Inorganic–organic composite electrolyte membranes were fabricated from Cs substituted heteropolyacids (CsHPAs) and polybenzimidazole (PBI) for application in intermediate temperature hydrogen fuel cells. Four caesium salts of heteropolyacid, (CsXH3−XPMo12O40 (CsPOMo), CsXH3−XPW12O40 (CsPOW), CsXH4−XSiMo12O40 (CsSiOMo) and CsXH4−XSiW12O40 (CsSiOW)), were used to form composite membranes with PBI. The membranes were characterized by using SEM, FTIR and XRD. The CsHPA powders were nano-sized as shown in the XRD and SEM data. The CsHPA/PBI composite membranes loaded with H3PO4 had high conductivity, greater than that of a phosphoric acid loaded PBI membrane. The conductivity increased with an increase in the percentage of the powder in the composite. The 30% CsPOMo/PBI/H3PO4 exhibited a conductivity of 0.12 S cm−1 under anhydrous conditions, although its mechanical strength was the poorest, but still promising with a value 40 MPa. The performance of the hydrogen fuel cell with composite membranes was better than that with a phosphoric acid-doped PBI membrane under the same conditions. The CsPOMo gave the best power density of around 0.6 W cm−2 with oxygen at atmospheric pressure.
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