Investigating ageing behaviours in supercapacitor (cells and modules) using EEC (electrical equivalent circuit) models

This thesis contributes to the reliability and aging studies of supercapacitors for more efficient use in EV/HEV applications. This thesis demonstrates the effect of aging/failure in supercapacitor cells and module cells using accelerated tests employed to expedite the aging process. The tests, as explained below were categorized based on operational and environmental aging factors associated with supercapacitor failure in EV/HEV applications to; • Investigate supercapacitor cell performance at high temperature and constant voltage individual conditions, and also simultaneously (known as calendar test) • Investigate the effect of voltage balancing/equalization circuits on supercapacitor module cells’ performance during constant current cycling tests under certain environmental and electrical factors • Investigate supercapacitor module cells’ cycling performance in a lab-scale designed electrical DC programmable motor load system that emulates supercapacitor operational conditions in an EV/HEV application. The aging behaviors characterized by the three factors mentioned above are quantified in this thesis through the periodic monitoring of their electrical and electrochemical state of health with Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, and Constant Current characterization tests. These tests help identity aging modes in supercapacitors, and it was observed that regardless of their aging factors; an increase in ESR and decrease of capacitance was determined. Although this information is required, the results from Electrochemical Impedance Spectroscopy (EIS) tests revealed more details distinctive to each aging factor. From this distinction, the aging mechanisms in relation to the aging factors, which causes the deterioration in the supercapacitor electrical performance, are identified and summarized as the following: 1. Loss of contact within supercapacitor electrode, given rise to the contact resistance due to the presence of high temperature as the main aging factor 2. Change of supercapacitor porous electrode emulating a charge transfer reaction thereby increasing its distributed resistance, caused by the effect of high voltage or cycling Mathematical models in the form of electrical equivalent circuits (EECs) distinctive of their aging factors are generated from EIS electrochemical behaviors to easily describe aging behaviors in supercapacitors. The EEC models developed using impedance modeling generated an initial model from dormant cells, which transitioned to aging models distinctive of their aging factors as soon as a 100% increase in ESR and/or an 80% decrease in capacitance is observed. The proposed EEC models were validated to show the dynamic interaction between aging of the supercapacitor cells on their electrical performance in both frequency and time domains. In summary, the EEC models encompass this thesis objective and as such considered the main contribution of this research work