Understanding the Precipitation Mechanism in Pentavalent Vanadium Electrolytes through Deep Learning Potential Molecular Dynamics

Abstract

Vanadium flow batteries (VFBs) represent one of the promising options for large-scale energy storage, yet the precipitation of pentavalent (V(V)) species under elevated temperature and high state-of-charge severely limits energy density and cycle life. However, due to the lack of approaches capable of tracking the liquid-to-solid transition at atomic resolution, the mechanism underlying this precipitation has remained elusive. Here, we employ deep potential molecular dynamics (DPMD) to investigate the precipitation process in vanadium electrolytes. A high-accuracy deep potential model, with energy errors below 1 meV and force errors below 60 meV Å−1, was developed through active learning. And complete transformation of V(V) from hydrated species to vanadium oxide precipitates was simulated. The results reveal that precipitation proceeds via hydroxyl dehydration-transformation following an SN2-type pathway with an activation barrier of approximately 40 kJ mol−1. Based on these mechanistic insights, an anion coordination strategy was proposed to suppress precipitation. Experimental validation confirmed that strongly coordinating anions such as phosphate and arsenate extend precipitation onset from 10 hours to 150-200 hours at 50 °C. This study elucidates the precipitation mechanism and provides guidance for electrolyte formulation optimization in vanadium flow batteries.