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A new high voltage alluaudite sodium battery insertion material

Barman, P and Jha, PK and Chaupatnaik, A and Jayanthi, K and Rao, RP and Sai Gautam, G and Franger, S and Navrotsky, A and Barpanda, P (2023) A new high voltage alluaudite sodium battery insertion material. In: Materials Today Chemistry, 27 .

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Official URL: https://doi.org/10.1016/j.mtchem.2022.101316


Large-scale stationary storage forms a key sector that can be economically served by sodium-ion batteries. In realizing practical sodium-ion batteries, discovery and development of novel cathodes is essential. In this spirit, alluaudite-type Na2Fe2(SO4)3 was reported in 2014 to have the highest Fe3+/Fe2+ redox potential (∼3.8 V vs. Na). This finding led to reports on various PO43− and SO42− based alluaudite compounds exhibiting high energy densities. In 2017, MoO42− based alluaudite, Na2.67Mn1.67(MoO4)3, was found as a 3.45 V cathode material. Exploring molybdenum chemistry further, this work reports alluaudite type Na3.36Co1.32(MoO4)3 (NCMo) as a novel versatile electroactive cathode for Li-ion and Na-ion batteries. It was synthesized by a wet solution-combustion route with a restricted annealing duration of 1 min at 600 °C. Calorimetric study revealed the formation enthalpy from component oxides (ΔH°f,ox = −575.49 ± 7.75 kJ/mol) to be highly exothermic. Unlike the sulfate class of alluaudites, this material is highly stable in air and moisture (ΔHds = 537.42 ± 0.78 kJ/mol). Having an ionic conductivity of 6.065 × 10−8 S/cm (at 50 °C), it offers a pseudo two-dimensional Na+ migration pathway. Without any material optimization, NCMo was found to work as a high-voltage insertion cathode (ca. 4.0 V vs. Na/Na+ and 4.1 V vs. Li/Li+) in sync with theoretically predicted potential of 3.98 V (vs. Na/Na+). Ex-situ X-ray diffraction and photoelectron spectroscopy studies revealed the occurrence of solid-solution redox mechanism solely involving Co3+/Co2+ redox centre. It benchmarks Na3.36Co1.32(MoO4)3 as a novel electrochemically active Mo-based alluaudite-type polyanionic cathode insertion material.

Item Type: Journal Article
Publication: Materials Today Chemistry
Publisher: Elsevier Ltd
Additional Information: The copyright for this article belongs to Elsevier Ltd.
Keywords: Ionic conductivity; Iron compounds; Lithium compounds; Lithium-ion batteries; Manganese compounds; Metal ions; Molybdenum compounds; Redox reactions; Sodium compounds; Sodium-ion batteries; Sulfur compounds; X ray photoelectron spectroscopy, Alluaudite; Battery; High-voltages; Insertion materials; Large-scales; Molybdate; New high; Novel cathode; Sodium battery; Sodium ion batteries, Cathodes
Department/Centre: Division of Chemical Sciences > Materials Research Centre
Date Deposited: 31 Jan 2023 07:03
Last Modified: 31 Jan 2023 07:03
URI: https://eprints.iisc.ac.in/id/eprint/79618

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