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用于高性能锂离子电池的具有立方中空结构的碳包覆锗纳米球的可控制备

Controllable preparation of carbon coating Ge nanospheres with a cubic hollow structure for high-performance lithium ion batteries.

作者信息

Zhao Ying, Li Yilin, Wang Tingyu, Zhao Xudong, Kong Xianglong, Li Gaofu, Wang Zicong, He Fei, Chang Xinghua, Liu Zhiliang, Wu Linzhi, Zhang Milin, Yang Piaoping

机构信息

Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, PR China.

Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, PR China.

出版信息

J Colloid Interface Sci. 2025 Jan;677(Pt A):655-664. doi: 10.1016/j.jcis.2024.08.006. Epub 2024 Aug 3.

DOI:10.1016/j.jcis.2024.08.006
PMID:39116563
Abstract

Germanium based nanomaterials are very promising as the anodes for the lithium ion batteries since their large specific capacity, excellent lithium diffusivity and high conductivity. However, their controllable preparation is still very difficult to achieve. Herein, we facilely prepare a unique carbon coating Ge nanospheres with a cubic hollow structure (Ge@C) via a hydrothermal synthesis and subsequent pyrolysis using low-cost GeO as precursors. The hollow Ge@C nanostructure not only provides abundant interior space to alleviate the huge volumetric expansion of Ge upon lithiation, but also facilitates the transmission of lithium ions and electrons. Moreover, experiment analyses and density functional theory (DFT) calculations unveil the excellent lithium adsorption ability, high exchange current density, low activation energy for lithium diffusion of the hollow Ge@C electrode, thus exhibiting significant lithium storage advantages with a large charge capacity (1483 mAh/g under 200 mA g), distinguished rate ability (710 mAh/g under 8000 mA g) as well as long-term cycling stability (1130 mAh/g after 900 cycles under 1000 mA g). Therefore, this work offers new paths for controllable synthesis and fabrication of high-performance Ge based lithium storage nanomaterials.

摘要

基于锗的纳米材料作为锂离子电池的负极极具潜力,因为它们具有高比容量、出色的锂扩散率和高导电性。然而,其可控制备仍然很难实现。在此,我们以低成本的GeO为前驱体,通过水热合成及后续热解,简便地制备出了具有立方中空结构的独特碳包覆锗纳米球(Ge@C)。这种中空的Ge@C纳米结构不仅提供了丰富的内部空间以缓解锗在锂化时巨大的体积膨胀,还促进了锂离子和电子的传输。此外,实验分析和密度泛函理论(DFT)计算揭示了中空Ge@C电极具有出色的锂吸附能力、高交换电流密度、低锂扩散活化能,因此展现出显著的储锂优势,具有大充电容量(200 mA g下为1483 mAh/g)、卓越的倍率性能(8000 mA g下为710 mAh/g)以及长期循环稳定性(1000 mA g下900次循环后为1130 mAh/g)。因此,这项工作为高性能锗基储锂纳米材料的可控合成与制备提供了新途径。

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