氧化还原液流电池碳基复合双极板材料研究进展

doi:10.19894/j.issn.1000-0518.240125

摘要/Abstract

摘要：

随着可再生能源的迅速发展，氧化还原液流电池作为一种容量高、灵活性好、扩展性强和循环使用寿命长的可再生能源储存系统，备受行业关注。其中，双极板作为氧化还原液流电池电堆的重要组成部分，发挥着支撑电极、传导电流、连接电池、支持电堆和分离正负极电解液等作用。由于所处的工作环境苛刻，双极板应同时具备导电性高、机械性能好、耐腐蚀性好、渗透性低和化学稳定等特点。因此，开发低成本的高性能双极板，已经成为液流电池发展的关键要素之一。本文将重点介绍氧化还原液流电池中碳基复合双极板近年来的发展现状，涵盖了不同流场设计、不同碳基材料和聚合物材料的选择等对双极板导电性能、机械性能、抗渗透性能、抗腐蚀性能和单电池性能的影响情况。最后，基于碳基复合双极板目前发展的需求及关键技术瓶颈做了简要分析和展望。

关键词: 氧化还原液流电池, 双极板, 碳基复合材料

Abstract:

With the rapid development of renewable energy， redox flow battery， as a renewable energy storage system with high capacity， good flexibility， strong scalability and long cycle life， has attracted much attention in the industry. The bipolar plate， as an important part of redox flow battery stack， plays the role of supporting electrode， conducting current， connecting battery， supporting stack and separating positive and negative electrolyte. Due to the harsh working environment， the bipolar plate should have the characteristics of high electrical conductivity， good mechanical properties， good corrosion resistance， low permeability and chemical stability. Therefore， the current development of low-cost high-performance bipolar plates has become one of the key elements of the development of flow batteries. This paper focuses on the recent development status of carbon composite bipolar plates in redox flow batteries since 2010， including the influence of different flow field designs， different carbon-based materials and polymer materials on the conductivity， mechanical properties， permeability resistance， corrosion resistance and single battery performance. Finally， based on the current development requirements and key technical bottlenecks of carbon based composite bipolar plates， a brief analysis and outlook are made.

Key words: Redox flow battery, Bipolar plate, Carbon-based composites

中图分类号:

O632

杨晓莹, 张保华, 蓝叶滢, 张玉微. 氧化还原液流电池碳基复合双极板材料研究进展[J]. 应用化学, 2024, 41(10): 1381-1398.

Xiao-Ying YANG, Bao-Hua ZHANG, Ye-Ying LAN, Yu-Wei ZHANG. Research Progress of Carbon Based Composite Bipolar Plate Materials for Redox Flow Batteries[J]. Chinese Journal of Applied Chemistry, 2024, 41(10): 1381-1398.

图/表 12

图1 氧化还原液流电池示意图

Fig.1 Schematic drawings of redox flow battery

图2 软层法：（A）压缩成型；（B）试样表面［20］

Fig.2 Soft layer method：（A） compression molding；（B） surface of the fabricated specimen［20］

图3 VRFB中使用的不同类型流场（FF）的示意图

Fig.3 Schematic of the different types of flow fields （FF） used in the VRFB

图4 （A）分级交错流场设计和（B）常规交错流场设计的示意图［27］

Fig.4 Schematic of （A） hierarchical interdigitated flow field design and （B） conventional interdigitated flow field design［27］

图5 双极板平面内电导率（A）和垂直平面电导率（B）测量示意图

Fig.5 （A） In-plane and （B） through-plane electrical conductivity measurement setup for BPPs

图6 复合材料电导率。（A）主要填充类型与总填充质量分数对复合材料电导率的影响（其中次要填充填料质量分数固定在6%），以及在（B）次要填充类型与总填充质量分数对复合材料电导率的影响（KB：ketjenblack carbon）［36］

Fig.6 Electrical conductivity of the composites. Effect on （A） major filler types versus total filler contents， in which minor filler contents were fixed to 6%， and （B） minor filler types versus total filler contents （KB： ketjenblack carbon）［36］

图7 气体渗透性测量装置的原理图［46］

Fig.7 Schematic diagram of the device for measuring a gas permeability［46］

图8 3D-石墨/环氧复合材料BP的制备工艺示意图［56］

Fig.8 Schematic diagram of fabrication process of the 3D-graphite/epoxy composite BP［56］

图9 碳/聚乙烯复合材料CFE集成BP与传统石墨双极板的充放电效率［61］

Fig.9 Charge/discharge efficiencies of the carbon/PE composite BP with CFE integration and the conventional graphite bipolar plate［61］

图10 （A） PP-弹性体/PP/炭黑/碳纤维复合材料集流体的VRFB单电池在电流密度为70 mA/cm2时的循环性能；（B）含有PP-弹性体/PP/炭黑/碳纤维复合材料集流体的VRFB电池堆栈在电流密度为50 mA/cm2时的循环性能［63］

Fig.10 （A） Cycling performance of a VRFB single cell equipped with current collectors of the PP-elastomer/PP/carbon black/carbon fiber composite at a current density of 70 mA/cm2；（B） Cycling performance of a VRFB cell stack equipped with current collectors of the PP-elastomer/PP/carbon black/carbon fiber composite at a current density of 50 mA/cm2［63］

图11 含有石墨集流器的VRFB电池堆栈在电流密度为50 mA/cm2时的循环性能［63］

Fig.11 Cycling performance of a VRFB cell stack equipped with graphite current collectors at a current density of 50 mA/cm2［63］

图12 展丝，UD和商用石墨双极板的单电池测试结果。（A）对应的充/放电图；（B）能量效率，库伦效率和电压效率［66］

Fig.12 Single cell test results of spread-tow， UD， and commercial graphite bipolar plates. （A） Representative charge/discharge graphs；（B） Energy efficiencies， coulombic efficiencies and voltage efficiencies［66］

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