Current state-of-the-art carbon dioxide (CO2) capture systems are often implemented at large scale thermal power plants and industrial facilities due to their capital-intensive designs.1 However, there are many smaller scale applications for CO2 separation, such as from commercial buildings, airplanes, and/or submarines, that could benefit from scalable technologies with lower energy requirements. Consequently, 2-stage electrochemical CO2 separators have been proposed as systems with the potential to achieve high energy efficiencies and to operate at the compact sizes required for space-constrained applications.2 While electrochemical capture systems most similar to thermochemical capture systems employ separation units such as absorption columns and flash tanks in addition to the electrochemical reactor, the envisioned 2-stage process combines the activation step with CO2 absorption and the deactivation step with CO2 desorption, all within a single unit. Unfortunately, experimental studies have thus far shown these devices cannot support high current densities and exhibit considerable losses. Understanding and mitigating these losses is key to improving the performance of these separators. Here, we develop a two-dimensional cell model to simulate the capture and release of CO2 from a 2-stage electrochemical separator with freely-solubilized, redox-active capture molecules. We first discuss the governing equations within the model and, using representative redox couples, we experimentally validate that the model can adequately predict voltage–current relationships. Through this validation, we observe that electrode reactions generate concentration gradients that induce natural convection within the device, enabling higher than expected current densities. To maximize the benefits of natural convection, we then explore the impacts of capture species and electrolyte properties, cell design, and operating conditions on performance by experimentally and computationally varying redox species concentrations, cell orientation, and electrode dimensions. Finally, we incorporate the CO2 binding/release reactions to predict the effect of natural convection on CO2 capture and release. We find that density gradients within the cell also impact the CO2 back-flux from the higher concentration anode to the lower concentration cathode, affecting the separation flux and minimum work. We anticipate that this model will support electrochemical reactor design campaigns leading to higher-performing devices for a range of CO2 separation applications. References M. Wang, A. Lawal, P. Stephenson, J. Sidders, and C. Ramshaw, Chem Eng Res Des, 89, 1609–1624 (2011). L. E. Clarke, M. E. Leonard, T. A. Hatton, and F. R. Brushett, Ind Eng Chem Res, 61, 10531–10546 (2022).
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