Dunne Harry, Liu Weiming, Ghaani Mohammad Reza, McKelvey Kim, Dooley Stephen
School of Physics, Trinity College Dublin, Dublin D02 PN40, Ireland.
MacDiarmid Institute for Advanced Materials and Nanotechnology and School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington 6012, New Zealand.
J Phys Chem C Nanomater Interfaces. 2024 Jun 27;128(27):11131-11144. doi: 10.1021/acs.jpcc.4c00690. eCollection 2024 Jul 11.
Electrochemical (EC) carbon dioxide (CO) reduction, where CO is converted to value-added products such as fuel precursors, plays a key role in helping the world's energy system reach net-zero carbon emissions. Simulations of EC cells provide valuable insight into their operation since detailed experimental results on short length and time scales are difficult to obtain. In this work, we construct a 1D simulation of a membrane-electrode-assembly EC cell for CO reduction, using a porous silver gas diffusion cathode. We run the simulation under different electrolyte conditions, showing how the cell performance is affected. We then perform a sensitivity analysis of all input parameters to the simulation, which has not been presented before in the literature. We show that the CO partial current density ( ) is significantly affected by each input parameter of the simulation. is most sensitive to EC kinetic parameters ( /α) of all EC reactions, with a 1% change in α resulting in up to 6% change in . Since there is uncertainty associated with the value of each input parameter, this indicates that infidelity between experiment and simulation is likely, and thus, caution should be practiced when comparing experimental results to simulation results. Further, we show that the large range of conditions simulated in literature helps to explain the large variance in reported values of and α. The results of this paper demonstrate the potential of sensitivity analysis methods to quickly optimize aspects of cell performance (CO utilization, Faradaic efficiency, etc.).
电化学（EC）二氧化碳（CO₂）还原可将CO₂转化为增值产品，如燃料前驱体，在帮助全球能源系统实现净零碳排放方面发挥着关键作用。由于难以在短长度和时间尺度上获得详细的实验结果，EC电池的模拟为其运行提供了有价值的见解。在这项工作中，我们使用多孔银气体扩散阴极构建了用于CO₂还原的膜电极组件EC电池的一维模拟。我们在不同的电解质条件下运行模拟，展示了电池性能是如何受到影响的。然后，我们对模拟的所有输入参数进行了敏感性分析，这在之前的文献中尚未有过报道。我们表明，CO₂的分电流密度（jCO₂）受到模拟的每个输入参数的显著影响。jCO₂对所有EC反应的EC动力学参数（k/α）最为敏感，α值1%的变化会导致jCO₂变化高达6%。由于每个输入参数的值都存在不确定性，这表明实验与模拟之间可能存在偏差，因此，在将实验结果与模拟结果进行比较时应谨慎。此外，我们表明文献中模拟的大范围条件有助于解释报道的jCO₂和α值的巨大差异。本文的结果证明了敏感性分析方法在快速优化电池性能（CO₂利用率、法拉第效率等）方面的潜力。
