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The hollow Si nanospheres modified by the mechanically robust titanium dioxide (TiO 2 ) shell and the uniform carbon layer are intentionally designed and successfully prepared as the anode active material of high performance lithium-ion batteries. The effects of the robust TiO 2 shell and the uniform carbon layer on the structure and electrochemical performances for the Si@TiO 2 @C nanospheres are studied in detail by X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray diffraction and charge/discharge tests. The results show that the hollow structure of the Si core can spontaneously absorb the huge volume expansion stress, the robust TiO 2 shell is used as a compact fence to promote the expansion towards the interior of the Si cavity instead of the exterior in the processes of charge/discharge, and the uniform carbon layer can effectively enhance the electrical conductivity and further control the integrity and stability of the well-wrapped core-shell-shell framework. Typically, the resultant hollow Si@TiO 2 @C nanospheres exhibit a high initial discharge capacity of 2557.1 mAh g −1 with coulombic efficiency of 86.06% as well as a large recuperative discharge capacity of 1270.3 mAh g −1 after 250 cycles at 1 A g −1 with a mean coulombic efficiency of 99.53%. Therefore, the hollow Si@TiO 2 @C nanospheres prepared by one-step sol-gel coating process show outstanding electrochemical properties and are considered as a prospective candidate to the adhibitions of the anode material for new generation power LIBs. [ABSTRACT FROM AUTHOR]