Imaging the 4D Chemical Heterogeneity of Single V ₂ O ₅ Particles During Charging/Discharging Processes

Abstract

Abstract Microparticle cathode materials are widely used in secondary batteries. However, obtaining dynamic chemical heterogeneities of these microparticles is challenging, hindering in‐depth mechanistic investigation of the underlying processes. For example, although vanadium pentoxide shows promise as an electrode material for zinc ion batteries, its poor performance's root cause is elusive. Herein, a fluorescence/scattering dual‐mode spinning disk confocal microscopy‐based approach is developed to visualize the 4D chemical heterogeneity of single V 2 O 5 particles during cycling. Dual‐mode in situ imaging identifies valence state changes of vanadium ions with high spatiotemporal resolution. A unique difference is observed between the scattering intensities of a particle's bottom electric contact points and the rest parts during the discharging process. In contrast, fluorescence intensity variation suggests high consistency across the particles. Correlative Raman, UV–Vis spectroscopy, and electrochemical impedance spectroscopy analyses suggest the precipitation of V 3+ species at the bottom interface of the V 2 O 5 electrode, leading to increased electron transfer resistance and compromised overall performance. A coordination strategy between ethylene diamine tetraacetic acid and V 3+ is proposed for inhibiting V 3+ precipitation, and its effectiveness is further verified by imaging and electrochemical impedance spectroscopy analyses. Insights from the imaging approach presented herein will enable the rational design of high‐performance batteries.