Doctoral Dissertations

Date of Award

12-2013

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemical Engineering

Major Professor

Thomas A. Zawodzinski

Committee Members

Matthew M. Mench, Stephen J. Paddison, Robert M. Counce

Abstract

The all-vanadium redox flow battery (VRFB) is an excellent prospect for large scale energy storage in an electricity grid level application. High battery performance has lately been achieved by using a novel cell configuration with advanced materials. However, more work is still required to better understand the reaction kinetics and transport behaviors in the battery to guide battery system optimization and new battery material development. The first part of my work is the characterization of the battery systems with flow-through or flow-by cell configurations. The configuration difference between two cell structures exhibit significantly different polarization behavior. The battery output can be increased by higher electrolyte feed rate, but electrolyte utilization was decreased correspondingly. The battery performance can be largely enhanced by non-wetproofed electrode material. The battery cell with higher vanadium crossover has lower energy efficiency and faster capacity decay in cycling test. Secondly, the state of charge (SOC) monitoring is of great importance for battery management. A SOC monitoring method is developed using UV-Vis spectrometric measurements on VRFB electrolyte solutions. The spectrum of the negative electrolyte is linearly dependent on its SOC. In the positive electrolyte, the nonlinear intensity dependence on SOC appears to be caused by formation of complex vanadium-oxygen ion. The characteristic molar UV-Vis spectrum of the complex vanadium-oxygen ion was separated from that of the pure positive vanadium electrolyte components. The SOC of the positive electrolyte can be then calculated from its UV-Vis spectrum by considering the complex vanadium ion equilibrium. Moreover, the understanding of ionic transport mechanism in the electrolyte separator is critical to reduce internal resistance and vanadium crossover in the battery. The properties of Nafion and sulfonated Alder Diels poly(phelynene) (SDAPP) were investigated after equilibration with different electrolyte compositions. Both sulfuric acid and vanadium ion in the membrane can cause membrane conductivity loss. Vanadium-oxygen ion in membrane can slow down proton mobility via an unknown mechanism. Transmission electron microscope imaging showed that SDAPP is a more homogeneous ion exchange polymer with less phase separation than Nafion. The SDAPP membranes have better ion conducting properties than Nafion because of their higher ionic selectivity.

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