Applications of Covalent Organic Frameworks in Li⁃S Battery Separators

doi:10.12422/j.issn.1672-6952.2023.04.004

Abstract

Abstract:

Due to the high storage capacity and multiple electron?transfer chemistry of sulfur (S), Li?S battery with virtues of high theoretical capacity/energy density, eco?friendliness and abundant supply has been considered as one of the most promising candidates for next?generation battery systems. The capacity of Li?S battery is much higher than that of traditional metal oxide cathode?based lithium?ion battery, which is regarded as the highest capacity of solid?state cathode?materials at current stage. As a vital component of Li?S battery, separator plays a profound role in resolving crucial issues (e.g., shuttling effect, volume expansion, poor conductivity and metal dendrites, etc.) of Li?S battery. So far, some pioneering works have been reported in the exploration of separators for Li?S battery. On this basis, covalent organic frameworks (COFs), possessing the advantages of low density, high porosity, well?defined structure, designable structure and functions, is a kind of potential materials for the functional modification of Li?S battery separators. This review will summarize the reported works about COFs in Li?S battery separators including their structural characteristics, preparation?methods, application forms and battery properties. It will also provide a brief perspective for the applications of COFs in Li?S battery separators and hope that it might give new insights for scientists in related fields.

Key words: Covalent organic frameworks, Li?S battery, Separator, Modification

摘要：

由于硫（S）的高存储容量和多电子转移化学性质，锂硫（Li?S）电池具有理论容量/能量密度高、生态友好和供应丰富等优点，被认为是下一代电池系统最有可能的候选之一。Li?S电池的容量远高于传统金属氧化物阴极基锂离子电池，被认为是现阶段固态正极材料的最高容量。隔膜作为Li?S电池的重要组成部分，在解决穿梭效应、体积膨胀、导电性差和锂枝晶生长等电池问题方面发挥着重要作用。迄今为止，在Li?S电池隔膜的探索方面，已有一些开创性的研究报道。其中，共价有机框架（COFs）作为一种功能材料，具有孔隙率高、结构明确可设计、功能可调等优点，可为Li?S电池隔膜的应用提供更多可能性。综述了Li?S电池隔膜中COFs的结构特点、制备方法、应用形式和电池性能。此外，还对COFs在Li?S电池隔膜应用中的挑战提出了简要的展望，以期为相关领域的科研人员提供借鉴和参考。

关键词: 共价有机框架, 锂硫电池, 隔膜, 改性

CLC Number:

TQ325.1

Yuluan Zhang, Can Guo, Luanhua Zhou, Xiaoman Yao, Yiwen Yang, Huifen Zhuang, Yirong Wang, Yifa Chen, Shunli Li, Yaqian Lan. Applications of Covalent Organic Frameworks in Li⁃S Battery Separators[J]. Journal of Liaoning Petrochemical University, 2023, 43(4): 19-29.

张玉銮, 郭璨, 周銮华, 姚晓曼, 杨仪雯, 庄惠芬, 王艺蓉, 陈宜法, 李顺利, 兰亚乾. 共价有机框架在锂硫电池隔膜中的应用综述[J]. 辽宁石油化工大学学报, 2023, 43(4): 19-29.

Figures/Tables 3

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序号	基底	修饰材料	方法	硫载量/(mg•cm^-2)	循环性能/(mA·h·g^-1)	文献
1	聚乙烯	COF⁃1⁃CNT	真空过滤	1.1	容量保留率84% (300次循环，2.0 C)	[48]
2	Celgard	TP⁃BPY⁃COF	刮涂	1.0~1.5	826.00 (250次循环，1.0 C)	[49]
3	Celgard 2325	SCOF⁃2	刮涂	1.2~2.0	497.00 (800次循环，1.0 C)	[50]
4	PP隔膜	COF⁃TpPa⁃SO₃H@rGO	刮涂	0.9	523.00 (1 000次循环,2.0 C)	[51]
5	Celgard 2400	TpPa⁃SO₃H@PP	原位界面聚合	1.0	645.62 (500次循环，1.0 C)	[52]
6	Celgard 2400	TAPP⁃ETTB@GO	真空过滤	1.5~2.0	920.00 (400次循环，0.2 A/g)	[53]
7	Celgard 2500	COF⁃IL/PP/MOF	刮涂	1.0~1.2	674.60 (100次循环，0.2 C)	[54]
8	陶瓷	DMTA⁃COF	刮涂	1.5	1 000.00 (100次循环，0.5 C)	[57]
9	Celgard	CTFs	刮涂	2.0	700.10 (800次循环，1.0 C)	[58]
10	Celgard 2500	CTF	真空过滤	-	684.00 (400次循环，1.0 C)	[59]
11	Celgard 2400	PyBBT⁃COF	真空过滤	1.0	905.00 (100次循环，0.2.0 C)	[60]
12	Celgard PP/PE/PP	TpPa⁃SO₃Li/CNT	真空过滤	1.5	482.00 (400次循环，4.0 C)	[61]
13	Celgard 2325	SCOF	刮涂	1.0	750.00 (120次循环，0.5 C)	[62]
14	PP 隔膜	4F⁃COF	刮涂	0.8~1.0	873.10 (100次循环，0.2 C)	[63]
15	Celgard 2400	CB⁃COF	刮涂	2.0	569.00 (1 000次循环，1.0 C)	[64]
16	陶瓷	CNT@DMTA⁃COF	刮涂	2.0	621.00 (500次循环，1.0 A/g)	[65]
17	Celgard 2500	Py⁃DPP⁃COF@CNT	刮涂	1.2~2.0	584.00(1 000次循环，1.0 C)	[66]
18	Celgard 2400	C@COF	真空过滤	1.2~1.5	655.70 (500次循环，1 C)	[67]
19	Celgard	HUT9@CNT	刮涂	1.1	750.00 (500次循环，1.0 C)	[68]
20	Celgard	COF⁃rGO	真空过滤	1.0~1.5	1 169.40 (50次循环，0.1 C)	[69]
21	Celgard	Li⁃CON	真空过滤	1.0~2.0	645.00 (600次循环，1.0 C)	[70]
22	Celgard 2400	Ti₃C₂@iCON	真空过滤	1.2	706.00 (2 000次循环，2 C)	[71]
23	Celgard 2500	TpPa⁃SO₃H	真空过滤	1.2	494.00 (500次循环，1.0 C)	[72]
24	Celgard 2400	PA COF⁃TiO₂	刮涂	1.8	371.50 (2 000次循环，1.0 C)	[73]
25	PP隔膜	TpTt/CNT	刮涂	-	1 214.00 (0.1 C)	[74]

