenson Institute for Renewable Energy, University of Liverpool, L69 7ZF, Liverpool, UK.; Rosseinsky MJ; Department of Chemistry, University of Liverpool, L69 7ZD, Liverpool, UK.
Source
Publisher: Wiley-VCH Country of Publication: Germany NLM ID: 0370543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1521-3773 (Electronic) Linking ISSN: 14337851 NLM ISO Abbreviation: Angew Chem Int Ed Engl Subsets: PubMed not MEDLINE; MEDLINE
Subject
Language
English
Abstract
Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg 2+ and the host structure. V 2 PS 10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g -1 is achieved with fast Mg 2+ diffusion of 7.2 × ${\times }$ 10 -11 -4 × ${\times }$ 10 -14 cm 2 s -1 . The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S 2 ) 2- site; enabled by reversible cleavage of S-S bonds, identified by X-ray photoelectron and X-ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)