@article{b427c23b26a949efb2060ab0efda129e,
title = "A new high voltage alluaudite sodium battery insertion material",
abstract = "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.",
keywords = "Alluaudite, Batteries, Cathodes, High-voltage, Ionic conductivity, Molybdates",
author = "P. Barman and Jha, {P. K.} and A. Chaupatnaik and K. Jayanthi and Rao, {R. P.} and {Sai Gautam}, G. and S. Franger and A. Navrotsky and P. Barpanda",
note = "Funding Information: The first author (PB) acknowledges the Department of Science and Technology (DST) for an INSPIRE fellowship (IF180127). PKJ and ACP are grateful to the Ministry of Human Resource Development (MHRD, Government of India) for fellowship. KJ and AN acknowledge financial support from the U.S. Department of Energy Office of Basic Energy Sciences (grant DE-SC0021987). GSG acknowledges the financial support from the Science and Engineering Research Board (SERB) of the DST, under the sanction number (IPA/2021/000007). We acknowledge the computational resources provided by the Supercomputer Education and Research Centre, IISc, for enabling some of the density functional theory calculations showcased in this work. The current work was financially supported by the Technology Mission Division (Department of Science and Technology, Govt. of India) under Materials for Energy Storage (MES-2018) program (DST/TMD/MES/2K18/207). PB is grateful to the Alexander von Humboldt Foundation (Bonn, Germany) for a 2022 Humboldt fellowship for experienced researchers. This manuscript has been authored by UT-Battelle, LLC under Contract No. DEAC05- 00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). Funding Information: This manuscript has been authored by UT-Battelle, LLC under Contract No. DEAC05- 00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Funding Information: The first author (PB) acknowledges the Department of Science and Technology (DST) for an INSPIRE fellowship (IF180127). PKJ and ACP are grateful to the Ministry of Human Resource Development (MHRD, Government of India) for fellowship. KJ and AN acknowledge financial support from the U.S. Department of Energy Office of Basic Energy Sciences (grant DE-SC0021987 ). GSG acknowledges the financial support from the Science and Engineering Research Board (SERB) of the DST, under the sanction number ( IPA/2021/000007 ). We acknowledge the computational resources provided by the Supercomputer Education and Research Centre, IISc, for enabling some of the density functional theory calculations showcased in this work. The current work was financially supported by the Technology Mission Division (Department of Science and Technology, Govt. of India) under Materials for Energy Storage (MES-2018) program ( DST/TMD/MES/2K18/207 ). PB is grateful to the Alexander von Humboldt Foundation (Bonn, Germany) for a 2022 Humboldt fellowship for experienced researchers. Publisher Copyright: {\textcopyright} 2022 Elsevier Ltd",
year = "2023",
month = jan,
doi = "10.1016/j.mtchem.2022.101316",
language = "English (US)",
volume = "27",
journal = "Materials Today Chemistry",
issn = "2468-5194",
publisher = "Elsevier Limited",
}