Lithium ion (Li-ion) batteries provide low mass and energy dense solutions necessary for space exploration, but thermal related safety concerns impede the utilization of Li-ion technology for human applications. Experimental characterization of thermal runaway energy release with accelerated rate calorimetry supports safer thermal management systems. ‘Standard’ accelerated rate calorimetry setup provides means to measure the addition of energy exhibited through the body of a Li-ion cell. This study considers the total energy generated during thermal runaway as distributions between cell body and hot gases via inclusion of a unique secondary enclosure inside the calorimeter; this closed system not only contains the cell body and gaseous species, but also captures energy release associated with rapid heat transfer to the system unobserved by measurements taken on the cell body. Experiments include Boston Power Swing 5300, Samsung 18650-26F and MoliCel 18650-J Li-ion cells at varied states-of-charge. An inverse relationship between state-of-charge and onset temperature is observed. Energy contained in the cell body and gaseous species are successfully characterized; gaseous energy is minimal. Significant additional energy is measured with the heating of the secondary enclosure. Improved calorimeter apparatus including a secondary enclosure provides essential capability to measuring total energy release distributions during thermal runaway.