Zinc ion exchange assisted synthesis of R-TiO2@C hollow spheres with superior lithium-ion storage performance

Abstract

Nanostructured anode materials hold the key to advance the performance of the corresponding lithium-ion batteries as advanced electrochemical energy storage devices. Here, we designed a zinc exchange assisted phase change strategy as an acid-free and well-controlled approach to successfully synthesize a kind of rutile phase TiO2 @C (R-TiO2 @C) hollow spheres with well-defined size by using SiO2 spheres as sacrificial templates. The exchanged zinc ions in an alcohol solvothermal reaction were considered as a phase transition medium to promote the formation of a high-quality rutile TiO2 crystal through a high temperature solid-state heat way. By this way, the final morphologies of rutile phase TiO2 nanocrystals were well controlled, and the rutile TiO2 phase transformation temperature was lower than that of conventional one-step high temperature calcination way (without zinc ions exchange). Note that it successfully avoided using acids as mediums to promote the formation of rutile phase TiO2 crystal in the nano process. Meanwhile, the carbon layer formed by a hydrothermal carbonization reaction not only provided self-supporting solid-state in situ reducing medium for Zn2+ to Zn vapor but also produced conductive porous carbon coating porous and robust R-TiO2 spherical shell with nanosized subunits. The reaction process and mechanism of zinc ions induced phase transformation were discussed. Benefiting from the nanoscale morphology-regulation and hollow structure with enhanced ability of ion and electron transfer as well as electrolyte transport, the resultant R-TiO2 @C hollow spheres can significantly promote Li ions storage and deliver a high reversible specific capacity of 115.6 mAh g-1 at 5.0 C over 1600 cycles. A typical electrochemical reaction on Li ions inserted into TiO2 crystal was simply elaborated as well. This work demonstrates its great potential for practical application in lithium-ion batteries.