有机介质体系锂离子电容器

doi:10.16085/j.issn.1000-6613.2018-1026

摘要/Abstract

摘要：

锂离子电容器（lithium ion capacitor，LIC）是一种新型的电化学储能器件，可以填补锂离子电池和超级电容器两者之间的性能空白，是下一代高能量密度超级电容器的前进方向。本文首先介绍了锂离子电容器的储能原理分为电解液消耗机制、锂离子交换机制以及混合机制，并围绕高能量密度的有机介质体系锂离子电容器，着重阐述了各类电容及电池型正负极材料的性质特点、优化方向及其研究现状，指出不同材料的优缺点及改性方法。同时叙述了与产业应用相关的预嵌锂技术、隔膜、电解液以及体系匹配等方面的研究现状，总结归纳了这些部件的研究对于比能量、功率、安全、稳定性等性能的提升。在产业化应用方面，针对锂离子电容器不同于锂离子电池和传统超级电容器的性能指标，总结其在智能物流、起重机电源、机器人电源及轨道交通等方面独特的应用前景。最后展望了电极材料微观结构优化及功能集成、电解液专用化，预嵌锂成本进一步压缩、以及检测及原位表征方法的开发等锂离子电容器未来的发展方向。

关键词: 锂离子电容器, 电极材料, 预嵌锂, 体系匹配

Abstract:

The lithium ion capacitor (LIC) is a new type of electrochemical energy storage device. It can fill the performance gap between supercapacitors and lithium ion batteries. Therefore, it is the way forward for the next generation of high energy density supercapacitors. This review first introduces the energy storage mechanisms of LIC, which are divided into electrolyte consumption mechanism, lithium ion exchange mechanism and a hybrid mechanism. Then, it focuses on the research progress of lithium ion capacitor with high energy density in organic electrolyte systems and elaborates on the characteristics, optimization direction and research status of various types of cathode and anode materials. It also points out advantages and drawbacks as well as modification ways of different materials and describes the pre-lithiated technology, separators, electrolytes, and system matching, which are relevant to industrial applications and summarizes these aspects’ impacts on the improvement of the performances of LIC such as specific energy, power density, safety, stability, etc. The unique application prospects in intelligent equipment, energy recovery, transportation, are generalized according to LIC performance, which is better than those of LIBs and supercapacitors. Finally, it looks forward to the future development of electrode structure optimization and functional integration, electrolyte specialization, cost reduction of pre-lithiation, and development of detection and in-situ characterization methods.

Key words: lithium ion capacitor, electrode materials, pre-lithiation, system matching

中图分类号:

叶成玉,颜冬,陆安慧,李文翠. 有机介质体系锂离子电容器[J]. 化工进展, 2019, 38(03): 1283-1296.

Chengyu YE,Dong YAN,Anhui LU,Wencui LI. Lithium ion capacitors with organic electrolyte[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1283-1296.

图/表 3

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电极材料	电解液	电压/V	比能量/W·h·kg^-1	比功率/kW·kg^-1	文献
磷酸钒锂-炭//活性炭	LiPF₆-EC/DEC	1~3	27	0.325	[2]
活性炭//钛酸锂	LiPF₆-EC/DMC	1~3	69	0.38	[6]
活性炭//硬炭	LiPF₆-EC/DMC/DEC	2~4	110	5.7	[7]
活性炭//四氧化三铁	LiPF₆-EC/DEC	2~4.5	103.7	4.687	[8]
石墨烯//氧化石墨烯	LiPF₆-EC/DMC/DEC	1.8~4.2	148.3	7.8	[9]
多孔炭-石墨烯//石墨	LiPF₆-EC/DEC	2.2~4.2	80	352	[11]
硫氮共掺杂石墨烯//硫氮共掺杂石墨烯	LiPF₆-EC/DEC	1.5~4.5	143	13.548	[12]
介孔炭//二氧化锡-炭	LiPF₆-EC/DMC/EC	0~4.5	110	2.96	[14]
氟磷酸钴锂//活性炭	LiPF₆-EC/DMC	0~3	47	1.607	[17]
硅酸锰锂//多孔炭	LiPF₆-EC/DMC	0~3	54	1.5	[18]
活性炭//中间相碳微球	LiPF₆-EC/DEC	1.5~3.8	97.9	0.53	[22]
活性炭//硬炭	LiPF₆-EC/DEC	2~4	97.2	5.412	[23]
活性炭//硬炭	LiPF₆-EC/DMC/DEC	2~4	81.1	22.3	[24]
多孔石墨烯// 钛酸锂-炭	LiPF₆-EC/DMC	1~3	72	8.3	[26]
活性炭//钛酸锂-碳纳米管	LiPF₆-EC/DMC	1.5~2.8	84.2	0.195	[28]
多孔氮掺杂炭//氧化锰-石墨烯	LiPF₆-EC/EMC/DMC	1~4	83.25	25	[30]
活性炭//四氧化三铁-石墨烯	LiPF₆-EC/DMC/DEC	1~4	120	45.4	[31]
多孔炭//三氧化二铁@炭	LiPF₆-EC/DEC	1~4	65	9.2	[32]
多孔氮掺杂炭//四氧化三铁@炭	LiPF₆-EC/EMC/DMC	1~4	185	28	[33]
碳纳米片//氧化锰-炭	LiPF₆-EC/DMC	1~4	100	20	[34]
多孔炭//B-Si/SiO₂/C	LiPF₆-EC/DMC/DEC	2~4.5	128	9.704	[37]
活性炭//中间相碳微球	LiPF₆-EC/DMC/DEC	2~4	83.7	8.8	[41]
活性炭//石墨烯纳米片	LiPF₆-EC/EMC/DMC	2~4	61.7	0.222	[44]
石墨烯//钒酸锂-碳纳米纤维	LiClO₄-EC/DMC/DEC	0~3.8	110	3.87	[50]
磷酸铁锂-活性炭//钛酸锂-炭	LiPF₆-EC/DMC/DEC	0~3.2	124.6	0.46	[51]

