Effect of Operating Temperature and Pressure on the Limiting Current Density of PEM Electrolysis Cell Based on Theoretical Prediction Model and Experiments

Abstract

Introduction The PEM electrolysis cell (PEMEC) exhibits great potential to produce hydrogen gas. However, the high cost associated with cell components, such as the iridium oxide catalyst and titanium porous transport layer, poses a challenge to the commercialization of PEMEC. So, continued research is needed to improve the cost-effectiveness of PEMEC. Operation at high current densities can minimize the electrode area and reduce capital expenses. However, high current density operation is limited by limiting current density (LCD), which causes a sharp increase in electrolysis voltage. At high current densities, the generation of oxygen gas bubbles creates additional flow restrictions to the water supply and increase overvoltage. Although previous studies have achieved relatively high current densities [1-2], the limit of operating current density and its mechanism still remain unknown.In this study, it reveals the impact of operating temperature and pressure on LCD of a lab-scale PEMEC. The experiments are conducted over a range of temperatures from 80 to 90 ℃ and pressures from 0.1 to 0.3 MPa. In conjunction with experiments, a mathematical model is developed to analyze the mechanism of LCD. The model includes mass and momentum equations for liquid water and oxygen gas through the porous transport layer. And the model also involves electrochemical equations to study overvoltages associated with mass transport. By combining experimental and theoretical analysis, this study provides valuable insights into the factors affecting LCD of PEMECs and facilitates the optimization of high-performance operation. Experimental apparatus The specifications of crucial components such as membrane (PEM), catalyst layer (CL), porous transport layer (PTL) is listed in Table.1 . Nafion NR212 is used as PEM, and the thickness is 51 μm. The catalyst is contained on CL, and its loading amount are 1.5 mg/cm2 IrO2 on anode and 0.5 mg/cm2 Pt on cathode, respectively. The anodic PTL is a Titanium mesh plated by Pt (Nikko Techno, NKT-1803-03), and the carbon paper (SGL 38BA) is used as cathodic GDL. For separators, the anode separator is fabricated from titanium, and the cathode separator is carbon. The anodic and cathodic flow pattern is designed as single-serpentine channels, and the channel depth, channel width, and rib width are 1 mm ×1 mm ×1 mm, respectively. Results and discussions Fig.1 shows the theoretical and experimental I-V curves. In Fig.1, the electrolysis voltage in both experiment and simulation raises abruptly, which is corresponding to LCD. The experimental LCD is 11.6 A/cm2 as indicated by the black circle, and the predicted LCD is 10.1 A/cm2. Although the prediction of LCD is qualitative, simulation could follow the IV characteristics obtained by experiment before LCD.Fig.2 and Fig.3 shows the effect of operating temperature and pressure on LCD. The electrolysis voltage “E” is experimentally determined, while the gas saturation at interface of PTL-CH “Sg” is obtained through simulation. As shown in Fig.2, the lower operation temperature enlarges the LCD, the experimental LCD increases 8% from 90 ℃ to 80 ℃. Theoretically, high operating temperature increases oxygen bubbles and then rises the gas saturation S g at the anode CL. So, the water supply flowing to CL is insufficient, and the electrochemical performance also decrease. Therefore, the overvoltages caused by mass transport becomes larger in higher operating temperature. As shown in Fig.3, higher operating pressure shrinks the volume of oxygen gas and enhance the water supply from CH to CL, leading to a larger LCD. Under 80 ℃, the experimental LCD rises by 17 % from 0.1 MPa to 0.3 MPa.Although the theoretical analysis reproduced the experimental results in a qualitative manner, the theoretical analysis suggests that, when electrolysis current density is quite close to the LCD, water mass transport at anode reaches a limitation, indicating that water saturation drops to zero at anodic catalyst layer. References Lee J K, et al. Cell Reports Physical Science, 2020:100147.A Zinser, et al. International Journal of Hydrogen Energy, 2019, 44(52): 28077-28087. Figure 1