The internal temperature of an electrochemical device may be probed without a thermocouple, infrared detector, or other auxiliary device to measure temperature. Some methods include exciting an electrochemical device with a driving profile; acquiring voltage and current data from the electrochemical device, in response to the driving profile; calculating an impulse response from the current and voltage data; calculating an impedance spectrum of the electrochemical device from the impulse response; calculating a state-of-charge of the electrochemical device; and then estimating internal temperature of the electrochemical device based on a temperature-impedance-state-of-charge relationship. The electrochemical device may be a battery, fuel cell, electrolytic cell, or capacitor, for example. The procedure is useful for on-line applications which benefit from real-time temperature sensing capabilities during operations. These methods may be readily implemented as part of a device management and safety system.