Show simple item record

Files in this item


Item metadata

dc.contributor.authorLinnell, Stephanie Frances
dc.contributor.authorManche, Alexis Gilles
dc.contributor.authorLiao, Yingling
dc.contributor.authorHirsbrunner, Moritz
dc.contributor.authorImada, Saki
dc.contributor.authorNaden, Aaron Benjamin
dc.contributor.authorIrvine, John T. S.
dc.contributor.authorDuda, Laurent
dc.contributor.authorArmstrong, Robert
dc.identifier.citationLinnell , S F , Manche , A G , Liao , Y , Hirsbrunner , M , Imada , S , Naden , A B , Irvine , J T S , Duda , L & Armstrong , R 2022 , ' Effect of Cu substitution on anion redox behaviour in P3-type sodium manganese oxides ' , Journal of Physics: Energy , vol. 4 , no. 4 , 044006 .
dc.identifier.otherPURE: 281701171
dc.identifier.otherPURE UUID: 37d04f57-be96-4ad6-9372-fb49575d5b29
dc.identifier.otherORCID: /0000-0002-8394-3359/work/120849378
dc.identifier.otherORCID: /0000-0003-2876-6991/work/120849819
dc.identifier.otherORCID: /0000-0003-1937-0936/work/120849938
dc.identifier.otherWOS: 000865871000001
dc.identifier.otherScopus: 85140016832
dc.descriptionFunding information: This work was supported by the Faraday Institution (Grant No. FIRG018). The authors gratefully acknowledge support from the Engineering and Physical Sciences Research Council (EPSRC), Grant Nos. EP/L017008/1, EP/R023751/1 and EP/T019298/1.en
dc.description.abstractSodium layered oxides which display oxygen anion redox behaviour are considered promising positive electrodes for sodium-ion batteries because they offer increased specific capacities. However, they suffer from irreversible structural changes resulting in significant capacity loss and limited oxygen redox reversibility. Here the effect of Cu substitution on the electrochemical performance of P3-type sodium manganese oxide is examined by evaluating the structural and electronic structural evolution upon cycling, supported by density functional theory (DFT) calculations. Over the voltage range 1.8–3.8 V vs. Na/Na+, where the redox reactions of the transition metal ions contribute entirely towards the charge compensation mechanism, stable cycling performance is maintained, showing a capacity retention of 90% of the initial discharge capacity of 166 mA h g−1 after 40 cycles at 10 mA g−1. Over an extended voltage range of 1.8–4.3 V vs. Na/Na+, oxygen anion redox is invoked, with a voltage hysteresis of 110 mV and a greater initial discharge capacity of 195 mA h g−1 at 10 mA g−1 is reached. Ex-situ powder x-ray diffraction patterns reveal distortion of the P3 structure to P'3 after charge to 4.3 V, and then transformation to O'3 upon discharge to 1.8 V, which contributes towards the capacity fade observed between the voltage range 1.8–4.3 V. DFT with projected density of states calculations reveal a strong covalency between the copper and oxygen atoms which facilitate both the cationic and anionic redox reactions in P3-type Na0.67Mn0.9Cu0.1O2.
dc.relation.ispartofJournal of Physics: Energyen
dc.rightsCopyright © 2022 The Author(s). Published by IOP Publishing Ltd. Open Access. Original content from this work may be used under the terms of the Creative Commons Attribution 4.0 license. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.en
dc.subjectSodium-ion batteriesen
dc.subjectCathode materialsen
dc.subjectLayered oxidesen
dc.subjectAnion redoxen
dc.subjectQD Chemistryen
dc.titleEffect of Cu substitution on anion redox behaviour in P3-type sodium manganese oxidesen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. Institute of Behavioural and Neural Sciencesen
dc.contributor.institutionUniversity of St Andrews. Centre for Energy Ethicsen
dc.contributor.institutionUniversity of St Andrews. Centre for Designer Quantum Materialsen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

This item appears in the following Collection(s)

Show simple item record