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Boosting the cycle and rate performance of Li1.2Mn0.54Ni0.13Co0.13O2 via single-crystal structure design

单晶结构设计提高Li1.2Mn0.54Ni0.13Co0.13O2的循环和倍率性能

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Abstract

Lithium-rich layered oxides (LROs) are regarded as promising cathode materials to build high-energy-density lithium-ion batteries (LIBs). However, conventional polycrystalline LROs suffer from irreversible structure changes and slow interfacial kinetics, leading to poor cycle and rate performance. Here we propose a polyvinylpyrrolidone (PVP)-assisted co-precipitation method to prepare single-crystal LRO (Li1.2Mn0.54Ni0.13Co0.13O2) nanosheets. PVP can adsorb on a specific crystal plane during precursor formation to obtain ideal nanosheet morphology. This method is simple, low-cost and easy to scale up. The prepared single-crystal nanosheets feature continuous lattice and no grain boundary inside, which shorten the path of Li+ intercalation/deintercalation and improve the electrode reaction kinetics. The single-crystal structure also inhibits the irreversible phase transformation from the layered phase to the spinel phase and the formation of cracks owing to suitable particle size, stabilizing the layered structure. As a result, the prepared single-crystal Li1.2Mn0.54-Ni0.13Co0.13O2 nanosheets deliver a reversible capacity of 254.5 mA h g−1 at a rate of 0.1 C and good cycling stability with a capacity retention of 71.9% after 1000 cycles at a high rate of 5 C. This work provides a facile method to prepare nano-sized single-crystal LRO materials for improving the cycle and rate performance of LIBs.

摘要

富锂层状氧化物是构筑高能量密度锂离子电池富有潜力的正极材料. 然而, 由于不可逆的结构变化和缓慢的界面动力学, 传统的多晶富锂层状氧化物正极材料循环和倍率性能较差. 本文提出了一种聚乙烯基吡咯烷酮(PVP-K30)辅助共沉淀制备单晶Li1.2Mn0.54Ni0.13Co0.13O2纳米片的方法. 这种方法操作简单、成本低且便于放大生产. 所制备的单晶纳米片内部晶格连续且无晶界, 缩短了Li+的嵌入/脱嵌路径, 加快了电极反应动力学过程. 单晶结构还能抑制层状相向尖晶石相的不可逆相变和颗粒内部裂纹的形成, 起到稳定层状结构的作用. 电化学测试结果表明, 所制备的Li1.2Mn0.54Ni0.13Co0.13O2单晶纳米片在0.1 C倍率下的可逆容量为254.5 mA h g−1, 在5 C高倍率下循环1000次后容量保持率为71.9%. 这种简单的制备纳米片单晶材料的方法为提高富锂层状氧化物正极材料的循环性能和倍率性能提供了新的思路.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22121005, 22020102002 and 21835004) and the Frontiers Science Center for New Organic Matter of Nankai University (63181206). We also appreciate Tianjin Lishen New Energy Technology Co., Ltd. for financial support

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Authors and Affiliations

  1. Renewable Energy Conversion and Storage Center (RECAST), Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin, 300071, China

    Zhenkun Hao  (郝振坤), Xiaoxia Gou  (苟晓夏), Zhuo Yang  (杨卓), Zhimeng Hao  (郝志猛), Gaojing Yang  (杨高靖), Yong Lu  (卢勇), Qing Zhao  (赵庆), Zhenhua Yan  (严振华) & Jun Chen  (陈军)

  2. Tianjin Lishen New Energy Technology Co., Ltd., Tianjin, 300450, China

    Hongyun Ma  (马洪运), Huifen Jin  (金慧芬) & Qiang Zhang  (张强)

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  1. Zhenkun Hao  (郝振坤)
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  2. Xiaoxia Gou  (苟晓夏)
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  4. Zhuo Yang  (杨卓)
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  11. Zhenhua Yan  (严振华)
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  12. Jun Chen  (陈军)
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Contributions

Chen J and Yan Z proposed the idea of this work. Hao Z and Gou X conducted the experiments. Hao Z and Gou X wrote the manuscript with support from Chen J, Yan Z, Zhao Q, Ma H, Lu Y, Jin H, and Zhang Q. Hao Z, Yang Z and Yang G organized the figures. The manuscript was discussed and revised by all authors.

Corresponding authors

Correspondence to Zhenhua Yan  (严振华) or Jun Chen  (陈军).

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The authors declare that they have no conflict of interest.

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Zhenkun Hao received his BS degree in applied chemistry from Qingdao University of Science and Technology (2020). He is currently a master candidate at the Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University under the supervision of Prof. Jun Chen. His research activities focus on high-voltage cathode materials in LIBs.

Zhenhua Yan is an associate professor at the College of Chemistry, Nankai University. He obtained his PhD from Nankai University in 2018 under the supervision of Prof. Fangyi Cheng. Then, he joined the College of Chemistry, Nankai University as a master’s supervisor and assistant of Prof. Jun Chen. His research interests involve the design and synthesis of nanomaterials for batteries and electrocatalysis.

Jun Chen obtained his BS and MS degrees from Nankai University (Tianjin) in 1989 and 1992, respectively. He received his PhD degree from the University of Wollongong (Australia) in 1999. His research mainly focuses on the synthetic chemistry of inorganic and organic solid functional materials and the development of batteries.

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Hao, Z., Gou, X., Ma, H. et al. Boosting the cycle and rate performance of Li1.2Mn0.54Ni0.13Co0.13O2 via single-crystal structure design. Sci. China Mater. 66, 3424–3432 (2023). https://doi.org/10.1007/s40843-023-2494-1

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