Development of a Capacitance versus Voltage Model for Lithium-Ion Capacitors

The capacitance of Lithium-ion Capacitors (LiCs) highly depends on their terminal voltage. Previous research found that it varies in a nonlinear manner with respect to the voltage. However, none of them modeled the capacitance evolution while considering the physicochemical phenomena that happen in a LiC cell. This paper focuses on developing a new capacitance model that is based on the Stern model of the electrochemical double layer capacitance. The model accounts for the asymmetric V-shape of the C(V) curve, which reflects the variation of the capacitance with respect to the voltage. The novelty of this study concerns the development of a model for LiCs that relies on the fundamental theory of Stern for the differential capacitance. The basic model of Stern is modified in order to account for the hybrid physicochemical structure of LiCs. Moreover, the model was applied to three aged cells to which accelerated calendar aging tests were applied at three voltage values: 2.2, 3 and 3.8 V. A drift of the voltage corresponding to the minimum capacitance was detected for the aged cells. This voltage is related to the neutral state of the positive electrode. The main cause of this phenomenon concerns the loss of lithium ions from the negative electrode of a LiC. In addition, capacitance values decreased after aging, showing an eventual blocking of the pores of the positive electrode. Therefore, the analysis of the C(V) curve was found to be an interesting tool for the interpretation of aging mechanisms.