基于3D固态负极的铁铅单液流电池研究

doi:10.6023/A21090440

摘要/Abstract

低成本的大规模电化学储能技术对于清洁可再生能源的高效利用具有重要意义. 设计了一种3D结构的铅负极, 并在此基础上构建了铁铅单液流电池. 其中采用硫酸亚铁/硫酸铁和铅/硫酸铅分别作为电池的正、负极活性物质, 硫酸水溶液为电解液. 负极采用高导电的乙炔黑构建了具有多孔结构的导电网络, 并通过加入硫酸钡或腐殖酸等添加剂显著提升了电池性能. 该电极的设计可以有效避免负极枝晶、析氢和不可逆硫酸化等问题. 通过对乙炔黑含量的研究发现, 负极中乙炔黑含量为活性物质质量的12.5%时, 电池显示出最佳性能, 能显著提高电池的能量效率、活性物质利用率和倍率性能. 在20 mA/cm²的电流密度下, 负极比容量可以达到89.3 mAh/g, 电流效率与能量效率分别达到了99.3%和88.6%, 且有稳定的循环性能. 此外, 此电池活性物质的估算成本仅为53.27 $/kWh, 在各种储能电池体系中具有成本优势, 因此作为低成本大规模电化学储能的电池技术, 铁铅单液流电池具有较好的研究前景.

关键词: 铁铅电池, 液流电池, 大规模储能, 电化学储能, 水系电池

Low-cost large-scale electrochemical energy storage technology is of great significance for the efficient use of clean and renewable energy such as solar and wind energy. In this work, a 3D lead electrode is designed as a high-performance negative electrode, and an iron-lead (Fe-Pb) semi-flow battery is constructed on this basis. The positive and negative active materials of the battery are ferrous sulfate/iron sulfate and lead/lead sulfate respectively, and sulfuric acid aqueous solution is used as the supporting electrolyte. The negative electrode uses acetylene carbon black (ACET) as an effective additive to form a highly conductive network with a porous structure, and the performance of the battery can be significantly improved by adding ACET in the native electrode. Moreover, benefiting from the novel design of the battery, problems of metal dendrites, hydrogen evolution and irreversible sulfation of the Pb electrode can be avoided. The results show that the introduction of ACET in the negative electrode as a conductive agent can effectively improve the energy efficiency, the utilization rate of the active material of the negative electrode and the rate performance of the battery. The effect of the ACET content on the performance including the current efficiency, voltage efficiency and energy efficiency of the battery has been studied. It is illustrated that an ACET mass content of 12.5% over the active materials in the negative electrode is preferred. At a current density of 20 mA/cm², the specific capacity of the negative electrode can reach 89.3 mAh/g, the battery current efficiency and energy efficiency can reach 99.3% and 88.6%, respectively. Cycling stability of the Fe-Pb semi-flow battery is also investigated in this work. The result shows that the designed battery has excellent cycling stability during the stability test. In addition, the estimated cost of the active material for this battery can be as low as 53.27 $/kWh, which is lower than most of the other energy storage battery systems. Therefore, as a low-cost large-scale electrochemical energy storage battery technology, the iron-lead semi-flow battery has a good research prospect.

Key words: iron-lead battery, flow battery, large-scale energy storage, electrochemical energy storage, aqueous battery

引用此文

张竹涵, 蒋峰景, 吴珂科, 申鹏. 基于3D固态负极的铁铅单液流电池研究[J]. 化学学报, 2022, 80(1): 56-62.

Zhuhan Zhang, Fengjing Jiang, Keke Wu, Peng Shen. Research on Iron-Lead Semi-Flow Battery Based on 3D Solid Electrode[J]. Acta Chimica Sinica, 2022, 80(1): 56-62.

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图/表 8

图1. 铁铅单液流单电池结构示意图

Figure 1. Schematic diagram of the iron-lead semi-flow single battery

图2. FeSO4溶液与含有或不含有乙炔炭黑的负极CV曲线

Figure 2. CV curves of FeSO4 solution and negative electrode with and without ACET

图3. 含有10%乙炔炭黑的负极电极(a~c)和(d)不含乙炔炭黑的负极电极的扫描电镜图像

Figure 3. SEM images of (a~c) negative electrode with 10% ACET and (d) negative electrode without ACET (a) Zoom in 5000 times; (b) Zoom in 20000 times; (c) Zoom in 50000 times

图4. 负极中含有乙炔炭黑和不含乙炔炭黑的电池的(a) 20 mA/cm2电流密度时充放电曲线和(b)阻抗曲线

Figure 4. (a) Charge and discharge curves of battery with and without ACET in negative electrode at 20 mA/cm2 and (b) Nyquist plots of battery with and without ACET in negative electrode

图5. 负极中乙炔炭黑含量为10%的单电池20 mA/cm2电流密度下的电流效率、电压效率、能量效率和放电比容量

Figure 5. Coulombic efficiency, voltage efficiency, energy efficiency and specific discharge capacity of single battery with 10% ACET in negative electrode at 20 mA/cm2

图6. (a)不同电流密度条件下的电池比容量和(b)不同电流密度条件下的电池电流效率、电压效率和能量效率

Figure 6. (a) Specific discharge capacity at various current density and (b) coulombic efficiency, voltage efficiency and energy efficiency at various current density

图7. 不同乙炔炭黑含量的电池在20 mA/cm2条件下的(a)电流效率、电压效率、能量效率和(b)放电比容量

Figure 7. (a) Coulombic efficiency, voltage efficiency, energy efficiency and (b) specific discharge capacity at 20 mA/cm2 of battery with different ACET content

图8. 负极中乙炔炭黑含量为12.5%的单电池在100个循环测试中的电流效率、电压效率、能量效率和放电比容量

Figure 8. Coulombic efficiency, voltage efficiency, energy efficiency and specific discharge capacity of the single cell with 12.5% ACET in the negative electrode during 100-cycle stability test

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