Vanadium Redox Flow Batteries Using <i>meta</i>-Polybenzimidazole-Based Membranes of Different Thicknesses

15, 25, and 35 μm thick <i>meta</i>-polybenzimidazole (PBI) membranes are doped with H₂SO₄ and tested in a vanadium redox flow battery (VRFB). Their performances are compared with those of Nafion membranes. Immersed in 2 M H₂SO₄, PBI absorbs about 2 mol of H₂SO₄ per mole of repeat unit. This results in low conductivity and low voltage efficiency (VE). In ex-situ tests, <i>meta</i>-PBI shows a negligible crossover of V³⁺ and V⁴⁺ ions, much lower than that of Nafion. This is due to electrostatic repulsive forces between vanadium cations and positively charged protonated PBI backbones, and the molecular sieving effect of PBI’s nanosized pores. It turns out that charge efficiency (CE) of VRFBs using <i>meta</i>-PBI-based membranes is unaffected by or slightly increases with decreasing membrane thickness. Thick <i>meta</i>-PBI membranes require about 100 mV larger potentials to achieve the same charging current as thin <i>meta</i>-PBI membranes. This additional potential may increase side reactions or enable more vanadium ions to overcome the electrostatic energy barrier and to enter the membrane. On this basis, H₂SO₄-doped <i>meta</i>-PBI membranes should be thin to achieve high VE and CE. The energy efficiency of 15 μm thick PBI reaches 92%, exceeding that of Nafion 212 and 117 (N212 and N117) at 40 mA cm<sup>–2