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Tuning the electron transport behavior at Li/LATP interface for enhanced cyclability of solid-state Li batteries

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Abstract

An interlayer is usually employed to tackle the interfacial instability issue between solid electrolytes (SEs) and Li metal caused by the side reaction. However, the failure mechanism of the ionic conductor interlayers, especially the influence from electron penetration, remains largely unknown. Herein, using Li1.3Al0.3Ti1.7(PO4)3 (LATP) as the model SE and LiF as the interlayer, we use metal semiconductor contact barrier theory to reveal the failure origin of Li/LiF@LATP interface based on the calculation results of density functional theory (DFT), in which electrons can easily tunnel through the LiF grain boundary with F vacancies due to its narrow barrier width against electron injection, followed by the reduction of LATP. Remarkably, an Al-LiF bilayer between Li/LATP is found to dramatically promote the interfacial stability, due to the highly increased barrier width and homogenized electric field at the interface. Consequently, the Li symmetric cells with Al-LiF bilayer can exhibit excellent cyclability of more than 2,000 h superior to that interlayered by LiF monolayer (∼ 860 h). Moreover, the Li/Al-LiF@LATP/LiFePO4 solid-state batteries deliver a capacity retention of 83.2% after 350 cycles at 0.5 C. Our findings emphasize the importance of tuning the electron transport behavior by optimizing the potential barrier for the interface design in high-performance solid-state batteries.

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Acknowledgements

This research was supported by the National Natural Science Foundation of China (Nos. 52072323, 52172240, and 11874307), Natural Science Foundation of Jiangxi Province (No. 20192ACBL20048), Natural Science Foundation of Jiangsu Province (No. BK20200800), Scientific Research Project of Fujian Provincial Department of Education (No. JAT191150), the Fundamental Research Funds for the Central Universities (No. 20720200075), and the Double-First Class Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University.

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  1. Linshan Luo, Feng Zheng, Haowen Gao, and Chaofei Lan contributed equally to this work.

Authors and Affiliations

  1. Department of Physics, Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Key Laboratory of Low Dimensional Condensed Matter Physics (Department of Education of Fujian Province), Jiujiang Research Institute, Xiamen University, Xiamen, 361005, China

    Linshan Luo, Feng Zheng, Chaofei Lan, Wei Huang, Ziqi Zhang, Pengfei Su, Shengshi Guo, Guangyang Lin, Jianfang Xu, Jianyuan Wang, Jun Li, Cheng Li, Shunqing Wu & Songyan Chen

  2. State Key Lab of Physical Chemistry of Solid Surfaces, College of Materials, Xiamen University, Xiamen, 361005, China

    Haowen Gao, Zhefei Sun, Qiaobao Zhang & Ming-Sheng Wang

  3. College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China

    Xiang Han

  4. Western Digital Corporation, 951 Sandisk Dr, Milpitas, CA, 95035, USA

    Peng Wang

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  1. Linshan Luo
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  2. Feng Zheng
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Correspondence to Shunqing Wu, Ming-Sheng Wang or Songyan Chen.

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Luo, L., Zheng, F., Gao, H. et al. Tuning the electron transport behavior at Li/LATP interface for enhanced cyclability of solid-state Li batteries. Nano Res. 16, 1634–1641 (2023). https://doi.org/10.1007/s12274-022-5136-2

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