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Development of nano-structured electrode materials for high performance energy storage system

Authors Huang, Zhendong
Issue Date 2012
Summary Systematic studies have been done to develop a low cost, environmental-friendly facile fabrication process for the preparation of high performance nanostructured electrode materials and to fully understand the influence factors on the electrochemical performance in the application of lithium ion batteries (LIBs) or supercapacitors. For LIBs, LiNi1/3Co1/3Mn1/3O2 (NCM) with a 1D porous structure has been developed as cathode material. The tube-like 1D structure consists of inter-linked, multi-facet nanoparticles of approximately 100-500nm in diameter. The microscopically porous structure originates from the honeycomb-shaped precursor foaming gel, which serves as self-template during the stepwise calcination process. The 1D NCM presents specific capacities of 153, 140, 130 and 118mAh⋅g-1 at current densities of 0.1C, 0.5C, 1C and 2C, respectively.. Subsequently, a novel stepwise crystallization process consisting of a higher crystallization temperature and longer period for grain growth is employed to prepare single crystal NCM nanoparticles. The modified sol-gel process followed by optimized crystallization process results in significant improvements in chemical and physical characteristics of the NCM particles. They include a fully-developed single crystal NCM with uniform composition and a porous NCM architecture with a reduced degree of fusion and a large specific surface area. The NCM cathode material with these structural modifications in turn presents significantly enhanced specific capacities of 173.9, 166.9, 158.3 and 142.3mAh⋅g-1 at 0.1C, 0.5C, 1C and 2C, respectively. Carbon nanotube (CNT) is used to improve the relative low power capability and poor cyclic stability of NCM caused by its poor electrical conductivity. The NCM/CNT nanocomposites cathodes are prepared through simply mixing of the two component materials followed by a thermal treatment. The CNTs were functionalized to obtain uniformly-dispersed MWCNTs in the NCM matrix. The electrochemical tests found reduced inner electron resistance and improved rate capability of the nanocomposite cathodes compared to the neat NCM, which were attributed to the 3D spatial conductive network formed by MWCNTs and Super p carbon black in the nanocomposites. The capacity retention ratios after 100 cycles of Li/NCM-CNTs cell were about 81%, much higher than that of Li/NCM cell (~72%). As for supercapacitor, the annealed GO/CNT films or papers the binder-free electrodes are prepared and use for high performance supercapacitors. The amphiphilic nature of graphene oxide (GO) sheets allows adsorption of CNTs onto their surface in water, capable of forming highly stable dispersion. Thus, the GO/CNT hybrid films or papers are self-assembled via simple casting or vacuum filtration of aqueous dispersion. The hybrid thin film electrode with a moderate CNT content, typically 12.5wt%, give rise to remarkable electrochemical performance with extremely high specific capacitances of 428 and 145 F⋅g-1 at current densities of 0.5 and 100 A⋅g-1, respectively, as well as a remarkable retention rate 98% of the initial value after 10,000 charge/discharge cycles. The same as film type electrode, the rGO/CNT sandwich papers gives rise to an excellent specific capacitance of 151 F⋅g-1 at a current density of 0.5 A⋅g-1, as well as a remarkable retention ratio of 86 % of the initial value after 6,000 charge/discharge cycles at 5 A⋅g-1. These improvements arise from the synergistic effects of the increased electronic conductivity and effective surface area associated with large electrochemical active sites. The synergistic effects arising from i) the enlarged surface area of electrodes due to the intercalation of CNTs between the stacked GO sheets with associated large electrochemical active sites and ii) the improved conductivity through the formation of 3D network aided by CNTs, are mainly responsible for these findings. The effects of reduction process are also studied on the supercapacitive behavior of electrodes made from flexible graphene oxide (GO) papers. It is found that the supercapacitive performance depends on several factors, including the presence of oxygenated functional groups after reuction, the interlayer spacing of GO papers and the wettability with electrolyte. A moderate reduction of GO papers using hydrazine or annealing at a low temperature, say 220°C, in air is proven to be more beneficial to achiving a high capacitance than the heavy reduction using a hydrazine vapor or a high temperature thermal treatment.
Note Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2012
Language English
Format Thesis
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