Barman, P and Dwibedi, D and Jayanthi, K and Meena, SS and Nagendran, S and Navrotsky, A and Barpanda, P (2022) Aqueous spray-drying synthesis of alluaudite Na2+2xFe2−x(SO4)3 sodium insertion material: studies of electrochemical activity, thermodynamic stability, and humidity-induced phase transition. In: Journal of Solid State Electrochemistry .
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Abstract
In pursuit of high-energy density sodium insertion materials, polyanionic frameworks can be designed with tuneable high-voltage operation stemming from inductive effect. Alluaudite Na2Fe2(SO4)3 polysulfate forms one such earth-abundant compound registering the highest Fe3+/Fe2+ redox potential (ca. 3.8 V vs. Na/Na+). While this SO4-based system exhibits high voltage operation, it is prone to thermal decomposition and moisture attack leading to hydrated derivatives, making its synthesis cumbersome. Also, the Na–Fe–S–O quaternary system is rich with (anhydrous to hydrated) phase transitions. Herein, we demonstrate scalable aqueous-based spray drying synthesis of alluaudite Na2+2xFe2−x(SO4)3 sodium insertion material involving the formation of bloedite Na2Fe(SO4)2·4H2O as an intermediate phase. Moreover, a reversible phase transition from alluaudite to bloedite under controlled conditions of temperature and relative humidity is reported for the first time. Thermochemistry measurements revealed the enthalpies of formation (ΔH°f) of alluaudite and bloedite are exothermic. Hydrated bloedite (ΔH°f = −117.16 ± 1.10 kJ/mol) was found to be significantly more energetically stable than anhydrous alluaudite (ΔH°f = −11.76 ± 1.25 kJ/mol). The calorimetric data support the observed synthesis and transformation (hydration-dehydration) pathways. Spray drying route led to spherical morphology delivering capacity ~80 mAh/g. Spray drying can be extended for rapid economic synthesis of sulfate class of battery materials.
| Item Type: | Journal Article |
|---|---|
| Publication: | Journal of Solid State Electrochemistry |
| Publisher: | Springer Science and Business Media Deutschland GmbH |
| Additional Information: | The copyright for this article belongs to the Authors. |
| Keywords: | Decomposition; Humidity control; Hydration; Iron compounds; Metadata; Phase transitions; Redox reactions; Sodium compounds; Sodium-ion batteries; Spray drying; Sulfur compounds, Alluaudite; Bloedite; Capacity; Cathode; Electrochemical activities; High-voltage operation; Insertion materials; Sodium insertions; Sodium ion batteries; Spray-drying, Metal ions |
| Department/Centre: | Division of Chemical Sciences > Materials Research Centre |
| Date Deposited: | 14 Jul 2022 04:38 |
| Last Modified: | 14 Jul 2022 04:38 |
| URI: | https://eprints.iisc.ac.in/id/eprint/74310 |
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