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    二维膜电极组件电解池中CO2电催化还原模拟研究

    Simulation of electrocatalytic CO2 reduction in an electrolyzer with 2D membrane electrode assembly

    • 摘要: 电催化CO2还原反应(eCO2RR)技术由于具有温和可控的反应条件且能够与清洁可再生能源相结合而具有广阔的发展前景。其中膜电极组件(MEA)电解池由于其紧密的结构、较高的能量效率以及低欧姆损耗,具有工业化应用的潜力。然而,现有的eCO2RR数字模型研究往往未能充分考虑溶液中酸碱平衡反应对电化学过程的影响,缺乏对气体扩散层(GDL)厚度以及催化剂层(CL)孔隙率的深入探讨。通过对流场、电化学反应、酸碱平衡反应、浓度场等多物理场的建立和耦合对MEA电解池进行几何建模,成功搭建了一个二维MEA电解池的动态综合模型,并利用此模型探究电解池中化学反应的不均匀分布现象、GDL厚度以及CL孔隙率对MEA电解池系统的影响。模拟结果揭示了不平衡的酸碱反应导致阴极区域出现局部pH波动,引发局部化学环境的变化,导致CL沿流道方向上电流密度分布不均。此外,GDL厚度和CL孔隙率的变化对气体传输和电极反应产生显著影响,改变原料和产物的分布以及产物产量。当GDL厚度从100 μm增加到400 μm时,CO总产量从7.01×10−14 mol增加到7.62×10−14 mol。但阴极流道中CO所占比例明显下降,影响产物的收集。当GDL厚度大于350 μm时,流道中CO含量呈现下降趋势。随着CL的孔隙率从0.3增加到0.8,CL中CO的产量增加到近3倍,但随之增强的析氢反应降低了CO的选择性。提出的二维动态MEA模型和对eCO2RR性能的探究有助于后续CO2还原电解池的设计与开发。

       

      Abstract: The electrocatalytic CO2 reduction reaction (eCO2RR) technology is promising due to its mild and controllable reaction conditions, and its compatibility with renewable energy sources. In particular, membrane electrode assembly (MEA) electrolytic cells, with their compact structure, high energy efficiency and low ohmic losses, have the potential for industrial applications. However, current numerical modeling studies of eCO2RR often overlook the influence of acid-base equilibrium reactions in solution on the electrochemical process, and lack performance. By geometrically modeling the MEA electrolytic cell, establishing and coupling the flow field, in-depth exploration of the role of gas diffusion layer (GDL) thickness and catalyst layer (CL) porosity on the system electrochemical reaction, acid-base equilibrium reaction, concentration field and other multi-physical fields, a dynamic and comprehensive model of a two-dimensional MEA electrolytic cell was successfully built. This model was utilized to explore the effects of the inhomogeneous distribution phenomenon of chemical reactions in the electrolytic cell, the thickness of the GDL, and the CL porosity on the MEA electrolytic cell system. Simulation indicate that unbalanced acid-base reactions cause localized pH fluctuations in the cathode region, altering the local chemical environment and leading to an inhomogeneous current density distribution along the flow path in CL. Furthermore, variations in GDL thickness and CL porosity significantly influence gas transport and electrode reaction, changing the feedstock distribution, products distribution and product yields. As the GDL thickness increased from 100 μm to 400 μm, the total CO production increased from 7.01×10−14 mol to 7.62×10−14 mol, but the proportion in the cathode flow channel decreased significantly, which was unfavourable for product collection. When the GDL thickness was greater than 350 μm, the CO content in the flow channel showed a decreasing trend. As the CL porosity increased from 0.3 to 0.8, the CO yield in the CL increased to nearly triple, but the enhancement of the hydrogen precipitation reaction was detrimental to the product selectivity. The proposed two-dimensional dynamic MEA model and the insights into the performance of eCO2RR offer valuable contributions to the design and development of future electrolyzers.

       

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