Effects of operating conditions on performance of high-temperature polymer electrolyte water electrolyzer

• Characterization was conducted for a PEWE in a wide temperature and pressure region.
• A large overvoltage at elevated temperature is attributed to concentration overvoltage.
• An increase in operating pressure is a solution for reducing the concentration overvoltage.
• Maintaining water in the liquid phase is critical in operating high-temperature PEWEs.

Effects of operating conditions of a high-temperature polymer electrolyte water electrolyzer (HT-PEWE) on the electrolysis voltage are evaluated, and the optimal conditions for a high performance are revealed. A HT-PEWE unit cell with a 4-cm2 electrode consisting of Nafion117-based catalyst-coated membrane with IrO2 and Pt/C as the oxygen and hydrogen evolution catalysts is fabricated, and its electrolysis voltage and high-frequency resistance are assessed. The cell temperature and pressure are controlled at 80–130 °C and 0.1–0.5 MPa, respectively. It is observed that increasing the temperature at a constant pressure of 0.1 MPa does not increase the ohmic overvoltage of the cell; however, it does increase the concentration overvoltage. It is also found that the increase in the overvoltage resulting from the rise in the temperature can be suppressed by elevating the pressure. When operating the cell at a temperature of 100 °C, pressure greater than 0.1 MPa suppresses the overvoltage, and so does pressures greater than 0.3 MPa at 130 °C. This behavior suggests that keeping the water in a liquid water phase by increasing the pressure is critical for operating PEWEs at high temperatures.