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α-CuV2O6 Nanowires: Hydrothermal Synthesis and Primary Lithium Battery Application

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Key Laboratory of Energy-Material Chemistry (Tianjin) and Engineering Research Center of Energy Storage & Conversion (Ministry of Education), Chemistry College, Nankai University, Tianjin 300071, People’s Republic of China
Cite this: J. Am. Chem. Soc. 2008, 130, 15, 5361–5367
Publication Date (Web):March 26, 2008
https://doi.org/10.1021/ja800109u
Copyright © 2008 American Chemical Society

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    Abstract

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    We report on the synthesis, characterization, and electrochemical lithium intercalation of α-CuV2O6 nanowires, mesowires, and microrods that were prepared through a facile hydrothermal route. The diameters of the as-synthesized α-CuV2O6 nanowires, mesowires, and microrods were about 100 nm, 400 nm, and 1 µm, respectively. It was found that by simply controlling the hydrothermal reaction parameters, such as the reagent concentration and the dwell time, the transformation of microrods to nanowires was readily achieved via a “ripening−splitting” mechanism. Electrochemical measurements revealed that the as-prepared α-CuV2O6 nanowires and mesowires displayed high discharge capacities (447−514 mAh/g at 20 mA/g and 37 °C) and excellent high-rate capability. In particular, the α-CuV2O6 nanowires showed capacities much higher than those of α-CuV2O6 mesowires, microrods, and bulk particles. The mechanisms for the electrochemical lithium intercalation into the α-CuV2O6 nanowires were also discussed. From the Arrhenius plot of lithium intercalation into α-CuV2O6 nanowires, the activation energies were calculated to be 39.3 kJ/mol at 2.8 V (low lithium uptake) and 35.7 kJ/mol at 2.3 V (high lithium uptake). This result indicates that the α-CuV2O6 nanowires are promising cathode candidates for primary lithium batteries used in long-term implantable cardioverter defibrillators (ICD).

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    The illustration of the working principle and configuration of the implantable cardioverter defibrillators (ICD); the picture of the experimental setup; SEM images of α-CuV2O6 synthesized from different concentrations of the reactant; SEM images of α-CuV2O6 bulk particles obtained from solid-state reaction; XRD patterns and SEM images of α-CuV2O6 obtained at different reaction time; illustration of the possible phase transformation in the synthesis of α-CuV2O6 nanowires; discharge curves for the electrodes made from the as-prepared α-CuV2O6 nanowires and bulk particles at the current densities of 40 and 80 mA/g and the temperature of 37 °C; discharge curves for the electrode made from the as-prepared α-CuV2O6 nanowires at the current densities of 20 mA/g after equilibrated at 37 °C for 2 months; cyclic voltammogram (CV) of the electrode made form the α-CuV2O6 nanowires in the first cycle at a scan rate of 1.0 mV/s and the temperature of 37 °C; the survey XPS spectra of the electrode made from the α-CuV2O6 nanowires at different discharge states; XRD patterns and SEM images of the electrodes with α-CuV2O6 nanowires and bulk particles after discharging to the cutoff voltage of 2.0 V; the equivalent circuit for the electrochemical impedance spectrum; table of charge-transfer resistance (Rct) and exchange current (i0) of α-CuV2O6 nanowires and bulk particels measured at different discharge states and temperatures. This material is available free of charge via the Internet at http://pubs.acs.org.

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