POLYMER ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE SYSTEMS: FUEL CELLS AND REDOX FLOW BATTERIES

Abstract

Direct methanol fuel cells (DMFCs) and redox flow batteries (RFBs) are well-known electrochemical energy conversion/storage systems that utilize redox reactions to convert or store electricity. Ion exchange membranes (IEMs) are used in DMFCs and RFBs as electrolyte separators. The critical requirements for IEMs in these applications are high ionic conductivity, low electrolyte permeability, high stability, and low cost. Silsesquioxane (SQO)-based sulfonated poly(etheretherketone) composite membranes were synthesized. Morphological changes in the composite membranes resulting from the introduction of SQO were studied using small-angle x-ray scattering. A sharp decrease in proton conductivity with SQO loading (> 20 wt%) was attributed to morphological changes in the membrane, including agglomeration and inhomogeneous dispersion of SQO particles within the ionic domains. Anion exchange membranes (AEMs) based on quaternized cardo-poly(etherketone) (QPEK-C) were prepared and evaluated for all-vanadium RFB (VRFB) applications. The QPEK-C AEMs with different degrees of functionalization (0.9–1.6) exhibited sulfate ion conductivities ranging between 5.6 and 15.2 mS cm-1 at 30 oC. The AEM had a lower VO2+ permeability (2.8×10-8 cm2 s-), compared to that of Nafion® 212 (2.9±0.2 ×10-7 cm2 s-1), which was attributed to the Donnan exclusion effect. The mechanical strength of QPEK-C AEM degraded by 35% after exposure to a 1.5 M VO2+ solution for 1500 hours due to the oxidation of aromatic rings. A single-cell VRFB employing the AEM separator yielded current and energy efficiencies (at 30 mA cm-2) of 97-99% and 80-82 %, respectively. Enhanced sulfate ion conductivity (8.4 ± 0.2 mS cm-1) and decreased VO2+ permeability (0.53×10-9 cm2 s-1) were achieved by incorporating 20 wt% of n-(trimethoxysilylpropyl)-n,n,n-trimethylammonium additives into QPEK-C, (the pristine QPEK-C AEM yielded corresponding values of 4.5 ± 0.5 mS cm-1 and 1.09×10-9 cm2 s-1). About 99% coulombic efficiency was achieved with the VRFBs employing the composite AEM. However, a rapid reduction of the ionic conductivity down to the value of the pristine membrane was observed when the composite AEM was immersed in 1.5 M VO2+ solution for 3 days. Vanadium-cerium RFBs (V-Ce RFBs) evaluated with QPEK-C AEM separators yielded identical energy efficiency (84%) to corresponding RFBs evaluated with Nafion® 212. However, after over 20 charge-discharge cycles, the V-Ce RFB with the AEM separator yielded unchanged efficiency and capacity, while a 50% loss of capacity was observed with the Nafion® separator. This suggested that QPEK-C AEMs are promising candidates for RFB separators when different cations are used in the two electrolyte solutions, in that they act as efficient barriers that preclude the intermixing of the cations due to the Donnan exclusion effect.Ph.D. in Chemical Engineering, December 201