Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)3 Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights

Debasmita Dwibedi, Chris D. Ling, Rafael B. Araujo, Sudip Chakraborty, Shanmugha sundaram Duraisamy, Nookala Munichandraiah, Prabeer Barpanda, Rajeev Ahuja

Research output: Contribution to journalArticle

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Abstract

Exploring future cathode materials for sodium-ion batteries, alluaudite class of Na2FeII2(SO4)3 has been recently unveiled as a 3.8 V positive insertion candidate (Barpanda et al. Nat. Commun. 2014, 5, 4358). It forms an Fe-based polyanionic compound delivering the highest Fe-redox potential along with excellent rate kinetics and reversibility. However, like all known SO4-based insertion materials, its synthesis is cumbersome that warrants careful processing avoiding any aqueous exposure. Here, an alternate low temperature ionothermal synthesis has been described to produce the alluaudite Na2+2xFeII2-x(SO4)3. It marks the first demonstration of solvothermal synthesis of alluaudite Na2+2xMII2-x(SO4)3 (M = 3d metals) family of cathodes. Unlike classical solid-state route, this solvothermal route favors sustainable synthesis of homogeneous nanostructured alluaudite products at only 300 °C, the lowest temperature value until date. The current work reports the synthetic aspects of pristine and modified ionothermal synthesis of Na2+2xFeII2-x(SO4)3 having tunable size (300 nm ∼5 μm) and morphology. It shows antiferromagnetic ordering below 12 K. A reversible capacity in excess of 80 mAh/g was obtained with good rate kinetics and cycling stability over 50 cycles. Using a synergistic approach combining experimental and ab initio DFT analysis, the structural, magnetic, electronic, and electrochemical properties and the structural limitation to extract full
LanguageEnglish
Pages6982-6991
JournalACS Applied Materials & Interfaces
Volume8
Issue number11
DOIs
Publication statusPublished - 23 Mar 2016

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Sodium
Electric potential
Cathodes
Kinetics
Electrochemical properties
Discrete Fourier transforms
Electronic properties
Structural properties
Magnetic properties
Demonstrations
Metals
Ions
Temperature
Processing

Cite this

Dwibedi, Debasmita ; Ling, Chris D. ; Araujo, Rafael B. ; Chakraborty, Sudip ; Duraisamy, Shanmugha sundaram ; Munichandraiah, Nookala ; Barpanda, Prabeer ; Ahuja, Rajeev. / Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)3 Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights. In: ACS Applied Materials & Interfaces. 2016 ; Vol. 8, No. 11. pp. 6982-6991.
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Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)3 Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights. / Dwibedi, Debasmita; Ling, Chris D.; Araujo, Rafael B.; Chakraborty, Sudip; Duraisamy, Shanmugha sundaram; Munichandraiah, Nookala; Barpanda, Prabeer; Ahuja, Rajeev.

In: ACS Applied Materials & Interfaces, Vol. 8, No. 11, 23.03.2016, p. 6982-6991.

Research output: Contribution to journalArticle

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AU - Dwibedi, Debasmita

AU - Ling, Chris D.

AU - Araujo, Rafael B.

AU - Chakraborty, Sudip

AU - Duraisamy, Shanmugha sundaram

AU - Munichandraiah, Nookala

AU - Barpanda, Prabeer

AU - Ahuja, Rajeev

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AB - Exploring future cathode materials for sodium-ion batteries, alluaudite class of Na2FeII2(SO4)3 has been recently unveiled as a 3.8 V positive insertion candidate (Barpanda et al. Nat. Commun. 2014, 5, 4358). It forms an Fe-based polyanionic compound delivering the highest Fe-redox potential along with excellent rate kinetics and reversibility. However, like all known SO4-based insertion materials, its synthesis is cumbersome that warrants careful processing avoiding any aqueous exposure. Here, an alternate low temperature ionothermal synthesis has been described to produce the alluaudite Na2+2xFeII2-x(SO4)3. It marks the first demonstration of solvothermal synthesis of alluaudite Na2+2xMII2-x(SO4)3 (M = 3d metals) family of cathodes. Unlike classical solid-state route, this solvothermal route favors sustainable synthesis of homogeneous nanostructured alluaudite products at only 300 °C, the lowest temperature value until date. The current work reports the synthetic aspects of pristine and modified ionothermal synthesis of Na2+2xFeII2-x(SO4)3 having tunable size (300 nm ∼5 μm) and morphology. It shows antiferromagnetic ordering below 12 K. A reversible capacity in excess of 80 mAh/g was obtained with good rate kinetics and cycling stability over 50 cycles. Using a synergistic approach combining experimental and ab initio DFT analysis, the structural, magnetic, electronic, and electrochemical properties and the structural limitation to extract full

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EP - 6991

JO - ACS Applied Materials and Interfaces

T2 - ACS Applied Materials and Interfaces

JF - ACS Applied Materials and Interfaces

SN - 1944-8244

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