Physical and electrochemical study of halide-modified activated carbons

The current thesis aims to improve the electrochemical capacity of activated carbon electrodes, which enjoy prominent position in commercial electrochemical capacitors. Our approach was to develop electrochemical capacity by developing faradaic pseudocapacitance in carbon through a novel mechanochemical modification using iodine and bromine. Various commercial carbons were mechanochemically modified via solid-state iodation and vapour phase iodine-incorporation. The halidation-induced changes in the structure, composition, morphology, electrical and electrochemical properties of carbon materials were studied using different characterization techniques encompassing XRD, XRF, XPS, Raman spectroscopy, BET study, TEM, SAXS and electrochemical testing followed by an intensive battery of physical and electrochemical characterization. The introduction of iodine into carbon system led to the formation of polyiodide species that were preferentially reacted within the micropore voids within the carbon leading to the development of a faradaic reaction at 3.1V. In spite of the lower surface area of modified carbon, we observed manyfold increase in its electrochemical capacity. Parallel inception of non-faradaic development and faradaic pseudocapacitive reaction led to promising gravimetric, surface area normalized and volumetric capacity in iodated carbons. With promising electrochemical improvement post halidation process, the chemical halidation method was extended to different class of carbons and halides. Carbons ranging from amorphous (activated) carbons to crystalline carbons (graphites, fluorographites) were iodine-modified to gain further insight on the local graphite-iodine chemical interaction. In addition, the effect of pore size distribution on chemical iodation process was studied by using in-house fabricated microporous carbon. A comparative study of commercial mesoporous carbons and in-house fabricated microporous carbons showed higher iodine-uptake ability and larger volumetric capacity development in case of microporous carbons. For halides, bromine was also tested in activated carbons, which showed similar set of physical and electrochemical modification, but to a smaller degree. Carbon-polyhalide nanocomposites form a very interesting system both for fundamental research and as new electrode systems for asymmetric hybrid capacitor and low-voltage high power battery type applications.Ph.D.Includes bibliographical references.by Prabeer Barpand