Sulfonated NbS₂-based proton-exchange membranes for vanadium redox flow batteries

Abstract

In this work, novel proton-exchange membranes (PEMs) based on sulfonated poly(ether ether ketone) (SPEEK) and two-dimensional (2D) sulfonated niobium disulphide (S-NbS₂) nanoflakes are synthesized by a solution-casting method and used in vanadium redox flow batteries (VRFBs). The NbS₂ nanoflakes are produced by liquid-phase exfoliation of their bulk counterpart and chemically functionalized with terminal sulfonate groups to improve dimensional and chemical stabilities, proton conductivity (<i>σ</i>) and fuel barrier properties of the as-produced membranes. The addition of S-NbS₂ nanoflakes to SPEEK decreases the vanadium ion permeability from 5.42 × 10^-7 to 2.34 × 10^-7 cm² min^-1. Meanwhile, it increases the membrane <i>σ</i> and selectivity up to 94.35 mS cm^-2 and 40.32 × 10⁴ S min cm^-3, respectively. The cell assembled with the optimized membrane incorporating 2.5 wt% of S-NbS₂ nanoflakes (SPEEK:2.5% S-NbS₂) exhibits high efficiency metrics, <i>i.e.</i>, coulombic efficiency between 98.7 and 99.0%, voltage efficiency between 90.2 and 73.2% and energy efficiency between 89.3 and 72.8% within the current density range of 100-300 mA cm^-2, delivering a maximum power density of 0.83 W cm^-2 at a current density of 870 mA cm^-2. The SPEEK:2.5% S-NbS₂ membrane-based VRFBs show a stable behavior over 200 cycles at 200 mA cm^-2. This study opens up an effective avenue for the production of advanced SPEEK-based membranes for VRFBs.