Advanced energy storage and power management systems designed through rigorous materials selection, testing and analysis processes are essential to ensuring mission longevity and success for space exploration applications. Comprehensive testing of Boston Power Swing 5300 lithium-ion (Li-ion) cells utilized by the National Aeronautics and Space Administration (NASA) to power humanoid robot Robonaut 2 (R2) is conducted to support the development of a test-correlated Thermal Desktop (TD) Systems Improved Numerical Differencing Analyzer (SINDA) (TD-S) model for evaluation of power system thermal performance. Temperature, current, working voltage and open circuit voltage measurements are taken during nominal charge-discharge operations to provide necessary characterization of the Swing 5300 cells for TD-S model correlation. Building from test data, embedded FORTRAN statements directly simulate Ohmic heat generation of the cells during charge-discharge as a function of surrounding temperature, local cell temperature and state of charge. The unique capability gained by using TD-S is demonstrated by simulating R2 battery thermal performance in example orbital environments for hypothetical extra-vehicular activities (EVA) exterior to a small satellite. Results provide necessary demonstration of this TD-S technique for thermo-electrochemical analysis of Li-ion cells operating in space environments. Published by Elsevier B.V.