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Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO2 fillers for high-performance all solid-state lithium metal batteries

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Abstract

Anion-immobilized solid composite electrolytes (SCEs) are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries (ASSLMBs). Herein, a novel SCEs based on metal-organic frameworks (MOFs, UiO-66-NH2) and superacid ZrO2 (S-ZrO2) fillers are proposed, and the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), thermo-gravimetric analyzer (TGA) and some other electrochemical measurements. The -NH2 groups of UiO-66-NH2 combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) chains by hydrogen bonds, leading to a high electrochemical stability window of 5 V. Owing to the incorporation of UiO-66-NH2 and S-ZrO2 in PVDF-HFP polymer, the open metal sites of MOFs and acid surfaces of S-ZrO2 can immobilize anions by strong Lewis acid-base interaction, which enhances the effect of immobilization anions, achieving a high Li-ion transference number (t+) of 0.72, and acquiring a high ionic conductivity of 1.05×10−4 S·cm−1 at 60°C. The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm−2 without the short-circuit occurring. Besides, the solid composite Li/LiFePO4 (LFP) cell with the anion-immobilized SCEs shows a superior discharge specific capacity of 158 mAh·g−1 at 0.2 C. The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.

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Acknowledgements

This work was financially supported by National Natural Science Foundation of China (No. 21701083), Zhenjiang Key Laboratory of Marine Power Equipment Performance (SS2018006), The Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. SJCX19_0612) and Project of Jiangsu University (High-Tech Ship) Collaborative Innovation Center (2019, 1174871801-11).

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  1. School of Energy and Power, Jiangsu University of Science and Technology, Zhenjiang, 212003, China

    Tao Wei, Zao-hong Zhang, Qi Zhang, Jia-hao Lu, Qi-ming ** Zhou

  2. Department of Chemistry, College of Science, Nan**g Agricultural University, Nan**g, 210095, China

    Wen-jia Zhao

  3. Power & Energy Storage System Research Center, College of Mechanical and Electrical Engineering, Qingdao University, Qingdao, 266071, China

    **ang-yun Qiu

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Wei, T., Zhang, Zh., Zhang, Q. et al. Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO2 fillers for high-performance all solid-state lithium metal batteries. Int J Miner Metall Mater 28, 1636–1646 (2021). https://doi.org/10.1007/s12613-021-2289-z

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