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Metal–Organic Frameworks as Electrolyte Additives To Enable Ultrastable Plating/Stripping of Li Anode with Dendrite Inhibition

  • Fulu Chu
    Fulu Chu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, China
    More by Fulu Chu
  • Jiulin Hu
    Jiulin Hu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    More by Jiulin Hu
  • Chenglong Wu
    Chenglong Wu
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    More by Chenglong Wu
  • Zhenguo Yao
    Zhenguo Yao
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    More by Zhenguo Yao
  • Jing Tian
    Jing Tian
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    More by Jing Tian
  • Zheng Li*
    Zheng Li
    School of Materials Science and Engineering, Xiangtan University, Xiangtan 411105, China
    *E-mail: [email protected] (Z.L.).
    More by Zheng Li
  • , and 
  • Chilin Li*
    Chilin Li
    State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding Xi Road, Shanghai 200050, China
    *E-mail: [email protected] (C.L.).
    More by Chilin Li
Cite this: ACS Appl. Mater. Interfaces 2019, 11, 4, 3869–3879
Publication Date (Web):December 28, 2018
https://doi.org/10.1021/acsami.8b17924
Copyright © 2018 American Chemical Society
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Abstract

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Suppressing the extrusion of Li dendrites and alleviating the volume expansion of Li anode during long-term cycling are of great significance to achieve highly reversible Li metal batteries of high energy density potential. However, the exploration of facile and effective solutions to smoothen anode surface is still a big challenge. Here, we propose a solid additive strategy by blending tailored metal–organic framework (MOF) grains with typical carbonate electrolyte to enable an ultrastable plating/stripping cycling of Li anode for at least 1400 h with evident inhibition of anode roughening and voltage polarization. Zr-based MOF (UiO-66) additive enables the smallest nucleation and plateau overpotentials (∼80 mV) during Li plating especially under high current density (2 mA/cm2) and large areal capacity (4 mAh/cm2). The kinetic and cyclic advantages of Li anode modulated by UiO-66 not only benefit from its intrinsic features (high surface area/porosity and thermal/electrochemical stability) but also from the reinforced solid electrolyte interface with low resistance, which consists of concentrated LiF and robust Zr–O–C moieties. Li–Li4Ti5O12 cell based on MOF additive can achieve a high reversibility for at least 900 cycles.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b17924.

  • Experimental detail; SEM, TEM, and EDX mapping of UiO-66, MIL-101-NH2, and HKUST-1; Li plating/stripping of Li∥Li symmetric cells with HKUST-1 and MIL-101-NH2; voltage profiles of Li∥Cu asymmetric cells with UiO-66, HKUST-1, MIL-101-NH2, and free of MOF additive; CE and voltage hysteresis based on Li∥Cu asymmetric cells with HKUST-1, MIL-101-NH2, and free of MOF additive; impedance spectra of Li∥Li symmetric cells with different MOF additives or free of additive; SEM images of cycled Li surface morphology modulated by MIL-101-NH2 and HKUST-1; and voltage curves of Li/LTO cells with UiO-66 and free of additive (PDF)

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Cited By


This article is cited by 11 publications.

  1. Binsong Li, Jiagang Xu, Xingcheng Xiao. Reinforced Composite Film on Lithium Metal Electrodes through Aryl Chlorosilane Treatment. Langmuir 2019, 35 (50) , 16459-16465. https://doi.org/10.1021/acs.langmuir.9b02533
  2. 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
  3. Lingdi Shen, Xin Liu, Jing Dong, Yuting Zhang, Chunxian Xu, Chao Lai, Shanqing Zhang. Functional lithiophilic polymer modified separator for dendrite-free and pulverization-free lithium metal batteries. Journal of Energy Chemistry 2021, 52 , 262-268. https://doi.org/10.1016/j.jechem.2020.04.058
  4. Xiaowan Zhang, Qingping Wu, Xiang Guan, Fahai Cao, Chilin Li, Jun Xu. Lithium dendrite-free and fast-charging for high voltage nickel-rich lithium metal batteries enabled by bifunctional sulfone-containing electrolyte additives. Journal of Power Sources 2020, 452 , 227833. https://doi.org/10.1016/j.jpowsour.2020.227833
  5. 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
  6. Ying Du, Xing Gao, Siwu Li, Lu Wang, Bo Wang. Recent advances in metal-organic frameworks for lithium metal anode protection. Chinese Chemical Letters 2020, 31 (3) , 609-616. https://doi.org/10.1016/j.cclet.2019.06.013
  7. 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
  8. 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
  9. Mohadeseh Safaei, Mohammad Mehdi Foroughi, Nasser Ebrahimpoor, Shohreh Jahani, Ali Omidi, Mehrdad Khatami. A review on metal-organic frameworks: Synthesis and applications. TrAC Trends in Analytical Chemistry 2019, 118 , 401-425. https://doi.org/10.1016/j.trac.2019.06.007
  10. 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
  11. Yi Zheng, Wei Fang, Hao Zheng, Yi Su, Xin Liang, Chunhua Chen, Hongfa Xiang. A Multifunctional Thiophene-Based Electrolyte Additive for Lithium Metal Batteries Using High-Voltage LiCoO 2 Cathode. Journal of The Electrochemical Society 2019, 166 (14) , A3222-A3227. https://doi.org/10.1149/2.0291914jes

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