电极材料	电解液	电压/V	比能量/W·h·kg^-1	比功率/kW·kg^-1	文献
磷酸钒锂-炭//活性炭	LiPF₆-EC/DEC	1~3	27	0.325	[2]
活性炭//钛酸锂	LiPF₆-EC/DMC	1~3	69	0.38	[6]
活性炭//硬炭	LiPF₆-EC/DMC/DEC	2~4	110	5.7	[7]
活性炭//四氧化三铁	LiPF₆-EC/DEC	2~4.5	103.7	4.687	[8]
石墨烯//氧化石墨烯	LiPF₆-EC/DMC/DEC	1.8~4.2	148.3	7.8	[9]
多孔炭-石墨烯//石墨	LiPF₆-EC/DEC	2.2~4.2	80	352	[11]
硫氮共掺杂石墨烯//硫氮共掺杂石墨烯	LiPF₆-EC/DEC	1.5~4.5	143	13.548	[12]
介孔炭//二氧化锡-炭	LiPF₆-EC/DMC/EC	0~4.5	110	2.96	[14]
氟磷酸钴锂//活性炭	LiPF₆-EC/DMC	0~3	47	1.607	[17]
硅酸锰锂//多孔炭	LiPF₆-EC/DMC	0~3	54	1.5	[18]
活性炭//中间相碳微球	LiPF₆-EC/DEC	1.5~3.8	97.9	0.53	[22]
活性炭//硬炭	LiPF₆-EC/DEC	2~4	97.2	5.412	[23]
活性炭//硬炭	LiPF₆-EC/DMC/DEC	2~4	81.1	22.3	[24]
多孔石墨烯// 钛酸锂-炭	LiPF₆-EC/DMC	1~3	72	8.3	[26]
活性炭//钛酸锂-碳纳米管	LiPF₆-EC/DMC	1.5~2.8	84.2	0.195	[28]
多孔氮掺杂炭//氧化锰-石墨烯	LiPF₆-EC/EMC/DMC	1~4	83.25	25	[30]
活性炭//四氧化三铁-石墨烯	LiPF₆-EC/DMC/DEC	1~4	120	45.4	[31]
多孔炭//三氧化二铁@炭	LiPF₆-EC/DEC	1~4	65	9.2	[32]
多孔氮掺杂炭//四氧化三铁@炭	LiPF₆-EC/EMC/DMC	1~4	185	28	[33]
碳纳米片//氧化锰-炭	LiPF₆-EC/DMC	1~4	100	20	[34]
多孔炭//B-Si/SiO₂/C	LiPF₆-EC/DMC/DEC	2~4.5	128	9.704	[37]
活性炭//中间相碳微球	LiPF₆-EC/DMC/DEC	2~4	83.7	8.8	[41]
活性炭//石墨烯纳米片	LiPF₆-EC/EMC/DMC	2~4	61.7	0.222	[44]
石墨烯//钒酸锂-碳纳米纤维	LiClO₄-EC/DMC/DEC	0~3.8	110	3.87	[50]
磷酸铁锂-活性炭//钛酸锂-炭	LiPF₆-EC/DMC/DEC	0~3.2	124.6	0.46	[51]

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