Effects of tin phosphate nanosheet addition on proton-conducting properties of sulfonated poly(ether sulfone) membranes

Organic/inorganic composite membranes were prepared by dispersing nanosheets of layered tin phosphate hydrate [Sn(HPO4)2·nH2O (SnP)] in sulfonated poly(ether sulfone) (SPES) at SnP contents of 0–40 vol.%. The stabilities and proton conductivities of SPES/SnP nanosheet (SnP-NS) composite membranes were investigated and compared with those of SPES/SnP particle (SnP-P) composite membranes. The chemical stabilities as evaluated by thermogravimetry, differential thermal analysis, and diffuse reflectance Fourier-transform infrared spectroscopy were improved in both composite membranes. The improvement in the structural stability of SPES/SnP-NS composite membranes was more evident than that in SPES/SnP-P. The results suggest that exfoliation of SnP increases the area of the SPES–SnP interface and extends the connectivity of the network of hydrogen bonds. A composite membrane containing 10 vol.% SnP-NS (SPES/SnP-NS10vol.%) showed a high conductivity of 5.9 × 10− 2 S cm− 1 at 150 °C under saturated water vapor pressure. Although less water was present in SPES/SnP-NS10vol.% than in SPES/SnP-P10vol.% or pure SPES, the conductivity of SnP-NS10vol.% was the highest among these samples at 130 °C under a high relative humidity (RH). However at a low RH, the proton-conducting property was not improved by changing the composition of the SnP-NS. These results suggest that the hydrogen-bond network operates effectively for proton conduction at a high RH, but at a low RH, the network fails to conduct as a result of a decrease in water content accompanied by structural stabilization.

► SPES/SnP nanosheet composite membranes were prepared.
► The composite membranes showed high chemical stability.
► The proton conductivity was enhanced with increasing SPES–SnP interfacial area.
► Well-connected SPES–SnP interfacial layer operates as a proton-conducting path.