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Nanostructured Li-Rich Fluoride Coated by Ionic Liquid as High Ion-Conductivity Solid Electrolyte Additive to Suppress Dendrite Growth at Li Metal Anode

  • Jiulin Hu
    Jiulin Hu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100039, China
    More by Jiulin Hu
    • , 
  • Keyi Chen
    Keyi Chen
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    University of Chinese Academy of Sciences, Beijing 100039, China
    More by Keyi Chen
    • , and 
  • Chilin Li*
    Chilin Li
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
    *E-mail: [email protected]
    More by Chilin Li
    Orcidhttp://orcid.org/0000-0002-5587-8617
Cite this: ACS Appl. Mater. Interfaces 2018, 10, 40, 34322–34331
Publication Date (Web):September 12, 2018
https://doi.org/10.1021/acsami.8b12579
Copyright © 2018 American Chemical Society
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Abstract

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Blending additive with electrolyte is a facile and effective method to suppress anode dendrite growth in Li metal batteries (LMBs), especially when a LiF-rich solid electrolyte interface (SEI) is formed as a consequence of additive decomposition or deposition. However LiF still suffers from poor bulk ion conductivity as well as the difficult access to tailored nanostructure. Exploring new Li fluoride of high Li-ion conductivity as SEI component is still a big challenge in view of the lacking of desired structure prototype or mineral phase. Here, we propose a Li-rich Li3AlF6 derivative from cryolite phase as solid electrolyte additive, which is characterized by textured nanoporous morphology and ionic liquid coating. Its room temperature ion conductivity is as high as ∼10–5 S/cm with a low activation energy of 0.29 eV, the best level among fluoride-based solid electrolytes. These features guarantee a homogenization of Li+ fluxing through bulk and grain boundary of Li3AlF6-rich SEI and reinforce the effect on Li dendrite suppression. Li3AlF6 additive enables a stable cyclability of Li∥Li symmetric cells for at least 100 cycles even under a high areal capacity of 3 mA h/cm2 and a significant improvement on capacity retention for various LMBs based on LiFePO4, FeS2, and S cathodes.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b12579.

  • Overview SEM images of LAF-60 and LAF-25; EDS mapping of LAF-60; XPS of LAF-60; zeta voltage table for of LAF-60, LAF-25, and LiF, Li plating/stripping of Li∥Li symmetric cells based on LAF-60 with different concentration, LAF-25, sintered LAF-60, commercial LiF, amorphous Al–F, AlF3·3H2O, and commercial AlF3; voltage profiles and hysteresis of Li∥Cu asymmetric cells free of additive and containing LAF-60; charge–discharge curves and cycling performance of Li–LiFePO4, Li–FeS2, and Li–S cells with and without LAF-60; XRD of sintered LAF-60 and Li-free aluminum fluorides; impedance of sintered LAF-60; and Li–LiFePO4 performance based on sintered LAF-60 (PDF)

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Cited By

This article is cited by 20 publications.

