Identifying the Activated Carbon Electrode Aging Pathways in Lithium-Ion Hybrid Capacitors

This paper reports on several mechanisms of carbon aging in a hybrid lithium-ion capacitor operating with 1 mol L^–1 LiPF₆ in an ethylene carbonate/dimethyl carbonate 1:1 vol/vol electrolyte. Carbon electrodes were subjected to a constant polarization protocol (i.e., floating) at various voltages and analyzed postmortem via several complementary techniques. The selected protocol was able to simulate the behavior of the real system. Due to the use of metallic lithium as the counter electrode, the influence of battery-like aging mechanisms was assumed to be limited. Our approach focused on the aging mechanisms related to the carbon electrode and determined the structural and chemical changes leading to energy fading in lithium-ion hybrid capacitors. It was shown that an increase in applied voltage not only results in faster system degradation but directs the aging chemistry to different pathways: at moderate voltage values, both capacitance loss and simultaneous increase in resistance predominate. This could be associated with the decrease in carbon surface area and possible pore clogging with by-products of electrolyte degradation and carbon oxidation disrupting the C sp² network. When high voltage is applied, further oxidation of carbon occurs with an increase in measured resistance that leads to the relevant end-of-life criterion to be reached. Detailed postmortem analysis results attributed it to the formation of phenol and ether groups together with electrolyte decomposition products, higher oxidation levels, and structure degradation. It was evidenced that the decrease in the overall carbon conductivity and, in certain cases, modification of the textural properties ultimately aggravates the capacitor performance.