Counter anion effects in anion exchange membrane-fabricated non-aqueous vanadium redox flow battery

In order to understand the counter anionic effects in a non-aqueous vanadium redox flow battery (VRFB), we synthesized four types of electrolyte salts (1-ethyltriethamine tertafluoroborate, [E-TEDA]⁺[BF₄]⁻, 1-ethyltriethamine hexafluorophosphate, [E-TEDA]⁺[PF₆]⁻, 1-butyltriethylamine tertafluoroborate, [B-TEDA]⁺[BF₄]⁻, and 1-buthyltriethamine hexafluorophosphate [B-TEDA]⁺[PF₆]⁻) by counter anion exchange reaction after the SN₂ reaction. We confirmed the successful synthesis of the electrolyte salts [E-TEDA]⁺[Br]⁻ and [B-TEDA]⁺[Br]⁻ via ¹H-NMR spectroscopy and GC-mass analysis before the counter anion exchange reaction. The electric potential of the vanadium acetylacetonate, V(acac)₃, as an energy storage chemical was shown to be 2.2 V in the acetonitrile solvent with each of the [E-TEDA]⁺[BF₄]⁻, [E-TEDA]⁺[PF₆]⁻, [B-TEDA]⁺[BF₄]⁻, and [B-TEDA]⁺[PF₆]⁻ electrolyte salts. In a non-aqueous VRFB with a commercial Neosepta AFN membrane, the maximum voltages reached 1.0 V and 1.5 V under a fixed current value of 0.1 mA in acetonitrile with the [E-TEDA]⁺[BF₄]⁻ and [E-TEDA]⁺[PF₆]⁻ electrolyte salts, respectively. The maximum voltage was 0.8 V and 1.1 V under a fixed current value of 0.1 mA in acetonitrile with the [B-TEDA]⁺[BF₄]⁻ and [B-TEDA]⁺[PF₆]⁻ electrolyte salts, respectively. From these results, we concluded that in the non-aqueous VRFB more of the [PF₆]⁻ counter anion than the [BF₄]⁻ counter anion was transported onto the commercial Neosepta AFN anion exchange membrane.