Computational framework for discovery of degradation mechanisms of organic flow battery electrolytes

Abstract

The stability of organic redox-active molecules is a key challenge for the long-term viability of organic redox flow batteries (ORFBs). Electrolyte degradation leads to capacity fade, reducing the efficiency and lifespan of ORFBs. To systematically investigate degradation mechanisms, we present a computational framework that automates the exploration of degradation pathways. The approach integrates local reactivity descriptors to generate reactive complexes and employs a single-ended process search to discover elementary reaction steps, including transition states and intermediates. The resulting reaction network is iteratively refined with heuristics and human-guided validation. The framework is applied to study the degradation mechanisms of quinone- and quinoxaline-based electrolytes under acidic and basic aqueous conditions. The predicted reaction pathways and degradation products align with experimental observations, highlighting key degradation modes such as Michael addition, disproportionation, dimerization, and electrochemical transformation. The framework provides a valuable tool for in silico screening of stable electrolyte candidates and guiding the molecular design of next-generation ORFBs.