Abstract

Improving the proton conductivity (σ) of proton exchange membranes at low temperatures is very important for expanding their application areas. Here, sulfonated poly ether ether ketone (SPEEK) membranes were prepared with different sulfonation degrees, and its maximum ion exchange capacity is 3.15 mmol/g for 10 h at 60 °C. Highly sulfonated SPEEK membrane exhibits ultra-high water uptake and excellent proton conductivity of 0.074 S/cm at −25 °C due to its abundant −SO3H. Nevertheless, its high swelling ratio and low mechanical strength are not conducive to the practical application of the membrane. Luckily, by employing the chelation of Cu2+ with −SO3− on the SPEEK chain, Cu2+-coordinated SPEEK membranes were prepared, and they not only retain high −SO3H content but also possess robust mechanical properties and good dimensional stability compared to pristine SPEEK membrane. Meanwhile, the σ of the SPEEK-Cu membrane reaches 0.054 S/cm at −25 °C, and its fuel cell maximum power (Wmax) reaches 0.42 W/cm2 at −10 °C, demonstrating superior low-temperature performance in comparison to other reported materials. Particularly, water states in the prepared membranes are quantified by low-temperature differential scanning calorimetry. Because much more water bound to the plentiful −SO3H and Cu2+ inside the membrane endows it with anti-freezing performance, the decay of the σ and the Wmax for the SPEEK-Cu membrane is retarded at sub-zero temperatures. It is envisioned that composite membranes comprising metal ions such as Cu2+-SPEEK have a high potential for sub-zero fuel cell applications.