Abstract
Inorganic-organic composite membranes were prepared by using partly cesium-substituted silicotungstic acid (CHS-WSiA) and polybenzimidazole (PBI, MRS0810H) for medium temperature polymer electrolyte fuel cells (MT-PEFCs). Cesium hydrogen sulfate (CsHSO4, CHS) and silicotungstic acid (H4SiW12O40, WSiA) were milled to obtain 0.5CHS-0.5WSiA composites by dry and wet mechanical millings. N,Ndimethylacetamide (DMAc) was used as a disperse medium in the preparation of the inorganic solid acids by wet mechanical milling and also a casting agent for fabrication of membrane. Finally, flexible and homogeneous composite membranes with several phosphoric acid doping levels (PADLs) were obtained. The wet mechanical milling using DMAc was found to effectively promote good substitution of H+ ion in WSiA by Cs+ ion of CHS and promoted the formation of smaller grain sizes of composites, compared with dry milling. A high maximum power density of 378 mWcm-2 and a good constant current stability test were obtained from a single cell test using the PBI composite membrane containing 20 wt% of 0.5CHS-0.5WSiA from wet milling and phosphoric acid doping level (PADL) of 8 mol, at 150 °C under an anhydrous condition. Wet milling CHS-WSiA crystallites were highly dispersed in PBI to give homogenized membranes and played a significant role in the enhancemance of acidity by increasing the number of proton sites in the electrolyte membrane. After the addition of CHS-WSiA into PBI membrane, the acid and water retention properties were improved and incorporated as new proton conduction path by adsorbing phosphoric acid in these composite electrolyte membranes. These observations suggest that composite membranes with 8 mol of PADL are good promising PA dopedmembranes with effective electrochemical properties for the medium temperature fuel cells.
Highlights
Environmental safety is of significant importance for human beings as well as the lives of future generations
After mechanical dry milling to fabricate CsxH4-xSiW12O40, noticeable changes are detected in the X-ray diffraction (XRD) results from 25.6 o to 26 o; and it showed broad diffraction peak comparing with composite fabricated from mechanical wet milling
The diffraction peak of composite slightly shifted to higher angle; that compared with composite from mechanical dry milling. Both composites synthesized by dry and wet milling showed the highest intensities with the high peak shifting to higher angles which indicates that the H+ ion in WSiA was partly substituted with large Cs+ ion in CHS to fabricate CsxH4-xSiW12O40 via mechanical dry and wet milling
Summary
Environmental safety is of significant importance for human beings as well as the lives of future generations. CHS-WSiA composite was created to enhance the anhydrous proton conductivity and reduce the particle sizes via wet mechanical milling as inorganic fillers for the application of membrane fabrication. For the MT-PEMFCs, proton conductivities and cell performances of CHS-WSiA/PBI membranes were improved after fabrication of composites doped-PBI.
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