As part of a research project on new lithium-ion secondary cells to store energy from renewable power sources, this work reports on the development of a new methodology for a laboratory-scale study of electrode materials for these cells under the specific constraints of photovoltaic charging. A first example is that of a cell containing the spinel anode Li4Ti5O12, charging under different solar irradiation regimes. This material is well suited to applications under discontinuous charge/discharge conditions. At the end of the test, after about 250 cycles, the two cells tested provide the same capacity and energetic efficiency of about 2.2mAh and 90%, respectively.