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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 reversible lithiation–delithiation

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Abstract

The solution-based preparation of a polyanionic inorganic compound sometimes introduces structural water into its chemical composition; however, to date, the positive impact of this structural water on the electrochemical properties of the hydrated sample is still ambiguous. Herein, hollow single-crystalline octahedra of hydrated hydroxyl ferric phosphate (Fe5(PO4)4(OH)3·2H2O; edge length: ∼1.0 μm; a known orthorhombic phase) and its dehydrated counterpart (Fe5(PO4)4(OH)3; edge length: ∼0.9 μm; a fitting orthorhombic phase) were uniformly prepared for the first time, facilitating 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 the initial discharge capacity of 176.6 mA h g−1 at 5 mA g−1, which is close to the theoretical value of 180.0 mA h g−1. By comparison, regardless of the charge–discharge current rate, the reversible capacity of the hydrated microcrystallites in each cycle was much higher than that of the dehydrated counterparts. In other words, the 1,2-propanediol solvent mainly determines the hydro-/solvothermal 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 the orthorhombic lattice and promotes the reversible lithiation–delithiation capability of microcrystallites.

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

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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, Advance Article

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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 reversible lithiation–delithiation

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

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