干法电极技术在超级电容器和锂离子电池中的研究进展

doi:10.19799/j.cnki.2095-4239.2024.0997

摘要/Abstract

摘要：

干法电极技术因其具有无溶剂、制造成本低、电极机械强度高和对环境友好等优点，被认为是未来高性能储能器件开发中的关键技术。本文分析了干法电极技术的原理，归纳总结了干法电极制备中常用粘结剂的性质和应用，阐述了干法电极技术的优点，回顾了干法电极技术的起源和发展历程，介绍了干法电极技术在超级电容器和锂离子电池领域的研究进展。从工艺原理、研究进展、关键设备、关键工艺参数及优缺点对比，重点论述了6种干法电极工艺技术：聚合物纤维化、干法喷涂沉积、气相沉积、热熔挤压、直接压制和3D打印。结果说明目前大规模干电极制造工艺仍存在挑战，现有工艺都存在生产规模小、所需原料需特殊处理以及与现有产线不兼容等共性问题。最后总结了干法电极技术在锂离子电池和超级电容器领域的未来研究方向：开发新型粘结剂、优化干混工艺、调节电极质量负载、优化生产路线和探索新的工艺。本文可为相关领域的科研工作者和技术人员工作的开展提供参考，也为干法电极技术在超级电容器和锂离子电池领域的发展提供方向指导。

关键词: 锂离子电池, 超级电容器, 电极制备, 干法电极

Abstract:

Dry electrode technology is recognized as a pivotal technology in the development of high-performance energy storage devices in the future due to its solvent-free, low manufacturing cost, high mechanical strength of electrodes, and environmental friendliness. This paper analyzes the principles of dry electrode technology, summarizes the properties and applications of commonly used binders in the preparation of dry electrodes, elucidates the advantages of dry electrode technology, reviews its origin and development history, and introduces the research progress of dry electrode technology in the fields of supercapacitors and lithium-ion batteries. Focusing on six dry electrode process technologies: polymer fibrillation, dry spray deposition, vapor deposition, hot-melt extrusion, direct pressing, and 3D printing, this paper discusses them in detail from the aspects of process principles, research progress, key equipment, critical process parameters, and comparisons of advantages and disadvantages. The results indicate that challenges still exist in the current large-scale manufacturing processes of dry electrodes, and common issues such as small production scale, special raw material treatment requirements, and incompatibility with existing production lines are prevalent in existing processes. Finally, the future research directions of dry electrode technology in the fields of lithium-ion batteries and supercapacitors are summarized: developing new binders, optimizing dry mixing processes, adjusting electrode mass loading, optimizing production routes, and exploring novel processes. This paper provides a reference for researchers and technicians in related fields and offers directional guidance for the development of dry electrode technology in the fields of supercapacitors and lithium-ion batteries.

Key words: lithium ion battery, supercapacitor, electrode preparation, dry electrode

中图分类号:

TM533

徐桂培, 刘浩, 赖洁文, 卢毅锋, 黄辉, 邸会芳, 王振兵. 干法电极技术在超级电容器和锂离子电池中的研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2024.0997.

Guipei Xu, Hao Liu, Jiewen Lai, Yifeng Lu, Hui Huang, Huifang Di, Zhenbing Wang. Research Progress of Solvent-free Electrode Technology for Supercapacitor and Lithium-ion Battery[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2024.0997.

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粘结剂	阳极稳定性	阴极稳定性	适用的干法电极技术	使用温度	粘结剂属性	参考文献
聚四氟乙烯（PTFE）	不稳定	稳定	聚合物纤维化	25 ℃-80 ℃	机械变形	^{[22, 23]}
聚偏二氟乙烯（PVDF）	部分稳定	稳定	干粉喷涂沉积	>80 ℃	热塑性	^{[21, 24]}
聚环氧乙烷	部分稳定	电位大于4 V不稳定	热熔挤压，3D打印	150 ℃-170 ℃	热塑性	^{[25, 26]}
聚丙烯	稳定	稳定	热熔挤压	160 ℃-190 ℃	热塑性	^{[27, 28]}
聚碳酸丙烯酯+氢化丁腈橡胶	不稳定	稳定	直接压制	40 ℃-90 ℃	热塑性	^{[29, 30]}

	湿法电极技术	干法电极技术	参考文献
成本	电极干燥/溶剂NMP回收相关成本（47%）、材料成本（溶剂占比1%-2%）	不使用溶剂NMP，无电极干燥和溶剂回收相关成本，总成本降低15%	^{[24, 31, 32]}
对环境的影响	有毒溶剂，能耗高，二氧化碳排放量大	无溶剂，能耗更低，每生产10 kWh的二氧化碳排放量减少1000 kg	^{[33, 34]}
生产效率	7个步骤，干燥、溶剂回收耗时长（大于3小时）	5个步骤，无需干燥时间，生产时间减少16.2%-21.4%	^{[24, 35]}
能量消耗	约47%的总能耗用于干燥和溶剂回收，每生产10 kWh，干燥和溶剂回收耗电420 Wh	无干燥和溶剂回收过程，能源成本降低38%-40%	^{[35, 36]}
兼容性	不适用于厚电极和固态电极的制备	在制备厚电极方面具有显著优势，可用于预锂化，可制备全固态电池的电极	^{[37, 38]}
电极性能	厚电极中的粘合剂表现出梯度变化，颗粒粘附性较差（<4 mAh/cm²），更高的孔隙率（4%-10%）	特定粘合剂分布，倍率性能提高，孔隙率降低，颗粒粘附的更好（>5 mAh/cm²），电极机械强度显著提高	^{[23, 39]}

干法技术	技术原理	优势	弊端	应用领域
聚合物纤维化	PTFE在高剪切力作用下纤维化	与现有的生产线兼容，可大规模生产	阳极不稳定，目前只能采用PTFE作为粘结剂	阴极，碳阳极，全固态电池的电极
干法喷涂沉积	干粉混合物在高压下沉积	电极厚度和密度可控，可用于柔性电极	设备昂贵，生产环境要求高	阳极，阴极
气相沉积	材料先蒸发汽化再沉积	多种汽化方法可选择	生产设备昂贵，规模扩大较难实现	小尺寸电极
热熔挤压	颗粒混合、挤出、脱粘和烧结	可制备厚电极	工艺复杂，能耗高，需要牺牲粘结剂	用于大规模生产的阴极，碳阳极
直接压制	活性材料充分混合后直接压制为电极	操作简单，粘结剂用量小	生产规模小，需要活性材料可压缩	阴极，阳极，全固态电池电极
3D打印	材料熔融后逐层打印	电极厚度和形貌可定制	设备昂贵，生产规模小，活性材料含量低	微电子和可穿戴设备用电极

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