序号	基底	修饰材料	方法	硫载量/(mg•cm^-2)	循环性能/(mA·h·g^-1)	文献
1	聚乙烯	COF⁃1⁃CNT	真空过滤	1.1	容量保留率84% (300次循环，2.0 C)	[48]
2	Celgard	TP⁃BPY⁃COF	刮涂	1.0~1.5	826.00 (250次循环，1.0 C)	[49]
3	Celgard 2325	SCOF⁃2	刮涂	1.2~2.0	497.00 (800次循环，1.0 C)	[50]
4	PP隔膜	COF⁃TpPa⁃SO₃H@rGO	刮涂	0.9	523.00 (1 000次循环,2.0 C)	[51]
5	Celgard 2400	TpPa⁃SO₃H@PP	原位界面聚合	1.0	645.62 (500次循环，1.0 C)	[52]
6	Celgard 2400	TAPP⁃ETTB@GO	真空过滤	1.5~2.0	920.00 (400次循环，0.2 A/g)	[53]
7	Celgard 2500	COF⁃IL/PP/MOF	刮涂	1.0~1.2	674.60 (100次循环，0.2 C)	[54]
8	陶瓷	DMTA⁃COF	刮涂	1.5	1 000.00 (100次循环，0.5 C)	[57]
9	Celgard	CTFs	刮涂	2.0	700.10 (800次循环，1.0 C)	[58]
10	Celgard 2500	CTF	真空过滤	-	684.00 (400次循环，1.0 C)	[59]
11	Celgard 2400	PyBBT⁃COF	真空过滤	1.0	905.00 (100次循环，0.2.0 C)	[60]
12	Celgard PP/PE/PP	TpPa⁃SO₃Li/CNT	真空过滤	1.5	482.00 (400次循环，4.0 C)	[61]
13	Celgard 2325	SCOF	刮涂	1.0	750.00 (120次循环，0.5 C)	[62]
14	PP 隔膜	4F⁃COF	刮涂	0.8~1.0	873.10 (100次循环，0.2 C)	[63]
15	Celgard 2400	CB⁃COF	刮涂	2.0	569.00 (1 000次循环，1.0 C)	[64]
16	陶瓷	CNT@DMTA⁃COF	刮涂	2.0	621.00 (500次循环，1.0 A/g)	[65]
17	Celgard 2500	Py⁃DPP⁃COF@CNT	刮涂	1.2~2.0	584.00(1 000次循环，1.0 C)	[66]
18	Celgard 2400	C@COF	真空过滤	1.2~1.5	655.70 (500次循环，1 C)	[67]
19	Celgard	HUT9@CNT	刮涂	1.1	750.00 (500次循环，1.0 C)	[68]
20	Celgard	COF⁃rGO	真空过滤	1.0~1.5	1 169.40 (50次循环，0.1 C)	[69]
21	Celgard	Li⁃CON	真空过滤	1.0~2.0	645.00 (600次循环，1.0 C)	[70]
22	Celgard 2400	Ti₃C₂@iCON	真空过滤	1.2	706.00 (2 000次循环，2 C)	[71]
23	Celgard 2500	TpPa⁃SO₃H	真空过滤	1.2	494.00 (500次循环，1.0 C)	[72]
24	Celgard 2400	PA COF⁃TiO₂	刮涂	1.8	371.50 (2 000次循环，1.0 C)	[73]
25	PP隔膜	TpTt/CNT	刮涂	-	1 214.00 (0.1 C)	[74]

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[10]	Zhang Li, Zhao Xuebo. Research Progress in Surface and Interface Control of Silicon⁃Based Anode Materials for Lithium Ion Batteries [J]. Journal of Liaoning Petrochemical University, 2020, 40(4): 49-58.
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