TY - JOUR
T1 - Ionothermal Synthesis of High-Voltage Alluaudite Na2+2xFe2-x(SO4)3 Sodium Insertion Compound: Structural, Electronic, and Magnetic Insights
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
PY - 2016/3/23
Y1 - 2016/3/23
N2 - 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
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
U2 - 10.1021/acsami.5b11302
DO - 10.1021/acsami.5b11302
M3 - Article
SN - 1944-8244
VL - 8
SP - 6982
EP - 6991
JO - ACS Applied Materials & Interfaces
JF - ACS Applied Materials & Interfaces
IS - 11
ER -