  1. Huanhuan Jia, Xinmiao Liang, Tao An, Linfeng Peng, Jiwen Feng, Jia Xie. Effect of Halogen Doping in Sodium Solid Electrolytes Based on the Na–Sn–Si–P–S Quinary System. Chemistry of Materials 2020, 32 (9) , 4065-4071. https://doi.org/10.1021/acs.chemmater.0c00872
  2. Jianwen Liang, Xiaona Li, Shuo Wang, Keegan R. Adair, Weihan Li, Yang Zhao, Changhong Wang, Yongfeng Hu, Li Zhang, Shangqian Zhao, Shigang Lu, Huan Huang, Ruying Li, Yifei Mo, Xueliang Sun. Site-Occupation-Tuned Superionic LixScCl3+xHalide Solid Electrolytes for All-Solid-State Batteries. Journal of the American Chemical Society 2020, 142 (15) , 7012-7022. https://doi.org/10.1021/jacs.0c00134
  3. Haojun Qi, Yongyuan Ren, Siyu Guo, Yuyue Wang, Shujin Li, Yin Hu, Feng Yan. High-Voltage Resistant Ionic Liquids for Lithium-Ion Batteries. ACS Applied Materials & Interfaces 2020, 12 (1) , 591-600. https://doi.org/10.1021/acsami.9b16786
  4. Tiancun Liu, Jiulin Hu, Chilin Li, Yong Wang. Unusual Conformal Li Plating on Alloyable Nanofiber Frameworks to Enable Dendrite Suppression of Li Metal Anode. ACS Applied Energy Materials 2019, 2 (6) , 4379-4388. https://doi.org/10.1021/acsaem.9b00573
  5. Min Liu, Nanping Deng, Jingge Ju, Liyuan Wang, Gang Wang, Yali Ma, Weimin Kang, Jing Yan. Silver Nanoparticle-Doped 3D Porous Carbon Nanofibers as Separator Coating for Stable Lithium Metal Anodes. ACS Applied Materials & Interfaces 2019, 11 (19) , 17843-17852. https://doi.org/10.1021/acsami.9b04122
  6. Zhixuan Wang, Yi Jiang, Juan Wu, Yong Jiang, Shoushuang Huang, Bing Zhao, Zhiwen Chen, Jiujun Zhang. Reaction mechanism of Li2S-P2S5 system in acetonitrile based on wet chemical synthesis of Li7P3S11 solid electrolyte. Chemical Engineering Journal 2020, 393 , 124706. https://doi.org/10.1016/j.cej.2020.124706
  7. Jiulin Hu, Zhenguo Yao, Keyi Chen, Chilin Li. High-conductivity open framework fluorinated electrolyte bonded by solidified ionic liquid wires for solid-state Li metal batteries. Energy Storage Materials 2020, 28 , 37-46. https://doi.org/10.1016/j.ensm.2020.02.018
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  9. Xiaona Li, Jianwen Liang, Xiaofei Yang, Keegan R. Adair, Changhong Wang, Feipeng Zhao, Xueliang Sun. Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energy & Environmental Science 2020, 13 (5) , 1429-1461. https://doi.org/10.1039/C9EE03828K
  10. Panlong Li, Wuliang Feng, Xiaoli Dong, Yonggang Wang, Yongyao Xia. A New Strategy of Constructing a Highly Fluorinated Solid‐Electrolyte Interface towards High‐Performance Lithium Anode. Advanced Materials Interfaces 2020, 29 , 2000154. https://doi.org/10.1002/admi.202000154
  11. Zhenxing Wang, Fulai Qi, Lichang Yin, Ying Shi, Chengguo Sun, Baigang An, Hui‐Ming Cheng, Feng Li. An Anion‐Tuned Solid Electrolyte Interphase with Fast Ion Transfer Kinetics for Stable Lithium Anodes. Advanced Energy Materials 2020, 10 (14) , 1903843. https://doi.org/10.1002/aenm.201903843
  12. Isheunesu Phiri, Chris Yeajoon Bon, Manasi Mwemezi, Louis Hamenu, Alfred Madzvamuse, Jeong Ho Park, Kwang Se Lee, Jang Myoun Ko, Yunfeng Lu. Enhanced electrolyte performance by adopting Zwitterionic lithium-silica sulfobetaine silane as electrolyte additive for lithium-ion batteries. Materials Chemistry and Physics 2020, 243 , 122577. https://doi.org/10.1016/j.matchemphys.2019.122577
  13. Xiang Guan, Qingping Wu, Xiaowan Zhang, Xuhong Guo, Chilin Li, Jun Xu. In-situ crosslinked single ion gel polymer electrolyte with superior performances for lithium metal batteries. Chemical Engineering Journal 2020, 382 , 122935. https://doi.org/10.1016/j.cej.2019.122935
  14. Qiushi Sun, Xiao Chen, Jian Xie, Xiongwen Xu, Jian Tu, Peng Zhang, Xinbing Zhao. Nonflammable quasi-solid-state electrolyte for stable lithium-metal batteries. RSC Advances 2019, 9 (72) , 42183-42193. https://doi.org/10.1039/C9RA08677C
  15. Lei Zheng, Feng Guo, Tuo Kang, Jin Yang, Ya Liu, Wei Gu, Yanfei Zhao, Hongzhen Lin, Yanbin Shen, Wei Lu, Liwei Chen. Highly stable lithium anode enabled by self-assembled monolayer of dihexadecanoalkyl phosphate. Nano Research 2019, 29 https://doi.org/10.1007/s12274-019-2565-7
  16. Shouyi Yuan, Junwei Lucas Bao, Jishi Wei, Yongyao Xia, Donald G. Truhlar, Yonggang Wang. A versatile single-ion electrolyte with a Grotthuss-like Li conduction mechanism for dendrite-free Li metal batteries. Energy & Environmental Science 2019, 12 (9) , 2741-2750. https://doi.org/10.1039/C9EE01473J
  17. Huan Yang, Ning Lun, Yong-Xin Qi, Hui-Ling Zhu, Jiu-Rong Liu, Jin-Kui Feng, Lan-ling Zhao, Yu-Jun Bai. Li2ZnTi3O8 coated with uniform lithium magnesium silicate layer revealing enhanced rate capability as anode material for Li-Ion battery. Electrochimica Acta 2019, 315 , 24-32. https://doi.org/10.1016/j.electacta.2019.05.087
  18. Junwei Meng, Fulu Chu, Jiulin Hu, Chilin Li. Liquid Polydimethylsiloxane Grafting to Enable Dendrite‐Free Li Plating for Highly Reversible Li‐Metal Batteries. Advanced Functional Materials 2019, 29 (30) , 1902220. https://doi.org/10.1002/adfm.201902220
  19. Peng Wang, Wenjie Qu, Wei‐Li Song, Haosen Chen, Renjie Chen, Daining Fang. Electro–Chemo–Mechanical Issues at the Interfaces in Solid‐State Lithium Metal Batteries. Advanced Functional Materials 2019, 500 , 1900950. https://doi.org/10.1002/adfm.201900950
  20. Han Wu, Qingping Wu, Fulu Chu, Jiulin Hu, Yanhua Cui, Congling Yin, Chilin Li. Sericin protein as a conformal protective layer to enable air-endurable Li metal anodes and high-rate Li-S batteries. Journal of Power Sources 2019, 419 , 72-81. https://doi.org/10.1016/j.jpowsour.2019.02.033

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