Proton transportation in an organic–inorganic hybrid polymer electrolyte based on a polysiloxane/poly(allylamine) network

A new class of proton‐conducting polymer was developed via the sol–gel process from amino‐containing organic–inorganic hybrids by the treatment of poly(allylamine) with 3‐glycidoxypropyltrimethoxysilane doped with ortho‐phosphoric acid. The polymer matrix contains many hydrophilic sites and consists of a double‐crosslinked framework of polysiloxane and amine/epoxide. Differential scanning calorimetry results suggest that hydrogen bonding or electrostatic forces are present between H3PO4 and the amine nitrogen, resulting in an increase in the glass‐transition temperature of the poly(allylamine) chain with an increasing P/N ratio. The 31P magic‐angle spinning NMR spectra indicate that three types of phosphate species are involved in the proton conduction, and the motional freedom of H3PO4 is increased with increasing P/N ratios. The conductivity above 80 °C does not drop off but increases instead. Under a dry atmosphere, a high conductivity of 10−3 S/cm at temperatures up to 130 °C has been achieved. The maximum activation energy obtained at P/N = 0.5 suggests that a transition of proton‐conducting behavior exits between Grotthus‐ and vehicle‐type mechanisms. The dependence of conductivity on relative humidity (RH) above 50% is smaller for H3PO4‐doped membranes compared with H3PO4‐free ones. These hybrid polymers have characteristics of low water content (23 wt %) and high conductivity (10−2 S/cm at 95% RH), making them promising candidates as electrolytes for fuel cells.