Electrochemical study of the Li-ion storage process in MWCNT@TiO2–SiO2 composites
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Tuning the Li-ion storage mechanism from battery-like to pseudocapacitive is a current strategy to improve the rate capability of intercalation materials. A widespread methodology is decreasing the particle size of the active material, offering larger number of active sites available to storage Li-ions on the surface of the materials. Core@shell composites were obtained by hydrolyzing TTIP and TEOS, at different ratios, over previously dispersed home-made MWCNTs in Isopropanol, in order to obtain a TiO2 shell modified with 1 mol% and 9 mol% of SiO2. This led to a detriment in the anatase crystalline size (TEM and XRD) and an increment in the specific surface area (BET) of the composite, but kept constant the TiO2 shell thickness formed around the MWCNTs. A change in the Li-ion storage process from mostly insertion (at SiO2 1 mol%) to entirely pseudocapacitive (at SiO2 9 mol%), was observed. This allowed a better capacity retention at high cycling rates, when the material was tested between 3 and 1 V vs. Li/Li+. Nonetheless, when the potential windows during cycling was increased from 3 to 0.5 V, the specific capacity of the composite modified with 9 mol% of SiO2, vanished at high cycling rates. The thoroughly EIS characterization in the whole potential window (from 3 to 0.5 V) of the tested half cells, evidenced the enlargement of charge transfer resistance; which was associated to highly reactive –OH groups (FTIR and TGA) present in the composite, promoted by the addition of SiO2 in the shell.
This work has been given the financial support from CONACyT (270810) and UNAM (project UNAM PAPIIT-IN103718). The authors are grateful with Professor Ignacio González from UAM-I and with Laboratorio Nacional de Conversión y Almacenamiento de Energía, for some of the infrastructure required to perform this research.
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