An experimental apparatus is described, in which Peltier elements are used for thermal control of lithium-ion cells under isothermal and non-isothermal conditions, i.e. to induce and maintain thermal gradients. Lithium-ion battery packs for automotive applications consist of hundreds of cells, and depending on the pack architecture, individual cells may experience non-uniform thermal boundary conditions. This paper presents the first study of the impact of artificially induced thermal gradients on cell performance. The charge transfer resistance of a 4.8 Ah is verified to have a strong temperature dependence following the Arrhenius law. Thermal cycling of the cell, combined with slow rate cyclic voltammetry, allows to rapidly identify phase transitions in electrodes, due to the thermal effect of entropy changes. A cell with a temperature gradient maintained across is found to have a lower impedance than one held at the theoretical average temperature. This feature is attributed to details of the inner structure of the cell, and to the non-linear temperature dependence of the charge transfer resistance.