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Issue 1, 2017
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Na2.32Co1.84(SO4)3 as a new member of the alluaudite family of high-voltage sodium battery cathodes

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Abstract

Electrochemical energy storage has recently seen tremendous emphasis being placed on the large-scale (power) grid storage. Sodium-ion batteries are capable of achieving this goal with economic viability. In a recent breakthrough in sodium-ion battery research, the alluaudite framework (Na2Fe2(SO4)3) has been reported, with the highest Fe3+/Fe2+ redox potential (ca. 3.8 V, Barpanda, et al., Nat. Commun., 2014, 5, 4358). Exploring this high-voltage sodium insertion system, we report the discovery of Na2+2xCo2−x(SO4)3 (x = 0.16) as a new member of the alluaudite class of cathode. Stabilized by low-temperature solid-state synthesis (T ≤ 350 °C), this novel Co-based compound assumes a monoclinic structure with C2/c symmetry, which undergoes antiferromagnetic ordering below 10.2 K. Isotypical to the Fe-homologue, it forms a complete family of solid-solution Na2+2x(Fe1−yCoy)2−x(SO4)3 [y = 0–1]. Ab initio DFT analysis hints at potential high voltage operation at 4.76–5.76 V (vs. Na), depending on the degree of desodiation involving a strong participation of the oxygen sub-lattice. With the development of safe organic electrolytes, Na2+2xCo2−x(SO4)3 can work as a cathode material (∼5 V) for sodium-ion batteries.

Graphical abstract: Na2.32Co1.84(SO4)3 as a new member of the alluaudite family of high-voltage sodium battery cathodes

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Publication details

The article was received on 28 Sep 2016, accepted on 12 Nov 2016 and first published on 14 Nov 2016


Article type: Paper
DOI: 10.1039/C6DT03767D
Citation: Dalton Trans., 2017,46, 55-63
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    Na2.32Co1.84(SO4)3 as a new member of the alluaudite family of high-voltage sodium battery cathodes

    D. Dwibedi, R. Gond, A. Dayamani, R. B. Araujo, S. Chakraborty, R. Ahuja and P. Barpanda, Dalton Trans., 2017, 46, 55
    DOI: 10.1039/C6DT03767D

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