Li-ion cells are used in a variety of mobile and stationary applications. Their use must be safe under all conditions, even for aged cells in second-life applications. In the present study, different aging mechanisms are taken into account for accelerating rate calorimetry (ARC) tests. 18650-type cells are cycled at 0 • C (Li plating expected) and at 45 • C (SEI growth expected). After extensive evaluation of the electrochemical results (voltage curve analysis, capacity fade, energy fade, Coulombic efficiency), the cells are tested by PostMortem analysis (CT, GD-OES, SEM) to reveal the main aging mechanisms and by ARC to test the safety behavior. Besides typical ARC results such as onset-of-self-heating, onset-of-thermal runaway and maximum temperatures, as well as acoustic responses of thermal runaway are evaluated and a method is developed to compare fresh cells and cells aged until different SOHs. It turns out that the safety of aged cells is not simply a function of the SOH. However, safety is strongly affected by the main aging mechanism and to the history of operating parameters during the life-time of the cell. Driven by the demand for higher capacity, lower volume, and lower weight, Li-ion technology was developed in the 1980s.1,2 Nowadays, Li-ion technology is used for energy storage in a large variety of applications, e.g. smartphones, tablets, or drones. In particular, electric vehicles in combination with renewable energy sources are promising for reducing climate change and the corresponding glacier melting and sea level rise which is influenced by burning fossil fuels.3-6 For all applications, the safety behavior under all specified operating conditions is most important.7-9 The same is true for aged Li-ion cells used in second-life applications, for example cells which are utilized in stationary energy storage applications after their usage in electric cars.In the past, failure of Li-ion cells led to product recalls which are very expensive for the manufacturers and unsettle customers, even if such incidents happen only in very few cases (ppm range).10 At the moment, safety tests have to be performed with Li-ion prototypes cells before market release. In these tests, fresh cells are always used, however, aged cells are usually neglected. Even if fresh cells show an acceptable safety behavior, this can change for aged cells. 7,[11][12][13][14][15] While some authors observed decreases for certain safety properties, 7,11,12 others found improvements. 12,13,15 It is well known that aging mechanisms change the properties of the materials inside Li-ion cells. [16][17][18][19] Operating conditions and materials have a strong influence on these aging mechanisms. 12,[20][21][22][23] We recently reported on a change of the aging mechanism with temperature for cycling aging of commercial 18650-type cells with graphite anodes and NMC/LMO cathodes. 20 This mechanism change is expressed by a V-shape in Arrhenius plots of the capacity fade rates obtained from cycling at different ambient temperatures. 20 This c...