共价有机框架（COFs）在锂离子电池中的应用

doi:10.16085/j.issn.1000-6613.2022-2041

摘要/Abstract

摘要：

锂离子电池（LIBs）具技术成熟、能量密度较高、使用寿命长等优点使其在储能领域研究应用广泛，但传统商业化LIBs由于本身电极材料及电解质的限制，存在可逆比容量有限、功率密度不高、循环性能较差、生产材料成本较高、工作过程面临安全隐患等不足。本文简述了由轻质元素构成的晶态有机多孔材料共价有机框架（covalent organic frameworks，COFs），其有序的大孔道、可预先设计的结构、较大比表面积、低密度、易功能化等优势，完全具备利用于LIBs关键材料的潜力。回顾了近年来研究者们设计的各种COFs及其在LIBs的应用，包括COFs在LIBs电极材料、隔膜、电解质中的应用，得出COFs应用于LIBs具有卓越的电化学性能，最后对其在LIBs的研究方向给予预测，以期为储能和再生能源产业的发展提供一定参考。

关键词: 共价有机框架, 多孔材料, 锂离子电池, 性能, 再生能源, 安全

Abstract:

Lithium-ion batteries (LIBs) have been widely used in the field of energy storage due to their advantages of mature technology, high energy density and long service life. However, due to the limitation of electrode materials and electrolytes, traditional commercial LIBs have the disadvantages of limited reversible specific capacity, low power density, poor cycle performance, high cost of production materials and potential safety hazards in the working process. In this paper, covalent organic frameworks (COFs), a crystalline organic porous material composed of light elements, were briefly described. Its ordered large pores, pre-designed structure, large specific surface area, low density, easy functionalization and other advantages fully had the potential to be used as key materials for LIBs. Various COFs designed by researchers in recent years and their applications in LIBs were reviewed, including the application of COFs in LIBs electrode materials, separators and electrolytes. It was concluded that COFs had excellent electrochemical properties when applied to LIBs, Finally. the research direction of COFs in LIBs was predicted in order to provide some reference for the development of energy storage and renewable energy industries.

Key words: covalent organic framework, porous material, lithium-ion battery, performance, renewable energy, safety

中图分类号:

TQ152

马文杰, 姚卫棠. 共价有机框架（COFs）在锂离子电池中的应用[J]. 化工进展, 2023, 42(10): 5339-5352.

MA Wenjie, YAO Weitang. Application of covalent organic frameworks ( COFs ) in lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5339-5352.

图/表 14

图1 COF-1和COF-5的合成

表1 典型导电高分子正极材料分子结构及特征

材料	特征	参考文献
聚乙炔	结构不稳定；应用自放电；无法应用于实际	[22,27]
聚噻吩	低速电化学反应动力学；易溶于电解质	[23,27]
聚苯胺	能量密度低	[24,27]
聚对苯	刚性共轭苯环，电化学反应受限	[25-27]

图2 DTP-ANDI-COF的AA堆积的示意图[30]

图3 DTP-ANDI-COF@CNTs性能示意图[30]

图4 Tp-DANT-COF电极在三种倍率条件下的性能实验图[33]红—放电；黑—充电；蓝—效率

图5 Tb-DANT COF电极在0.34C和3.4C下的循环性能[33]（放电红、充电黑和效率蓝）

图6 PIBN和PIBN-G的合成路线[37]

图7 COF形成示意图 [40]绿色—氨基衍生物；蓝色—1,3,5-三甲酰基苯单元

图8 以N2-COF和N3-COF为阳极制备的LiBs的电化学性能[40]红色曲线—效率，即充放电容量之比

图9 锂离子电池Na-NiPC、PPDA-NiPC和DAB-NiPC电极的SEM图像[42](a)、(c)、(e)—未活化；(b)、(d)、(f)—300次循环后

图10 BA、PA和TA-COF的制备路线BA—小分子；PA—线性聚合物；TA-COF—TA‐共价有机骨架

图11 BA、PA和TA‐COF电极的循环性能[44]。BA—小分子；PA—线性聚合物；TA‐COF—TA‐共价有机框架

图12 阳离子COFs基固体电解质的图解

图13 TpPa-SO3Li的合成

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