Highly Conductive Proton Selectivity Membrane Enabled by Hollow Carbon Sieving Nanospheres for Energy Storage Devices

Ion conductive membranes (ICMs) with highly conductive proton selectivity are of significant importance and greatly desired for energy storage devices. However, it is extremely challenging to construct fast proton-selective transport channels in ICMs. Herein, a membrane with highly conductive proton selectivity was fabricated by incorporating porous carbon sieving nanospheres with a hollow structure (HCSNs) in a polymer matrix. Due to the precise ion sieving ability of the microporous carbon shells and the fast proton transport through their accessible internal cavities, this advanced membrane presented a proton conductivity (0.084 S·cm⁻¹) superior to those of a commercial Nafion 212 (N212) membrane (0.033 S·cm⁻¹) and a pure polymer membrane (0.049 S·cm⁻¹). The corresponding proton selectivity of the membrane (6.68 × 10⁵ S·min·cm⁻³) was found to be enhanced by about 5.9-fold and 4.3-fold, respectively, compared with those of the N212 membrane (1.13 × 10⁵ S·min·cm⁻³) and the pure membrane (1.56 × 10⁵ S·min·cm⁻³). Low-field nuclear magnetic resonance (LF-NMR) clearly revealed the fast proton-selective transport channels enabled by the HCSNs in the polymeric membrane. The proposed membrane exhibited an outstanding energy efficiency (EE) of 84% and long-term stability over 1400 cycles with a 0.065% capacity decay per cycle at 120 mA·cm⁻² in a typical vanadium flow battery (VFB) system.