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Title: 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

Journal Article · · Journal of Solid State Electrochemistry
 [1];  [2];  [3];  [4];  [5];  [3]; ORCiD logo [6]
  1. Indian Institute of Science, Bangalore (India)
  2. Indian Institute of Science, Bangalore (India); Univ. of Tokyo (Japan)
  3. Arizona State Univ., Tempe, AZ (United States)
  4. Bhabha Atomic Research Centre (BARC), Mumbai (India)
  5. Bangalore University (India); Univ. of Cambridge (United Kingdom)
  6. Indian Institute of Science, Bangalore (India); Helmholtz Institut Ulm (HIU) (Germany)
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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.

Research Organization:
Univ. of California, Davis, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC). Basic Energy Sciences (BES); Science and Engineering Research Broad, India (SERB)
Grant/Contract Number:
FG02-03ER46053; ECR/2015/000525
OSTI ID:
1976653
Journal Information:
Journal of Solid State Electrochemistry, Vol. 26, Issue 9; ISSN 1432-8488
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

References (19)

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Off-Stoichiometry in Alluaudite-Type Sodium Iron Sulfate Na 2+2 x Fe 2− x (SO 4 ) 3 as an Advanced Sodium Battery Cathode Material journal April 2015
Sustainable Aqueous Synthesis and Electrochemical Insights on High-Voltage Sodium Alluaudite Insertion Materials journal October 2017
The enthalpy of solution of SRM 1655 (KCl) in H2O journal November 1980
Energetics of the Local Environment of Structure-Directing Agents Influence Zeolite Synthesis journal March 2021
Marinite Li 2 Ni(SO 4 ) 2 as a New Member of the Bisulfate Family of High-Voltage Lithium Battery Cathodes journal July 2021
Na 2.32 Co 1.84 (SO 4 ) 3 as a new member of the alluaudite family of high-voltage sodium battery cathodes journal January 2017
Ionothermal Synthesis of High-Voltage Alluaudite Na 2+2x Fe 2-x (SO 4 ) 3 Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights journal March 2016
Thermodynamic stability and correlation with synthesis conditions, structure and phase transformations in orthorhombic and monoclinic Li 2 M(SO 4 ) 2 (M = Mn, Fe, Co, Ni) polymorphs journal January 2015
Na 2.44 Mn 1.79 (SO 4 ) 3 : a new member of the alluaudite family of insertion compounds for sodium ion batteries journal January 2015
A 3.8-V earth-abundant sodium battery electrode journal July 2014
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries journal April 1997
An alluaudite Na2+2xFe2−x(SO4)3(x=0.2) derivative phase as insertion host for lithium battery journal February 2015
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Pursuit of Sustainable Iron-Based Sodium Battery Cathodes: Two Case Studies journal February 2016
Top-down synthesis of muscle-inspired alluaudite Na 2+2x Fe 2−x (SO 4 ) 3 /SWNT spindle as a high-rate and high-potential cathode for sodium-ion batteries journal January 2016
Influence of relative humidity on the structure and electrochemical performance of sustainable LiFeSO 4 F electrodes for Li-ion batteries journal January 2015
Research Development on Sodium-Ion Batteries journal October 2014

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Related Subjects

25 ENERGY STORAGE
Electrochemistry
sodium-ion battery
cathode
alluaudite
capacity
phase transition