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High-performance sodium storage for cobalt phosphide composite array electrodes

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Abstract

Transition metal phosphides hold great potential as sodium-ion batteries anode materials owing to their high theoretical capacity and modest plateau. However, volume changes and low intrinsic conductivity seriously largely hinder the further development of metal phosphide anodes. The design of phosphide anode materials with reasonable structure is conducive to solving the problems of volume expansion and slow reaction kinetics during the reaction. In this work, a composite material integrating zeolite imidazolate backbone (ZIF) and carbon materials was synthesized by the original growth method. Furthermore, by the oxidation-phosphating process, CoP nanoarray composites riveted to carbon fiber (CoP@CF) were obtained. In the CoP@CF, CoP nanoparticles are uniformly distributed on ZIF-derived carbon, reducing agglomeration and volume change during cycling. CF also provides a highly conductive network for the active material, improving the electrode kinetics. Therefore, when evaluated as an anode for sodium-ion batteries, CoP@CF electrode displays enhanced reversible capacity (262 mAh·g−1 at 0.1 A·g−1 after 100 cycles), which is much better than that of pure CF electrode (57 mAh·g−1 at 0.1 A·g−1 after 100 cycles) prepared without the addition of CoP. The rate performance of CoP@CF electrode is also superior to that of pure CF electrode at various current densities from 0.05 to 1 A·g−1. The sodium storage behavior of CoP@CF was revealed by ex-situ X-ray photoelectron spectroscopy, X-ray diffraction, and synchrotron radiation absorption spectroscopy. This method provides a reference for the design and synthesis of anode materials in sodium-ion batteries.

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摘要

因为过渡金属磷化物具有较高的理论比容量和合适的电压平台, 所以在用作钠离子电池负极材料时具有较大的潜力。然而, 体积变化大、本征电导率低的问题严重阻碍了金属磷化物阳极的进一步发展。设计结构合理的磷化物负极材料, 有利于解决反应过程中体积膨胀和反应动力学缓慢等问题。本工作原位合成了一种ZIF与碳材料结合的复合材料。进一步通过氧化-磷化工艺, 获得了铆接在碳纤维上的CoP纳米阵列复合材料 (CoP@CF) 。在CoP@CF中, CoP纳米颗粒均匀分布在ZIF衍生碳上, 有利于减循环过程中的团聚和体积变化。此外, CF为活性材料提供了高导电性网络, 改善了电极动力学。因此, 当作为钠离子电池的负极时, CoP@CF显示出增强的可逆容量 (100次循环后0.1 A g−1时为262 mAh g−1), 远优于未添加CoP的纯CF电极 (100次循环后0.1 A g−1时为57 mAh·g−1) 。在0.05 A g−1至1 A g−1的各种电流密度下, CoP@CF电极的倍率性能也优于纯CF电极。通过准原位X射线光电子能谱、X射线衍射和同步辐射吸收光谱揭示了CoP@CF的储钠行为。本文为钠离子电池负极材料的设计与合成提供了参考。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (No. 52250710161). This work was supported by Beijing Synchrotron Radiation 4B9A Work Station in China.

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Authors and Affiliations

  1. School of Material Science and Engineering, Shaanxi University of Science and Technology, Xi’an, 710021, China

    Man Zhang, Xiao-Xu Liu, Tian-Yi Ji, Yang Li, Da-Wei Sheng, Shao-Dong Li & Pei-Pei Ren

  2. School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, 637371, Singapore

    Ze-Xiang Shen

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Zhang, M., Liu, XX., Ji, TY. et al. High-performance sodium storage for cobalt phosphide composite array electrodes. Rare Met. (2024). https://doi.org/10.1007/s12598-024-02697-7

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