Oriented Proton-Conductive Nanochannels Boosting a Highly Conductive Proton-Exchange Membrane for a Vanadium Redox Flow Battery

In this work, we propose a sulfonated poly (ether ether ketone) (SPEEK) composite proton-conductive membrane based on a 3-(1-hydro-imidazolium-3-yl)-propane-1-sulfonate (Him-pS) additive to break through the trade-off between conductivity and selectivity of a vanadium redox flow battery (VRFB). Specifically, Him-pS enables an oriented distribution of the SPEEK matrix to construct highly conductive proton nanochannels throughout the membrane arising from the noncovalent interaction. Moreover, the “acid–base pair” effect from an imidazolium group and a sulfonic group further facilitates the proton transport through the nanochannels. Meanwhile, the structure of the acid–base pair is further confirmed based on density functional theory calculations. Material and electrochemical characterizations indicate that the nanochannels with a size of 16.5 nm are vertically distributed across the membrane, which not only accelerate proton conductivity (31.54 mS cm–1) but also enhance the vanadium-ion selectivity (39.9 × 103 S min cm–3). Benefiting from such oriented proton-conductive nanochannels in the membrane, the cell delivers an excellent Coulombic efficiency (CE, ≈ 98.8%) and energy efficiency (EE, ≈ 78.5%) at 300 mA cm–2. More significantly, the cell maintains a stable energy efficiency over 600 charge–discharge cycles with only a 5.18% decay. Accordingly, this work provides a promising fabrication strategy for a high-performance membrane of VRFB.