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Issue 10, 2016
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Structurally stable Mg-doped P2-Na2/3Mn1−yMgyO2 sodium-ion battery cathodes with high rate performance: insights from electrochemical, NMR and diffraction studies

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Abstract

Sodium-ion batteries are a more sustainable alternative to the existing lithium-ion technology and could alleviate some of the stress on the global lithium market as a result of the growing electric car and portable electronics industries. Fundamental research focused on understanding the structural and electronic processes occurring on electrochemical cycling is key to devising rechargeable batteries with improved performance. We present an in-depth investigation of the effect of Mg doping on the electrochemical performance and structural stability of Na2/3MnO2 with a P2 layer stacking by comparing three compositions: Na2/3Mn1−yMgyO2 (y = 0.0, 0.05, 0.1). We show that Mg substitution leads to smoother electrochemistry, with fewer distinct electrochemical processes, improved rate performance and better capacity retention. These observations are attributed to the more gradual structural changes upon charge and discharge, as observed with synchrotron, powder X-ray, and neutron diffraction. Mg doping reduces the number of Mn3+ Jahn–Teller centers and delays the high voltage phase transition occurring in P2-Na2/3MnO2. The local structure is investigated using 23Na solid-state nuclear magnetic resonance (ssNMR) spectroscopy. The ssNMR data provide direct evidence for fewer oxygen layer shearing events, leading to a stabilized P2 phase, and an enhanced Na-ion mobility up to 3.8 V vs. Na+/Na upon Mg doping. The 5% Mg-doped phase exhibits one of the best rate performances reported to date for sodium-ion cathodes with a P2 structure, with a reversible capacity of 106 mA h g−1 at the very high discharge rate of 5000 mA g−1. In addition, its structure is highly reversible and stable cycling is obtained between 1.5 and 4.0 V vs. Na+/Na, with a capacity of approximately 140 mA h g−1 retained after 50 cycles at a rate of 1000 mA g−1.

Graphical abstract: Structurally stable Mg-doped P2-Na2/3Mn1−yMgyO2 sodium-ion battery cathodes with high rate performance: insights from electrochemical, NMR and diffraction studies

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Publication details

The article was received on 17 Jun 2016, accepted on 19 Aug 2016 and first published on 19 Aug 2016


Article type: Paper
DOI: 10.1039/C6EE01750A
Citation: Energy Environ. Sci., 2016,9, 3240-3251
  • Open access: Creative Commons BY license
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    Structurally stable Mg-doped P2-Na2/3Mn1−yMgyO2 sodium-ion battery cathodes with high rate performance: insights from electrochemical, NMR and diffraction studies

    R. J. Clément, J. Billaud, A. Robert Armstrong, G. Singh, T. Rojo, P. G. Bruce and C. P. Grey, Energy Environ. Sci., 2016, 9, 3240
    DOI: 10.1039/C6EE01750A

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