Lithium-ion batteries (LIBs) are widely used for energy storage, and their functionality is directly related to electrode structure. The article analyzes how electrode thickness, porosity, and material composition affect the overall performance of 18650 LIBs. The report also provides a comparison of the various commercialized electrode types and their effects on energy density, charging/discharging rate, and cycle life. The article explores the correlations among electrode structure, ionic transport, reaction kinetics, and thermal stability, and provides meaningful insights into the key factors that can be considered among the most glaring determinants of battery efficacy. By summarizing the current evidence, this review suggests that optimizing the electrode structure can significantly increase output and lifespan of 18650 LIBs and, consequently, their ability to be utilized in high-performance energy storage systems.