Extensive numerical analysis was performed for the unsteady state, natural convection in the annular cylinders. The cylinder’s boundaries were thermally insulated, except the inner surface. The fluid (water) in the cylinder initially was assumed at a cold temperature while the inner surface was subjected to a high temperature. The time history for the heat transfer by diffusion and advection was studied. The time needed for fully charging the storage tank and rate of heat transfer was calculated. The predicted results were compared with the pure heat diffusion process and with a steady-state convection system. Therefore, CFD simulations were performed for natural convection in the storage tank. The main objective of this study was to establish correlations for the rate of heat transfer as a function of time and other controlling parameters. The correlation is needed in designing a thermal energy storage system for domestic and industrial heating processes. One of the drawbacks of the conventional thermal storage systems is the slow charging and discharging, where the heat transfer is mainly diffusion dominated. To overcome such a problem, a system was designed based on the natural convective heat transfer mechanism. Therefore, the heat transfer and fluid flow in a cylindrical storage tank were simulated for a range of Rayleigh numbers (104 to 108) and radius ratio. It was found that a convection-operated storage tank reduces the thermal charging process time drastically compared with the thermally diffusion charging process. The rate of reduction in the charging time mainly depends on the rate of heating and geometric parameter of the tank. To the best of the authors’ knowledge, the work is novel.