As lithium-ion batteries (LIB) see increasing use in areas beyond consumer electronics, such as the transportation sector, research has been directed at improving LIBs to better suit these applications. Of particular interest are materials and methods to increase Li(+) capacity at various charge/discharge rates, to improve retention of Li(+) capacity from cycle-to-cycle, and to enhance various safety aspects of electrode synthesis, cell construction, and end use. This work focuses on the synthesis and testing of three-dimensionally ordered macroporous (3DOM) TiO2/C LIB anode materials prepared using low toxicity precursors, including ammonium citratoperoxotitanate(IV) and sucrose, which provide high capacities for reversible Li(+) insertion/extraction. When the composites are pyrolyzed at 700 °C, the carbon phase restricts sintering of TiO2 crystallites and keeps the size of these crystallites below 5 nm. Slightly larger crystallites are produced at higher temperatures, alongside a titanium oxycarbide phase. The composites exhibit excellent capacities as LIB anodes at low to moderate charge/discharge rates (in the window from 1 to 3 V vs Li/Li(+)). Composites pyrolyzed at 700 °C retain over 200 mAh/g TiO2 of capacity after 100 cycles at a C/2 rate (C = 335 mA/g), and do not suffer from extensive cycle-to-cycle capacity fading. A substantial improvement of overall capacities, especially at high rates, is attained by cycling the composite anodes in a wider voltage window (0.05 to 3 V vs Li/Li(+)), which allows for Li(+) intercalation into carbon. At currents of 1500 mA/g of active material, over 200 mAh/g of capacity is retained. Other structural aspects of the composites are discussed, including how rutile TiO2 is found in these composites at sizes below the thermodynamic stability limit in the pure phase.
Keywords: carbon; confined crystallization; lithium-ion battery; nanocomposite; titania.