In this study, passive flat-plate closed-loop pulsating heat pipe (CLPHP) cooling is proposed to address the structural characteristics and cooling requirements of proton exchange membrane fuel cells (PEMFCs). Through visual images, non-visualized temperature and pressure measurements, and theoretical analysis, the effect of surfactant cetyltrimethylammonium bromide (CTAB) on the performance of a binary non-azeotropic mixed working medium flat-plate CLPHP with a 40% filling ratio (FR) and 5:1 mass ratio of methanol and deionized water was studied. It was found that the addition of surfactant CTAB reduced the surface tension and increased the shear friction force of the working fluid. The optimal CTAB concentration was 20 ppm, at which the start-up critical heat flux of the flat-plate CLPHP was reduced. At a heating power of 400 W, the heat transfer resistances reduced by 29.9%, which improved the heat transfer power of the flat-plate CLPHP. The backflow of the liquid-phase working medium at the bottom of the elbow in the evaporation section was promoted, dry-out phenomenon was avoided, temperature fluctuation of the flat-plate CLPHP was reduced, and temperature stability of the PEMFC was improved.