Towards more Durable Electrochemical Capacitors by Elucidating the Ageing Mechanisms under Different Testing Procedures

Electrical double‐layer capacitors (EDLCs) commonly denoted supercapacitors are rechargeable energy storage devices with excellent power and energy delivery metrics intermediate to conventional capacitors and batteries. High‐voltage aqueous electrolyte based EDLCs are particularly attractive due to their high‐power capability, facile production, and environmental advantages. EDLCs should last for thousands of cycles and evaluation of future cell chemistries require long‐term and costly galvanostatic cycling. Voltage holding tests have been proposed to shorten evaluation time by accelerating cell degradation processes. Whether voltage holding can replace cycling completely remains undemonstrated. In this work, a systematic investigation of the influence of testing procedure on cell performance is presented. The state‐of‐the‐art post‐mortem and operando experimental techniques are implemented to elucidate ageing mechanisms and kinetics inside EDLC cells under different testing procedures. Carbon corrosion occurring on the positively polarized electrode leads to the lower active surface area and higher oxygen content. On the contrary, an increase of surface area and micropore volume are observed on the negatively polarized electrode. Repeated galvanostatic cycles at U<1.6 V appears to facilitate the depletion of oxygen species on the positively polarized electrode in comparison with voltage holding, which indicates a more complex degradation mechanism during cycling. Caution is advised when comparing results from different test procedures.