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Issue 31, 2015
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Improving the energy density of Na3V2(PO4)3-based positive electrodes through V/Al substitution

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Abstract

The crystal chemistry and the electrochemical properties upon Na+ extraction/insertion of NASICON-type Na3AlyV2−y(PO4)3 compositions (y = 0.1, 0.25 and 0.5) were investigated. It was found that this family of V/Al substituted NASICON materials undergoes multiple reversible phase transitions between −50 °C and 250 °C upon heating, from monoclinic to rhombohedral symmetry, related to progressive disordering of Na+ ions within the framework. Na+ insertion/extraction mechanisms were monitored by operando X-ray diffraction. It is shown for the first time that substitution of aluminum for vanadium in Na3Al0.5V1.5(PO4)3 increases significantly the theoretical energy density of these promising positive electrodes (425 W h kg−1) due to its lighter molecular weight and the possibility of reversible operation on the V4+/V5+ redox couple at 3.95 V vs. Na+/Na.

Graphical abstract: Improving the energy density of Na3V2(PO4)3-based positive electrodes through V/Al substitution

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Supplementary files

Article information


Submitted
13 May 2015
Accepted
28 Jun 2015
First published
30 Jun 2015

J. Mater. Chem. A, 2015,3, 16198-16205
Article type
Paper
Author version available

Improving the energy density of Na3V2(PO4)3-based positive electrodes through V/Al substitution

F. Lalère, V. Seznec, M. Courty, R. David, J. N. Chotard and C. Masquelier, J. Mater. Chem. A, 2015, 3, 16198
DOI: 10.1039/C5TA03528G

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