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

IF 9.5 2区材料科学 Q1 CHEMISTRY, PHYSICAL

Nano Research Pub Date : 2024-07-31 DOI:10.1007/s12274-024-6886-9

Danru Huang, Lin Wu, Qi Kang, Zhiyong Shen, Qiaosheng Huang, Wenjie Lin, Fei Pei, Yunhui Huang

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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 LiNi_0.6Co_0.2Mn_0.2O₂ (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.

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用于高压固态锂金属电池的氨基改性 UiO-66-NH2 增强聚氨酯基聚合物电解质

固态聚合物电解质（SPE）与传统液态电解质相比，具有更好的机械和电化学稳定性，是满足先进锂电池安全性和能量密度需求的候选方案。然而，传统高压锂金属电池（LMB）的低离子电导率和副反应阻碍了它们的实际应用。在这里，具有丰富缺陷的氨基修饰金属有机框架（UiO-66-NH2）作为多功能填料加入到聚氨酯基固相萃取剂中，实现了机械强度和室温离子电导率的协同提升。表面修饰的氨基可作为聚合物链氧原子的锚定点，与聚碳酸酯基聚氨酯框架形成牢固的氢键界面。UiO-66-NH2 与聚合物之间丰富的界面大大减少了聚合物链的结晶，降低了离子传输阻抗，从而使离子电导率显著提高到 2.1 × 10-4 S-cm-1，Li+转移数高达 0.71。因此，LiFePO4∣SPEs∣锂电池在 0.5 摄氏度条件下可循环使用 700 次，容量保持率高达 96.5%。LiNi0.6Co0.2Mn0.2O2 (NCM622)∣SPEs∣锂电池在环境条件下可循环 260 次，容量保持率高达 91.9%，平均库仑效率高达 98.5%，具有出色的长期使用寿命。这种简单有效的混合 SPE 设计策略为高压金属锂电池的发展带来了里程碑式的意义。

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来源期刊

Nano Research 化学-材料科学：综合

CiteScore

14.30

自引率

11.10%

发文量

2574

审稿时长

1.7 months

期刊介绍： Nano Research is a peer-reviewed, international and interdisciplinary research journal that focuses on all aspects of nanoscience and nanotechnology. It solicits submissions in various topical areas, from basic aspects of nanoscale materials to practical applications. The journal publishes articles on synthesis, characterization, and manipulation of nanomaterials; nanoscale physics, electrical transport, and quantum physics; scanning probe microscopy and spectroscopy; nanofluidics; nanosensors; nanoelectronics and molecular electronics; nano-optics, nano-optoelectronics, and nano-photonics; nanomagnetics; nanobiotechnology and nanomedicine; and nanoscale modeling and simulations. Nano Research offers readers a combination of authoritative and comprehensive Reviews, original cutting-edge research in Communication and Full Paper formats. The journal also prioritizes rapid review to ensure prompt publication.