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The effect of copper doping in α-MnO2 as cathode material for aqueous Zinc-ion batteries

阴极 循环伏安法 电化学 扫描电子显微镜 介电谱 兴奋剂 材料科学 电解质 分析化学(期刊) 冶金 化学工程 电极 化学 复合材料 色谱法 物理化学 光电子学 工程类
作者
Rong Lan,Evangelos I. Gkanas,Ali Jawad Sahib Sahib,Agata Greszta,Rohit Bhagat,Alexander J. Roberts
出处
期刊:Journal of Alloys and Compounds [Elsevier]
卷期号:992: 174528-174528 被引量:4
标识
DOI:10.1016/j.jallcom.2024.174528
摘要

Copper-doped Manganese Dioxide has been synthesised through a simple hydrothermal method at different doping levels. The synthesised materials have been characterized by X-ray diffraction (XRD), and scanning electron microscopy (SEM) to determine composition, structure, and morphology. All the Cu doped MnO2 are found to be single phased. Their electrochemical properties as cathode for Zinc-ion batteries are studied by cyclic voltammetry (CV), galvano-static charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS), using 3 M ZnSO4 + 0.3 MnSO4 solution as electrolyte. 3.8% Cu doped MnO2 has shown the highest initial capacity of 379.5 mAh g−1 at 0.02 A·g−1, and 304.4 mA h g−1 at 0.5 A g−1, but experienced fast fading with a poor capacity retention of 56.8% after 100 cycles. 7.4% Cu doping gives lower capacity, while 5.9% doping shows a higher discharging capacity (320.0 mAh·g−1 at 0.02 A·g−1 and 269.3 mAh·g−1 at 0.5 A·g−1) and improved stability (85.8% capacity retention after 100 cycles), better than non-doped MnO2 electrode (284.4 mAh g−1 at 0.02 A g−1 and 252.1 mAh·g−1 at 0.5 A g−1, capacity retention 76.7%). The samples show satisfactory capacity and rate capability while the cycling stability is not ideal, which may relate to the needle like morphology and nanoscale particle size. CV tests revealed that the electrochemical process is mainly diffusion controlled. The zinc ion diffusion coefficient is tested to be in the range of 10-12 cm2·s-1 from both CV and EIS tests and showed the same trend in their electrochemical capacity. Doping of Copper in MnO2 reduced the polarization on electrode, improved the electrochemical reversibility, as evidenced by the reduction of the redox peak potential difference from 0.31 to 0.24 V at 1.1 mV·s−1, and from 0.45 V to 0.31 V at 5 mV·s−1. Whilst the cell resistance of non-doped MnO2 increased from 1.78 Ω to 7.39 Ω after cycling, the cell resistances of all Cu-doped cathodes reduced, indicating improved electronic conductivities after cycling. These results indicate that Cu-doping is effective to increase the conductivity of the materials, reduce the polarization during charge and discharge, and improve the cycling stability of MnO2 cathode.
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