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Research Article

Amino-modified UiO-66-NH2 reinforced polyurethane based polymer electrolytes for high-voltage solid-state lithium metal batteries

Danru Huang1,§, Lin Wu2,§, Qi Kang2,3,§, Zhiyong Shen1, Qiaosheng Huang1, Wenjie Lin2, Fei Pei1,2( ), Yunhui Huang2
State Key Laboratory of Low-carbon Smart Coal-fired Power Generation and Ultra-clean Emission, China Energy Science and Technology Research Institute Co., Ltd., Nanjing 210023, China
State Key Laboratory of Materials Processing and Die and Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

§ Danru Huang, Lin Wu, and Qi Kang contributed equally to this work.

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Graphical Abstract

Amino-modified Zr-carboxylate metal-organic frameworks (MOFs) (UiO-66-NH2) were designed as multifunctional fillers in forming a rich hydrogen bond network with polyurethane based electrolyte, achieving the collaborative promotion of the mechanical strength and room temperature ionic conductivity.

Abstract

Solid-state polymer electrolytes (SPEs) are candidate schemes for meeting the safety and energy density needs of advanced lithium-based battery because of their improved mechanical and electrochemical stability compared to traditional liquid electrolytes. However, low ionic conductivity and side reactions occurring in traditional high-voltage lithium metal batteries (LMBs) hinder their practical applications. Here, amino-modified metal-organic frameworks (UiO-66-NH2) with abundant defects as multifunctional fillers in the polyurethane based SPEs achieve the collaborative promotion of the mechanical strength and room temperature ionic conductivity. The surface modified amino groups serve as anchoring points for oxygen atoms of polymer chains, forming a firmly hydrogen-bond interface with polycarbonate-based polyurethane frameworks. The rich interfaces between UiO-66-NH2 and polymers dramatically decrease the crystallization of polymer chains and reduce ion transport impedance, which markedly boosted the ionic conductivity to 2.1 × 10−4 S·cm−1 with a high Li+ transference numbers of 0.71. As a result, LiFePO4|SPEs|Li cells exhibit prominent cyclability for 700 cycles under 0.5 C with 96.5% capacity retention. The LiNi0.6Co0.2Mn0.2O2 (NCM622)|SPEs|Li cells deliver excellent long-term lifespan for 260 cycles with a high capacity retention of 91.9% and high average Coulombic efficiency (98.5%) under ambient conditions. This simple and effective hybrid SPE design strategy sheds a milestone significance light for high-voltage Li-metal batteries.

Keywords

solid-state polymer electrolytemetal-organic frameworkspolyurethanelithium metal batterieshigh voltage interface

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Nano Research
Volume 17 Issue 11,
November 2024
Pages 9662-9670
DOI: 10.1007/s12274-024-6886-9
Cite this article:
Huang D, Wu L, Kang Q, et al. Amino-modified UiO-66-NH2 reinforced polyurethane based polymer electrolytes for high-voltage solid-state lithium metal batteries. Nano Research, 2024, 17(11): 9662-9670. https://doi.org/10.1007/s12274-024-6886-9
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Received: 05 June 2024
Revised: 28 June 2024
Accepted: 15 July 2024
Published: 31 July 2024
© Tsinghua University Press 2024
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