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Hollow single-crystalline octahedra of hydrated/dehydrated hydroxyl ferric phosphate and crystal water enhanced electrochemical properties of the hydrated sample for the reversible lithiation-delithiation

Abstract

Solution-based preparation of a polyanionic inorganic compound sometimes introduces structural water into its chemical composition, but the positive effect of structural water on the electrochemical properties of hydrated sample is still ambiguous so far. Herein, hollow single-crystalline octahedra of hydrated hydroxyl ferric phosphate (Fe5(PO4)4(OH)3·2H2O, edge length ~1.0 m, a known orthorhombic phase) and its dehydrated counterpart (Fe5(PO4)4(OH)3, edge length ~0.9 m, a fitting orthorhombic phase) are uniformly prepared for the first time, facilitating the comparative studies on their structural and electrochemical properties. As a lithium-ion battery cathode within 1.5-4.5 V vs. Li+/Li, the hydrated sample can deliver an initial discharge capacity of 176.6 mAh g-1 at 5 mA g-1, which is close to the theoretical value of 180.0 mAh g-1. By comparison, no matter how many is charge-discharge current rate, reversible capacity of the hydrated microcrystallites in each cycle is much higher than that of the dehydrated counterparts. In a word, it is the solvent of 1,2-propanediol that mainly determines the hydro-/solve-thermal formation of Fe5(PO4)4(OH)3·2H2O hollow single-crystalline octahedra, and it is the presence of crystal water that modifies the cell parameters of orthorhombic lattice and promotes the reversible lithiation-delithiation capability of microcrystallites.

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Publication details

The article was received on 05 Mar 2019, accepted on 07 Apr 2019 and first published on 09 Apr 2019


Article type: Paper
DOI: 10.1039/C9CE00310J
Citation: CrystEngComm, 2019, Accepted Manuscript

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    Hollow single-crystalline octahedra of hydrated/dehydrated hydroxyl ferric phosphate and crystal water enhanced electrochemical properties of the hydrated sample for the reversible lithiation-delithiation

    Q. Shen, X. Ma, H. Jiang, F. Tian, Y. Ti and M. Zhang, CrystEngComm, 2019, Accepted Manuscript , DOI: 10.1039/C9CE00310J

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