Li-ion batteries possess significant advantages like large energy density, fast recharge, and high reliability; hence, they are widely adopted in electric vehicles, portable electronics, and military and aerospace applications. Albeit having their merits, accurate battery modeling is subjected to problems like prior information on internal chemical reactions, complexity in problem formulation, a large number of unknown parameters, and the need for extensive experimentation. Hence, this article presents a reliable Spotted Hyena Optimizer (SHO) to determine the equivalent circuit parameters of lithium-ion (Li-ion) batteries. The methodology of the SHO is derived from the living and hunting tactics of spotted hyenas, and it is efficiently applied to solve the battery parameter estimation problem. Nine unknown battery model parameters of a Samsung INR 18650-25R are determined using this method. The model parameters estimated are endorsed for five different datasets with various discharge current values. Further, the effect of parameter range and its selection is also emphasized. Secondly, for validation, various performance metrics such as Integral Squared Error, mean best, mean worst, and Standard Deviation are evaluated to authenticate the superiority of the proposed parameter extraction. From the computed results, the SHO algorithm is able to explore the search area up to 89% in the case of larger search ranges. The chosen model and range of the SHO precisely predict the behavior of the proposed Li-ion battery, and the results are in accordance with the catalog data.