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A new high voltage alluaudite sodium battery insertion material

Journal Article · · Materials Today Chemistry
 [1];  [1];  [1];  [2];  [3];  [1];  [4];  [5];  [6]
  1. Indian Institute of Science, Bangalore (India)
  2. Arizona State Univ., Tempe, AZ (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. National Univ. of Singapore (Singapore)
  4. Univ. of Paris-Sud, Orsay (France). Inst. de Chimie Moleculaire et Materiaux d'Orsay (ICMMO); Centre National de la Recherche Scientifique (CNRS) (France); Université Paris-Saclay, Orsay (France)
  5. Arizona State Univ., Tempe, AZ (United States)
  6. Indian Institute of Science, Bangalore (India); Helmholtz Institute Ulm (HIU) (Germany); Karlsruhe Inst. of Technology (KIT) (Germany)
+ Show Author Affiliations

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. Finally, it benchmarks Na3.36Co1.32(MoO4)3 as a novel electrochemically active Mo-based alluaudite-type polyanionic cathode insertion material.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Science and Engineering Research Board (SERB)
Grant/Contract Number:
AC05-00OR22725; SC0021987
OSTI ID:
1908072
Journal Information:
Materials Today Chemistry, Journal Name: Materials Today Chemistry Journal Issue: 2023 Vol. 27; ISSN 2468-5194
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

25 ENERGY STORAGE
alluaudite
batteries
cathodes
high voltage
ionic conductivity
molybdates