Importance of superstructure in stabilizing oxygen redox in P3- Na0.67Li0.2Mn0.8O2
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Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium-ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3-type Na0.67Li0.2Mn0.8O2 is reinvestigated and a ribbon superlattice is identified for the first time in P3-type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3d–O 2p favors ligand-to-metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.
Kim , E J , Maughan , P , Bassey , E , Clément , R J , Ma , L A , Duda , L C , Sehrawat , D , Younesi , R , Sharma , N , Grey , C & Armstrong , A R 2022 , ' Importance of superstructure in stabilizing oxygen redox in P3- Na 0.67 Li 0.2 Mn 0.8 O 2 ' , Advanced Energy Materials , vol. 12 , no. 3 , 2102325 . https://doi.org/10.1002/aenm.202102325
Advanced Energy Materials
Copyright © 2021 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
DescriptionThis work was supported by the Faraday Institution (grant number FIRG018) and the Australian Research Council (discovery and future fellowship programs DP170100269/DP200100959 and FT200100707). E.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018 and is also grateful for use of the ARCHER UK National Supercomputing Service via our membership in the UK's HEC Materials Chemistry Consortium, funded by the EPSRC (EP/L000202).
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