No abstract

No abstract

It is known that uniaxially drawn perfluoronated sulfonic-acid ionomers (PFSAs) show diffusion anisotropy because of the aligned water channels along the deformation direction. We apply the uniaxially stretched membranes to vanadium redox flow batteries (VRFBs) to suppress the permeation of active species, vanadium ions through the transverse directions. The aligned water channels render much lower vanadium permeability, resulting in higher Coulombic efficiency (>98%) and longer self-discharge time (>250 h). Similar to vanadium ions, proton conduction through the membranes also decreases as the stretching ratio increases, but the thinned membranes show the enhanced voltage and energy efficiencies over the range of current density, 50-100 mA/cm. Hydrophilic channel alignment of PFSAs is also beneficial for long-term cycling of VRFBs in terms of capacity retention and cell performances. This simple pretreatment of membranes offers an effective and facile way to overcome high vanadium permeability of PFSAs for VRFBs.

Achieving high proton conductivity, low vanadium ion permeability, and high chemical stability using a single material remains a key challenge for hydrocarbon-based membranes for use in vanadium redox flow batteries (VRFBs). Herein, we report amorphous poly(2,5benzimidazole) (ABPBI) membranes with alkyl spacers which can meet these requirements. Spacer-grafted poly(2,5-benzimidazole)s (ABPBIs) with different grafting ratios were synthesized via an N-substitution reaction and denoted as ABPBI-0, -10, -25, -40, and -50, respectively. The structure to battery performance relationship was investigated through spectroscopic and electrochemical analysis. As the grafting ratio increased, the microstructure of the ABPBI derivative membranes was transformed from a semicrystalline to an amorphous structure because of reduced chain packing, increasing H 2 SO 4 -absorption capability and consequently reducing area-specific resistances. Also, they exhibited lower vanadium permeabilities compared with Nafion 115 owing to Donnan exclusion effect. As a combined effect of these characteristics, the membranes outperformed Nafion 115 membrane with notably high coulomb efficiencies and energy efficiencies. Furthermore, a grafted ABPBI membrane showed stable battery cycling performance more than 500 cycles at 200 mAcm −2 , and 1000 h continuous operation at 1C-rate, demonstrating excellent chemical stability against highly oxidizing VO 2 + solution.