Species Transport Mechanisms Governing Crossover and Capacity Loss in Vanadium Redox Flow Batteries

Vanadium redox flow batteries (VRFBs) are an emerging energy storage technology that offers unique advantages for grid-scale energy storage due to their flexible design and decoupled power/energy feature. Despite their popularity, a series of technical challenges hinder their widespread implementation. Among these, capacity loss (i.e., loss of energy storage capability) due to the undesired species crossover across the membrane has been identified as the key issue limiting the longevity of these systems. This issue is primarily governed by the properties of the membrane and can be mitigated by using proper membrane architectures with desired features. Presently, identifying proper membrane architectures for VRFB systems is hampered by the lack of a fundamental understanding of the nature of species transport mechanisms and how they are related to the membrane properties and key operating conditions.;This Ph.D. study seeks to address this critical challenge by exploring the fundamental mechanisms responsible for species transport within the membrane. The overall objective of this dissertation study is to establish a fundamental understanding of the multi-ionic transport in VRFB membranes by investigating the ionic transport mechanisms responsible for crossover, and utilize this understanding to reveal the role of membrane properties and operating conditions on the capacity loss. To achieve these goals, a combined experimental and computational study was designed. An experimentally validated, 2-D, transient VRFB model that can track the vanadium crossover and capture the related capacity loss was developed. In addition to the model, several electrochemical techniques were used to characterize different types of membrane and study the effects of various operating conditions on the species crossover. Using these computational and experimental tools, an in-depth understanding of the species transport mechanisms within the membrane and how they are related to membrane properties and operating conditions of VRFBs has been obtained. Finally, this understanding was utilized to identify effective mitigation strategies to minimize the capacity fade and improve the long-term performance of these systems.