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High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi)3O4 (X = Fe, Cr) for high-performance anode of Li-ion batteries

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Abstract

High entropy oxides (HEOs), as a new type of single-phase multielement solid solution materials, have shown many attractive features and promising application prospect in the energy storage field. Herein, six-element HEOs (CoNiZnFeMnLi)3O4 and (CoNiZnCrMnLi)3O4 with spinel structure are successfully prepared by conventional solid-phase method and present outstanding lithium storage performances due to the synergy effect of various electrochemically active elements and the entropy stabilization. By contrast, (CoNiZnFeMnLi)3O4 delivers higher initial discharge specific capacity of 1104.3 mAh·g−1, better cycle stability (84% capacity retention after 100 cycles at 100 mA·g−1) and rate performance (293 mAh·g−1 at 2000 mA·g−1) in the half-cell. Moreover, the full-cell assembled with (CoNiZnFeMnLi)3O4 and LiCoO2 provides a reversible specific capacity of 260.2 mAh·g−1 after 100 cycles at 500 mA·g−1. Ex situ X-ray diffraction reveals the electrochemical reaction mechanism of HEOs (CoNiZnFeMnLi)3O4, and the amorphous phase and the large amount of oxygen vacancies were obtained after the initial discharge process, which are responsible for the excellent cycle and rate performance. This research puts forward fresh insights for the development of advanced energy storage materials for high-performance batteries.

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摘要

作为一种新型单相多主元固溶体材料, 高熵氧化物具有诸多优异的特性, 在储能领域应用潜力巨大。此文通过传统的固相法成功制备出了两种六元尖晶石结构的高熵氧化物(CoNiZnFeMnLi)3O4和(CoNiZnCrMnLi)3O4。基于多重活性元素的协同作用以及熵稳定的机制, 所制备的材料均表现出了优异的储锂性能。相比而言, 在半电池测试中, (CoNiZnFeMnLi)3O4 的电化学性能表现更为优异, 其首次放电比容量高达1104.3 mAh·g-1, 在100 mA·g-1电流密度下经100次循环后容量保持率可达84% , 同时在2000 mA·g-1的大电流充放下, 容量仍能保持在293 mAh·g-1。此外, 我们以LiCoO2为正极, (CoNiZnFeMnLi)3O4为负极组装为全电池进行测试, 在500 mA·g-1的电流密度下经100周循环, 电池可获得260.2 mAh·g-1的可逆比容量。利用非原位XRD对(CoNiZnFeMnLi)3O4材料的电化学反应机制进行了分析, 研究发现, 在首次放电后, 材料向非晶相转变, 同时出现了大量的氧空位, 这一现象可以合理的解释其优异的循环和倍率性能。本研究为高性能电池用储能材料的开发提供了新的视角和思路。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 51902046, 51871046, 52071073, 51771046 and 51971055), Natural Science Foundation of Hebei Province (Nos. E2019501097, E2018501091 and E2020501004), the Science and Technology Project of Hebei Province (No. 15271302D). The Fundamental Research Funds for the Central Universities (N2123032).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Northeastern University, Shenyang, 110819, China

    Kang-Hui Tian, Chan-Qin Duan, Qun Ma, Xing-Long Li, Zhi-Yuan Wang, Hong-Yu Sun, Shao-Hua Luo, Dan Wang & Yan-Guo Liu

  2. Key Laboratory of Dielectric and Electrolyte Functional Materials, Qinhuangdao, 066004, China

    Zhi-Yuan Wang & Yan-Guo Liu

  3. School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao, 066004, China

    Zhi-Yuan Wang

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  1. Kang-Hui Tian
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Tian, KH., Duan, CQ., Ma, Q. et al. High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi)3O4 (X = Fe, Cr) for high-performance anode of Li-ion batteries. Rare Met. 41, 1265–1275 (2022). https://doi.org/10.1007/s12598-021-01872-4

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