KOH辅助水相合成双金属有机骨架及其衍生的硒化物复合材料用于高效储锂研究

张书亚; 薛艳春; 张玉堂; 朱骋兴; 郭兴梅; 曹福; 郑祥俊; 孔庆红; 张俊豪; 范同祥

doi:10.1007/s12613-022-2539-8

Volume 30 Issue 4

Apr. 2023

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文章导航 > 矿物冶金与材料学报（英文） > 2023 > 30(4): 601-610

Shuya Zhang, Yanchun Xue, Yutang Zhang, Chengxing Zhu, Xingmei Guo, Fu Cao, Xiangjun Zheng, Qinghong Kong, Junhao Zhang, and Tongxiang Fan, KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage, Int. J. Miner. Metall. Mater., 30(2023), No. 4, pp. 601-610. https://doi.org/10.1007/s12613-022-2539-8

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Shuya Zhang, Yanchun Xue, Yutang Zhang, Chengxing Zhu, Xingmei Guo, Fu Cao, Xiangjun Zheng, Qinghong Kong, Junhao Zhang, and Tongxiang Fan, KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage, Int. J. Miner. Metall. Mater., 30(2023), No. 4, pp. 601-610. https://doi.org/10.1007/s12613-022-2539-8

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研究论文

KOH辅助水相合成双金属有机骨架及其衍生的硒化物复合材料用于高效储锂研究

1)
江苏科技大学环境与化学工程学院，镇江 212003，中国
2)
上海交通大学材料科学与工程学院，上海 200240，中国
3)
江苏大学环境与安全工程学院，镇江 212013，中国
4)
佛山(华南)新材料研究院，佛山 528200，中国

* 共同第一作者

通讯作者:
郭兴梅 E-mail: guoxm@just.edu.cn

范同祥 E-mail: txfan@sjtu.edu.cn

文章亮点

(1) 开发了一种KOH辅助水相合成双金属有机框架材料的绿色高效合成方法。

(2) 该双金属硒化物/碳复合材料可缓解储锂过程中体积膨胀并促进电化学反应动力学。

(3) 总结并提出了KOH辅助水系合成双金属有机框架材料的方法具有普适性。

中文摘要

金属有机框架（MOFs）是一类很有前景的多孔材料，其水稳定性和绿色环保的合成是当今工业界及学术界研究的两个重要课题。大部分MOFs材料通过溶剂热法制备，制备过程中使用的有机溶剂（如DMF）会限制其商业生产规模。因此，如果能够使用水作为溶剂宏量制备MOFs材料具有十分重要的研究意义。本文旨在开发具有结构优势和高存储容量的双金属硒化物作为锂离子电池的负极材料，利用KOH辅助的水性策略宏量合成双金属有机框架材料，并衍生制备多种双金属硒化物氮/碳（NC）复合材料，采用扫描、透射电镜观察、电化学测试等研究。其中，以Fe–Co–Se/NC为例，作为锂离子电池负极材料时，Fe–Co–Se/NC在1.0 A·g⁻¹时实现了1165.9 mAh·g⁻¹的优异初始比容量，经过550次循环后Fe–Co–Se/NC负极的可逆容量为1247.4 mAh·g⁻¹。这些优异的性能与其介孔三维（3D）多面体结构有关，其稳定的三维结构保证了结构稳定性和电解质的润湿性，均匀分布的Fe–Co–Se纳米颗粒尺寸加速了电化学反应动力学并极大地抑制了体积膨胀。由此总结并提出，KOH辅助水相合成双金属MOFs的策略具有普适性，并且衍生制得的双金属硒化物氮/碳复合材料保留了双金属MOFs的三维多孔多面体结构，可将该技术扩展到其他MOFs的合成及储能与转换领域的应用。

关键词:

Research Article

KOH-assisted aqueous synthesis of bimetallic metal-organic frameworks and their derived selenide composites for efficient lithium storage

+ Author Affiliations

1)
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
2)
School of Materials Science and Engineering, Shanghai Jiaotong University, Shanghai 200240, China
3)
School of the Environment and Safety Engineering, Jiangsu University, Zhenjiang 212013, China
4)
Foshan (Southern China) Institute for New Materials, Foshan 528200, China

*These authors contributed equally to this work.

Corresponding authors:
Xingmei Guo E-mail: guoxm@just.edu.cn

Tongxiang Fan E-mail: txfan@sjtu.edu.cn
Received: 23 May 2022; Revised: 17 August 2022; Accepted: 19 August 2022; Available online: 21 August 2022

Abstract

Abstract

To solve low efficiency, environmental pollution, and toxicity for synthesizing zeolitic imidazolate frameworks (ZIFs) in organic solvents, a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons, which are used as precursors to prepare bimetallic selenide and N-doped carbon (NC) composites. Among them, Fe–Co–Se/NC retains the three-dimensional (3D) polyhedrons with mesoporous structure, and Fe–Co–Se nanoparticles are uniform in size and evenly distributed. When assessed as anode material for lithium-ion batteries, Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 mAh·g⁻¹ at 1.0 A·g⁻¹, and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 mAh·g⁻¹ after 550 cycles. It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites, the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte, and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.

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