New proton conducting membranes are made of sulfonated poly(arylene sulfide) polymers (SPAS) and a perfluorosulfonic acid polymer. A preferred poly(arylene sulfide) polymer is poly(p-phenylene sulfide). The membranes are used as a proton exchange membrane in PEM fuel cells operating at temperatures above 6OSUP0/SUPC, or at low relative humidity. According to methods of the invention, sulfonated poly(phenylene sulfide) (SPPS) films may be provided with a wide range of physical properties, which depend in part on the ion exchange capacity of the films. In particular, the degree or level of sulfonation can be tailored by adjusting reaction conditions such as temperature and time. In a preferred embodiment, an ionomer comprising perfluorosulfonic acid polymer is imbibed into the insoluble SPAS films by immersing the films in a solution or dispersion of the ionomers.
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