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Nano Research 2023, 16(1): 1634-1641 https://doi.org/10.1007/s12274-022-5136-2
Research Article | Issue | Published: 08 November 2022

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

Show Author's Information Linshan Luo1,§,  Feng Zheng1,§,  Haowen Gao2,§,  Chaofei Lan1,§,  Zhefei Sun2,  Wei Huang1,  Xiang Han3,  Ziqi Zhang1,  Pengfei Su1,  Peng Wang4,  Shengshi Guo1,  Guangyang Lin1,  Jianfang Xu1,  Jianyuan Wang1,  Jun Li1,  Cheng Li1,  Qiaobao Zhang2,  Shunqing Wu1( ),  Ming-Sheng Wang2( ),  Songyan Chen1( )
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
State Key Lab of Physical Chemistry of Solid Surfaces, College of Materials, Xiamen University, Xiamen 361005, China
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
Western Digital Corporation, 951 Sandisk Dr, Milpitas, CA 95035, USA

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

Keywords:
Li metal, solid-state electrolyte, electron transport, LiF, Al, interfacial barrier
Topics:
Magnetic properties
Cite this article:
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 Research, 2023, 16(1): 1634-1641. https://doi.org/10.1007/s12274-022-5136-2
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Abstract Full text Electronic supplementary material About this article

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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Electronic supplementary material
About this article

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

Show Author's information Linshan Luo1,§, Feng Zheng1,§, Haowen Gao2,§, Chaofei Lan1,§, Zhefei Sun2, Wei Huang1, Xiang Han3, Ziqi Zhang1, Pengfei Su1, Peng Wang4, Shengshi Guo1, Guangyang Lin1, Jianfang Xu1, Jianyuan Wang1, Jun Li1, Cheng Li1, Qiaobao Zhang2, Shunqing Wu1( ), Ming-Sheng Wang2( ), Songyan Chen1( )
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
State Key Lab of Physical Chemistry of Solid Surfaces, College of Materials, Xiamen University, Xiamen 361005, China
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China
Western Digital Corporation, 951 Sandisk Dr, Milpitas, CA 95035, USA

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

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.

Keywords: Li metal, solid-state electrolyte, electron transport, LiF, Al, interfacial barrier

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Publication history
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Acknowledgements

Publication history

Received: 14 August 2022
Revised: 20 September 2022
Accepted: 04 October 2022
Published: 08 November 2022
Issue date: January 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

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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