Abstract: | The effect of operating temperature on performance degradation of direct methanol fuel cell (DMFCs) is examined to disclose the main parameter of the degradation mechanism and the degradation pattern in the membrane electrode assemblies (MEAs). The DMFC MEA degradation phenomenon is explained through the use of various electrochemical/physicochemical tools, such as electrochemical impedance spectroscopy, electrode polarization, methanol stripping voltametry, field emission‐scanning electron microscopy, X‐ray diffraction, inductively coupled plasma‐atomic emission spectroscopy, and X‐ray photoelectron spectroscopy analysis. The operation of DMFC under high temperature accelerates the degradation process of the DMFC. The higher degradation rate under high temperature DMFC operation is mainly attributed to the formation of membrane pinhole with interfacial delamination and cathode degradation. A high operating temperature may result in more considerable thermal and mechanical stress of the polymeric membrane continuously due to frequent dry–wet cycling mode and substantial uneven distribution of water between the anode and the cathode during a long period of DMFC operation. On the other hand, the electrochemical surface area deterioration by Pt coarsening and ionomers loss is not directly related to the larger DMFC performance decay at high temperature. |