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A novel acetic acid induced Na-rich Prussian blue nanocubes with iron defects as cathodes for sodium ion batteries

Abstract

Prussian blue cathode holds great potential for sodium-ion batteries in view of its high gravimetric capacity, facile synthetic procedure and low cost. The main challenges for Prussian blue are the structural degradation caused by [Fe(CN)6] vacancies and coordinated water in its lattice, and low average voltage due to insufficiently activating low-spin FeLS(C) redox-couple reactions. Here, Na-enriched Prussian blue with low coordinated water and free [Fe(CN)6] vacancies has been successfully synthesized by defect engineering, using acetic acid as an iron defect inducer. In particular, Na-rich Na3.27Fe0.35[Fe(CN)6]·0.85H2O nanocubes with hole centres, low amount of coordinated water and free [Fe(CN)6] vacancies exhibit a high specific capacity, impressive cycling stability and good Coulombic efficiency. This Na-rich material shows a low charge-transfer resistance (201.1 Ω), a high Na+ apparent diffusion coefficient (3.56×10-11 cm2 s-1) and an additional capacity contribution at approximately 4.1 V, demonstrating the sufficient activation of low-spin FeLS(C) redox couples in the Na-involved reactions. The Na3.27Fe0.35[Fe(CN)6]·0.85H2O cathode undergoes a reversible redox reaction, which converts the structure from cubic Na2Fe0.35[Fe(CN)6] to rhombohedral Na3.24Fe0.35[Fe(CN)6]. More significantly, this work for the first time realizes the rational composition and architecture design of the Prussian blue materials by defect engineering for a broad range of potential applications.

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Publication details

The article was received on 21 Feb 2019, accepted on 09 Apr 2019 and first published on 09 Apr 2019


Article type: Paper
DOI: 10.1039/C9TA01965K
Citation: J. Mater. Chem. A, 2019, Accepted Manuscript

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    A novel acetic acid induced Na-rich Prussian blue nanocubes with iron defects as cathodes for sodium ion batteries

    L. Li, P. Nie, Y. Chen and J. Wang, J. Mater. Chem. A, 2019, Accepted Manuscript , DOI: 10.1039/C9TA01965K

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