Nanoscientific investigations of electrode materials for supercapacitors

University dissertation from Stockholm : KTH

Abstract: This doctoral thesis gives background to the field of electrochemical energy storage in supercapacitors. It attempts to place the supercapacitor device in context of available and future technologies for alternative energy systems for transportation. Limitations of cells and electrodes and key challenges in the supercapacitor development are introduced. One objective of the thesis is to investigate and describe ionic transport in active carbon and possible restrictions in nanostructured porous systems with focus on small (micro and meso) pores. Another is to develop a model suitable for investigations of concentration and potential profiles from a single particle perspective. The results from the studies are presented in this thesis together with the scientific papers this thesis is based on.Studying electrochemical gradients (concentration and potential) of large electrodes and single particles may give important information of the limitations of the material. In larger three-electrode experimental set-ups, these gradients can be studied for electrodes but single particles are not available for experimental studies to the same extent since the matrix of an electrode consist of many particles, all adding to the total gradient of the electrode. The experimental part of this thesis is based on different experimental techniques: Three-electrode experiments for larger electrodes, microelectrode experiments for single particles, numerical simulations using Multiphysics (software) of large electrodes consisting of single particles.Four Papers are appended to the thesis. They present results and discussions regarding ionic transport, surface functionalities and modeling of a particle based supercapacitor electrode. Estimated effective diffusivities for an active carbon containing micro, meso and macropores are presented. Surface functionalities in the form of oxygen-containing groups were present in a carbon studied using two experimental set-ups. Faradaic peaks, previously not reported in activated carbon were seen. The occurrence of Faradaic phenomena in one experimental set-up but not the other is further analyzed and the origin of these peaks discussed. The particle based mathematical model, where galvanostatic and cyclic voltammetry is simulated, is presented. Concentration profiles both in the particles and electrodes are discussed and some of the numerical results are compared with experimental data.