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A strong Lewis acid imparts high ionic conductivity and interfacial stability to polymer composite electrolytes towards all-solid-state Li-metal batteries

强路易斯酸诱导构筑高离子电导率和界面稳定的复合电解质及其全固态锂金属电池

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Abstract

The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy density. However, the low ionic conductivity of solid polymer electrolytes and their unstable electrolyte/electrode interfaces have hindered their widespread utilization. To address these critical challenges, a strong Lewis acid (aluminum fluoride (AlF3)) with dual functionality is introduced into polyethylene oxide) (PEO)-based polymer electrolyte. The AlF3 facilitates the dissociation of lithium salt, increasing the iontransfer efficiency due to the Lewis acid-base interaction; further the in-situ formation of lithium fluoride-rich interfacial layer is promoted, which suppresses the uneven lithium deposition and continuous undesired reactions between the Li metal and PEO matrix. Benefiting from our rational design, the symmetric Li/Li battery with the modified electrolyte exhibits much longer cycling stability (over 3600 h) than that of the pure PEO/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte (550 h). Furthermore, the all-solid-state LiFePO4 full cell with the composite electrolyte displays a much higher Coulombic efficiency (98.4% after 150 cycles) than that of the electrolyte without the AlF3 additive (63.3% after 150 cycles) at a large voltage window of 2.4–4.2 V, demonstrating the improved interface and cycling stability of solid polymer lithium metal batteries.

摘要

开发高性能固态聚合物电解质是高安全、 高比能固态锂金属电池的关键. 然而, 固态聚合物电解质的低离子电导率和不稳定的电解质/电极界面阻碍了其广泛应用. 针对上述关键问题, 本文基于聚环氧乙烷(PEO)基电解质, 引入具有双功能的氟化铝(AlF3)做为添加剂, 以提高复合电解质的离子电导率和界面稳定性. 一方面, AlF3做为一种强 路易斯酸, 在和锂盐阴离子相互作用下可以促进锂盐的解离, 同时可以固定阴离子, 从而提高锂离子传输效率; 另一方面, AlF3在电解质/电极界面可以和锂金属原位反应生成富含LiF的界面层, 从而抑制锂金属的不均匀沉积以及与PEO基体之间持续的副反应. 得益于我们的合理设计, 匹配改性后电解质的Li/Li对称电池可以稳定循环3600 h以上. 同时, 在2.4–4.2 V电压区间内, 匹配复合电解质的全固态LiFePO4全电池在150个循环之后库伦效率比没有AlF3添加剂PEO基电解质大大提升(98.4% vs. 63.3%), 匹配复合固态电解质的固态锂金属电池显示出优异的界面稳定性和循环稳定性.

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Acknowledgements

This work was supported by the research fund of Shenzhen Science and Technology Innovation Committee (SGDX20201103093600003), the University of Macau, Macau SAR (MYRG2018-00079-IAPME and MYRG2019-00115-IAPME), the Science and Technology Development Fund, Macau SAR (0092/2019/A2, 0059/2018/A2, and 009/2017/AMJ), the National Thousand Young Talent plan, and the National Natural Science Foundation of China (21875040 & 21905051).

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Authors and Affiliations

  1. Institute of Applied Physics and Materials Engineering, University of Macau, Avenida da Universidade, Taipa, Macau SAR, 999078, China

    Litong Wang  (王立通), Yunlei Zhong  (仲云雷), Zhaorui Wen  (文钊锐), Chaowei Li  (李朝威), Jingxin Zhao  (赵景新), Mingzheng Ge  (葛明政), Pengfei Zhou  (周鹏飞) & Guo Hong  (洪果)

  2. College of Chemical Engineering, Fuzhou University, Fuzhou, 350116, China

    Yanyan Zhang  (张焱焱) & Yuxin Tang  (汤育欣)

  3. Department of Physics and Chemistry, Faculty of Science and Technology, University of Macau, Avenida da Universidade, Taipa, Macau SAR, 999078, China

    Guo Hong  (洪果)

  4. School of Textile and Clothing, Nantong University, Nantong, 226019, China

    Mingzheng Ge  (葛明政)

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  1. Litong Wang  (王立通)
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Contributions

Author contributions Wang L, Hong G and Tang Y designed the research and wrote the manuscript. Hong G and Tang Y supervised the project and analyzed the data. Wang L, Zhong Y, and Wen Z carried out the experiments and discussions. Li C, Zhao J, Ge M, Zhou P and Zhang Y analyzed the data and refined the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yuxin Tang  (汤育欣) or Guo Hong  (洪果).

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

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

Litong Wang is currently a PhD candidate at the Institute of Applied Physics and Materials Engineering, University of Macau. His research interest focuses on the development of solid-state lithium metal batteries/fast charging electrode materials for electrochemical energy conversion and storage systems.

Yuxin Tang is a Professor at the College of Chemical Engineering, Fuzhou University. He obtained his BSc and MSc degrees from Nanjing University of Aeronautics and Astronautics in 2006 and 2009, respectively, and graduated from Nanyang Technological University (NTU) with a PhD degree in materials science (2013). After postdoctoral training in NTU, he joined the Institute of Applied Physics and Materials Engineering, University of Macau as an assistant professor in 2018. His research interests are the development of extreme energy storage devices and realtime electrochemical reaction monitoring techniques.

Guo Hong received his PhD degree in physical chemistry from Peking University in 2011. He was a postdoctoral researcher at the City University of Hong Kong from 2011 to 2013, and a postdoctoral researcher at Swiss Federal Institute of Technology, Switzerland from 2013 to 2016. He joined BTR New Energy Materials Inc., China as the deputy director of the research center in 2016. Currently, he is an assistant professor at the Institute of Applied Physics and Materials Engineering, and Faculty of Science and Technology, University of Macau. His research interests focus on low-dimensional materials, flexible devices, energy storage and conversion.

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40843_2021_1908_MOESM1_ESM.pdf

A Strong Lewis Acid Imparts High Ionic Conductivity and Interfacial Stability to Polymer Composite Electrolytes towards All Solid-State Li Metal Batteries

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Wang, L., Zhong, Y., Wen, Z. et al. A strong Lewis acid imparts high ionic conductivity and interfacial stability to polymer composite electrolytes towards all-solid-state Li-metal batteries. Sci. China Mater. 65, 2179–2188 (2022). https://doi.org/10.1007/s40843-021-1908-x

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