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Given the relevance of lithium and post-lithium batteries as electrochemical energy storage systems, the peculiar crystalline structure of V₂O₅ and its doping capacity play key roles in lithium-ion battery technology. To integrate them in high-efficiency modules, systematic methodologies are required to estimate the state of charge in a reliable way and predict the Li-V₂O₅ battery’s performance according to their electrochemical phenomena, including two plateaus in the galvanostatic cycling curves and the dynamic behavior governed by the energy demand. Most state of charge estimation and battery modeling procedures are focused on conventional Li-batteries that show a unique plateau. In this work, we propose a systematic methodology based on the galvanostatic intermittent titration technique and electrochemical impedance spectroscopy to study battery performance in the time and frequency domains, respectively. The proposed methodology, with a time–frequency correlation, promotes a deeper understanding of the electrochemical phenomena and general behavior of Li-V₂O₅ batteries, allowing for its subsequent extrapolation to more complex and higher-capacity lithium and post-lithium batteries used in high-power applications with a minimum error.