物理化学学报 >> 2022, Vol. 38 >> Issue (6): 2106008.doi: 10.3866/PKU.WHXB202106008

所属专题: 面向电化学储能与转化的表界面工程

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提升液流电池能量密度的策略

从广涛1,*(), 卢怡君2,*()   

  1. 1 深圳大学化学与环境工程学院,低维材料基因工程研究院,广东 深圳 518060
    2 香港中文大学机械与自动化工程系,电化学能源与界面实验室,香港 999077
  • 收稿日期:2021-06-02 录用日期:2021-07-01 发布日期:2021-07-07
  • 通讯作者: 从广涛,卢怡君 E-mail:gtcong@szu.edu.cn;yichunlu@mae.cuhk.edu.hk
  • 作者简介:Guangtao Cong received his Ph.D.degree in Mechanical and Automation Engineering from The Chinese University of Hong Kong (CUHK) in 2018. Dr.Cong worked as a research associate under the supervision of Prof.Yi-Chun Lu at CUHK before he joined the College of Chemistry and Environmental Engineering at Shenzhen University as an Assistant Professor.Dr.Cong's research interests focus on organic electrodes.
    Prof. Yi-Chun Lu received her B.S. degree in Materials Science & Engineering from National Tsing Hua University, Taiwan in 2007 and earned her Ph.D. degree in Materials Science & Engineering from Massachusetts Institute of Technology in 2012. Prof. Lu worked as a Postdoctoral Fellow in the Department of Chemistry at the Technische Universität München, Germany in 2013. She is currently an Associate Professor of Mechanical and Automation Engineering at The Chinese University of Hong Kong. Prof. Lu’s research interest centers on fundamental redox chemistry and developing functional materials for clean energy storage and conversion

Strategies to Improve the Energy Density of Non-Aqueous Organic Redox Flow Batteries

Guangtao Cong1,*(), Yi-Chun Lu2,*()   

  1. 1 Institute of Low-dimensional Materials Genome Initiative, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, China
    2 Electrochemical Energy and Interfaces Laboratory, Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, Shatin, N.T. 999077, Hong Kong SAR, China
  • Received:2021-06-02 Accepted:2021-07-01 Published:2021-07-07
  • Contact: Guangtao Cong,Yi-Chun Lu E-mail:gtcong@szu.edu.cn;yichunlu@mae.cuhk.edu.hk
  • About author:Email: yichunlu@mae.cuhk.edu.hk (Y.L.)
    Email: gtcong@szu.edu.cn (G.C.)
  • Supported by:
    the Science and Technology Innovation Commission of Shenzhen, China(JCYJ20190808114803804);the Science and Technology Innovation Commission of Shenzhen, China(20200812104042001);the Research Grant Council (RGC) of the Hong Kong Special Administrative Region, China(T23-601/17-R)

摘要:

液流电池因为具有高储能效率,低成本,以及可解耦的能源储存和功率输出设计,被广泛认为是适用于大型储能的首选技术。但是长期以来,液流电池在电网中的大规模部署一直受限于现有的金属基活性材料的高成本和较低的储能密度。因其潜在的低成本,丰富的原材料来源,高度可调的分子结构,具有氧化还原活性的有机分子作为潜在的液流电池活性材料,受到越来越多的关注。本文首先介绍了液流电池的工作机制,以提升非水系有机液流电池的储能密度的策略为重点,总结了非水系液流电池中有机活性材料的研究进展。并讨论了这些策略存在的问题和未来的发展方向。

关键词: 具有氧化还原活性的有机分子, 液流电池, 储能密度, 功率输出密度

Abstract:

Redox flow batteries (RFBs) have been widely recognized as the primary choice for large-scale energy storage due to their high energy efficiency, low cost, and versatile design of decoupled energy storage and power output. However, the broad deployment of RFBs in the power grid has long been plagued by the high cost and low energy density of existing inorganic metal-based electrodes. Redox-active organic molecules (ROMs), on the other hand, have recently been extensively explored as the potentials electrodes in RFBs for their potential low cost, abundant resources, and highly tunable structure. The energy density of RFBs is proportional to the number of electrons transferred per unit reaction, the concentration of active materials, and the cell voltage. Therefore, strategies to improve the energy density of RFBs could be categorized into three classes: (1) expanding the cell voltage; (2) maximizing the practical concentration of active materials; (3) realizing multi-redox process. Benefited by the highly tunable structure and properties of ROMs, the cell voltage of RFBs could be realized by lowering the redox potentials of anolytes or/and increasing the redox potentials of catholytes. To fully exploit the low-potential anolytes and high-potential catholytes, non-aqueous electrolytes with wider electrochemical potential windows (EPWs) are preferred over the aqueous systems. However, the solubility of most ROMs in commonly used non-aqueous electrolytes is very limited. Several effective strategies to improve the practical concentrations of ROMs have been proposed: (1) the solubility of ROMs could be easily tailored by adjusting the intermolecular interactions between ROMs and the interactions between ROMs and electrolytes via molecular engineering; (2) the redox-active eutectic systems remain liquid at or near room temperature, allowing us to reduce or completely remove the inactive solvent used in the conventional electrolyte of RFBs, which leads to an enhanced practical concentration of the redox-active components; (3) the semi-solid suspension achieves a high practical concentration of ROMs by combining the advantages of solid ROMs with high energy density and liquid electrolytes with flowability; (4) the redox-targeting approach breaks the solubility limitation by realizing remote charge exchange between the solid active materials deposited in the tanks and the current collectors of the electrochemical stacks via ROMs dissolved in electrolytes. The first three strategies employ a homogeneous flowing redox-active fluid which suffers from deteriorated physical and electrochemical properties as the practical concentration of ROMs increase, e.g., high viscosity, phase separation, and salt precipitation. The redox-targeting approach uses a hybrid flowing liquid/static solid system, which avoids the aforementioned unfavorable changes in electrolyte properties, however, this design introduces additional chemical reactions between the ROMs and the solid active materials, which may reduce the power output. Another efficient method to improve the energy density of RFBs without affecting the properties of the electrolyte is achieved by realizing the multi-redox process of ROMs, however, the generated high valence state ROMs are highly reactive. Further optimization of the structure of these ROMs is required to improve their lifetime at high valence states. In this perspective, we summarize the general working principle of the RFBs, highlight the recent developments of the ROMs in non-aqueous redox flow batteries (NRFBs), with an emphasis on the strategies to improve the energy density of NRFBs, and discuss the remaining challenges and future directions of the non-aqueous organic redox flow batteries (NORFBs).

Key words: Redox-active organic molecule, Flow battery, Energy density, Power output

MSC2000: 

  • O646