Fluorine Compounds, Inorganic, Oxygen

A convenient approach for a controlled and high-yield synthesis of copper-deficient Cu 3−x P (0.1 < x < 0.7) is reported that makes use of ionic liquids with highly nucleophilic "naked" halide anions. Halide anions drastically enhance the reactivity of the white phosphorus precursor and kinetically disfavour the formation of phosphorus-rich side products. Cu 3−x P shows a high degree of tolerance for cation vacancies without mayor structural reorganisation, as evidenced by X-ray diffraction and solid-state nuclear magnetic resonance spectroscopy. Measurements of the electric properties reveal that Cu 3−x P is a bad metallic p-type conductor. The resistivity is composition-dependent and displays a distinct anomaly from a phase transition, leading to the discovery and structural characterisation of two hitherto unknown low temperature polymorphs. Electrochemical evaluation of copper-deficient Cu 3−x P as anode material for lithium ion batteries reveals a drastic change in the cycling mechanism leading to an increase of the initial capacities by about 70 %. This work gives a comprehensive insight into the chemical and structural features of copper-deficient Cu 3−x P and should lead to an improved understanding of its properties, not only for battery applications.

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Resource-Efficient High-Yield Ionothermal Synthesis of Microcrystalline Cu_3–xP

Wolff¹,

Pallmann²,

Boucher³

et al. 2016

Inorg. Chem.

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Polycrystalline Cu3-xP was successfully synthesized in different ionic liquids comprising imidazolium and phosphonium cations. The reaction of elemental copper and red phosphorus in trihexyltetradecylphosphonium chloride at 200 °C led to single-phase Cu3-xP (x = 0.05) within 24 h with a quantitative yield (99%). Liquid-state nuclear magnetic resonance spectroscopy of the ionic liquids revealed degeneration of the imidazolium cations under the synthesis conditions, while phosphonium cations remain stable. The solid products were characterized with X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and elemental analysis. A reinvestigation of the electronic transport properties of Cu2.95(4)P showed metallic behavior for the bulk material. The formation of CuP2 during the synthesis of phosphorus-rich Cu3-xP (x ≥ 0.1) was observed.

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Fluorine Compounds, Inorganic, Oxygen

Cited by 5 publications

References 61 publications

Method for Mitigating Electrochemical Migration on Printed Circuit Boards

Method for Mitigating Electrochemical Migration on Printed Circuit Boards

Low-Temperature Tailoring of Copper-Deficient Cu_3–xP—Electric Properties, Phase Transitions, and Performance in Lithium-Ion Batteries

Resource-Efficient High-Yield Ionothermal Synthesis of Microcrystalline Cu_3–xP

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Fluorine Compounds, Inorganic, Oxygen

Cited by 5 publications

References 61 publications

Method for Mitigating Electrochemical Migration on Printed Circuit Boards

Method for Mitigating Electrochemical Migration on Printed Circuit Boards

Low-Temperature Tailoring of Copper-Deficient Cu3–xP—Electric Properties, Phase Transitions, and Performance in Lithium-Ion Batteries

Resource-Efficient High-Yield Ionothermal Synthesis of Microcrystalline Cu3–xP

Contact Info

Product

Resources

About

Low-Temperature Tailoring of Copper-Deficient Cu_3–xP—Electric Properties, Phase Transitions, and Performance in Lithium-Ion Batteries

Resource-Efficient High-Yield Ionothermal Synthesis of Microcrystalline Cu_3–xP