Novel characterization of thermal properties of a battery has been introduced by defining its frequency-dependent thermal impedance function. Thermal impedance function can be approximated as a thermal impedance spectrum by analyzing experimental temperature transient which is related to the thermal impedance function through Laplace transformation. In order to obtain temperature transient, a process has been devised to generate external heat pulse with heating wire and to measure the response of battery. This process is used to study several commercial Li-ion batteries of cylindrical type. The thermal impedance measurements have been performed using potentionstat/galvanostate controlled digital signal processor, which is more commonly available than flow-meter usually applied for thermal property measurements. Thermal impedance spectra obtained for batteries produced by different manufactures are found to differ considerably. Comparison of spectra at different states of charge indicates independence of thermal impedance on charging state of battery. It is shown that thermal impedance spectrum can be used to obtain simultaneously thermal capacity and thermal conductivity of battery by non-linear complex least-square fit of the spectrum to thermal impedance model. Obtained data is used to simulate a response of the battery to internal heating during discharge. It is found that temperature inside the battery is by one-third larger that on its surface. This observation has to be considered to prevent damage by overheating.