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Defect-mediated Jahn-Teller effect in layered LiNiO2

层状LiNiO2中的缺陷调制Jahn-Teller效应

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摘要

LiNiO2 (LNO)基态的晶体结构和电子结构长期以来存在着实验与理论计算不一致的争议. 实验上观测到LNO是空间群为\(R\overline3m\)的半导体并且有局部的Jahn-Teller (JT)畸变, 但理论计算却表明它是处于亚稳态的金属并且没有任何的JT畸变. 本文基于杂化密度泛函理论HSE06, 首次模拟了与实验等同浓度(~3%)的Ni/Li反位缺陷对LNO的影响, 发现缺陷能够有效调控LNO中的JT效应. 在LNO中引入Ni/Li反位缺陷后, 其结构发生了局部的JT畸变, 并且其带隙值约为0.5 eV, 这些计算结果都和实验现象非常吻合. Ni/Li反位通过粒径效应和库伦作用, 既能诱发JT畸变, 又能阻碍畸变之间的协同作用, 避免相变到C2/m, 而只产生局部的JT畸变. 本文提出了一种新的策略来解释LNO基态晶体结构和电子结构长期以来的争议, 对推动富镍层状材料的设计和应用具有重要意义.

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Acknowledgements

The study was financially supported by the Starting Fund of Peking University Shenzhen Graduate School and Fujian Science & Technology Innovation Laboratory for Energy Devices of China (21C-LAB), and the National Natural Science Foundation of China (12174162). The authors thank Prof. Qihang Liu from Southern University of Science and Technology for the helpful discussions.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen, 518055, China

    Weicheng Lin  (林伟成), Yaokun Ye  (叶耀坤), Taowen Chen  (陈涛文), Feng Pan  (潘锋) & Jiaxin Zheng  (郑家新)

  2. Fujian Science & Technology Innovation Laboratory for Energy Devices of China (21C-LAB), Ningde, 352100, China

    Yao Jiang  (蒋耀), Chuying Ouyang  (欧阳楚英) & Jiaxin Zheng  (郑家新)

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  1. Weicheng Lin  (林伟成)
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Contributions

Author contributions Zheng J supervised this work. Lin W and Ye Y designed the idea and wrote the paper. Lin W, Ye Y, and Chen T performed the data analysis and visualization. All authors contributed to the general discussion and conceptualization.

Corresponding authors

Correspondence to Feng Pan  (潘锋) or Jiaxin Zheng  (郑家新).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Weicheng Lin received his BSc degree from Northeastern University in 2019. Now he is a master student under the supervision of Prof. Jiaxin Zheng at Peking University. His research interests include computational materials and energy materials.

Yaokun Ye received his BSc degree from Jinan University in 2018. Now he is a PhD candidate under the supervision of Prof. Jiaxin Zheng at Peking University. His research interests include computational materials and energy materials.

Feng Pan is the Chair-Professor, Founding Dean of School of Advanced Materials, Peking University Shenzhen Graduate School. He received his PhD from the Department of P&A Chemistry, University of Strathclyde, Glasgow, U.K., receiving the “Patrick D. Ritchie Prize” for the best PhD in 1994. Prof. Pan has been engaged in the fundamental research and product development of novel optoelectronic and energy storage materials and devices.

Jiaxin Zheng received his PhD in condensed physics from Peking University in 2013. He is currently working as an Associate Professor at the School of Advanced Materials, Peking University. His research interests include computational materials and energy materials.

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Lin, W., Ye, Y., Chen, T. et al. Defect-mediated Jahn-Teller effect in layered LiNiO2. Sci. China Mater. 65, 1696–1700 (2022). https://doi.org/10.1007/s40843-021-1946-9

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  • DOI: https://doi.org/10.1007/s40843-021-1946-9

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