Non-Isothermal Operation of Membrane Electrode Assembly-Based CO2 Electrolyzer for Enhanced Energy Efficiency
Authors: Li Jieyang , Luo Changhao , Zhang Huanlei , Xu Wanping , Lin Meng 
Published: August 2024

The utilization of membrane electrode assemblies (MEA) in carbon dioxide (CO2) electrochemical conversion showcases the promising potential for stable and scalable industrial applications in fuel production, attributed to efficient gas diffusion and minimized system resistance. The electrochemical performance of MEA-based CO2 electrolyzers relies on the chemical reactivity and product selectivity optimization which is dependent on three factors: CO2 mass transport, charge transport, and ionic transport. Elevating the overall system temperature benefits the performance of the oxygen evolution reaction (OER) at the anode. Furthermore, the elevated temperature enables higher conductivity of anion exchange membranes (AEM), thereby further diminishing cell voltage. However, the downside emerges as CO2 solubility decreases at higher temperatures, fostering a scenario where the catalytic reaction leans toward hydrogen evolution, thereby undermining product selectivity.
Herein, we propose an innovative approach involving thermal management for separate temperature control for the anode and cathode, forming a non-isothermal MEA by maintaining an elevated anodic temperature while cooling the cathode. This approach simultaneously addresses the need for a high-temperature anode and a low-temperature cathode. This study exhibits a temperature gradient of approximately 20°C between the anodic and cathodic planes achieved through efficient thermal modulation of water cooling and heating within the electrode plates.
We showcase the benefit of non-isothermal operation with an Ag-based cathode and IrO2-based anode using 1 M KOH as the anolyte for CO2 conversion into CO. The non-isothermal condition, i.e., maintaining an anodic temperature of 80°C and a cathode temperature of 60oC, demonstrated a 65% enhancement in CO partial current density (j
co), 195.6 mA cm-2, compared to the isothermal 80°C condition, 118.6 mA cm-2. The optimal performance across all temperature regimes is found to be the non-isothermal condition with anode temperature at 60°C and cathode temperature at 40 oC, yielding a j
co of 243.5 mA cm-2 at 3.25 V, marking a 13.3% improvement over the isothermal 60°C condition (j
co = 214.9 mA cm-2). The increase in the j
co can be attributed to the lower temperature at the cathode (40 oC for the non-isothermal condition vs. 60oC for the isothermal ccondition) resulting in higher CO faradaic efficiency.The CO faradaic efficiency remained above 80% (cell potential < 2.7V) for the non-isothermal 60°C condition, whereas it dropped below 80% throughout the entire region cell potential range for the isothermal 60°C condition. This study presents a novel non-isothermal operation for advanced thermal management for MEA-based CO2 electrolyzers for simultaneous enhancement in anode activity as well as cathode selectivity. We believe this thermal management strategy is promising for engineering high-performing MEA-based CO2 electrolyzers at industrial scales.