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[Display omitted] • Self-assembly by electrostatic interaction between silane and MOF ligand. • The activation mechanism of electrochemical inert metal Co in SiO x materials was investigated. • The catalytic action of atomic Co site activates Si O bond and Li O bond to increase SiO x capacity and coulomb efficiency. • High mechanical strength and high conductivity Co nanoparticles enhance the conductivity and cycling stability of SiO x. The ultra-high theoretical capacity of silicon-based (Si) materials makes them promising anode materials for high energy density lithium-ion batteries. Unfortunately, the dramatic volume change (∼300%) and low electrical conductivity of silicon have severely hindered the commercial use of silicon anodes. Silicon suboxide (SiO x) is one of the ideal candidates for high energy density batteries due to its reduced swelling and lower cost as compared to silicon. However, it remains a huge challenge to address the low conductivity, low (initial) coulombic efficiency and apparent volume effects of SiO x. In this paper, SiO x /Co@C composite anode materials loaded with metal Co nanoparticles were uniformly and efficiently prepared by using 3-aminopropyl triethoxysilane (APTES) as silicon source and Co-MOF as Co source via molecular self-assembly strategy. The experimental results and density functional theory (DFT) calculation showed that the catalytic action of embedded Co nanoparticles had activated the silico-oxygen bond of SiO x and the irreversible product Li 2 O, thereby improving the initial coulombic efficiency (ICE) and enhancing the reversible capacity. At the same time, the metal Co with mechanical rigidity and electrical conductivity alleviated the volume fluctuation during alloying and improved the charge transfer capacity and ion transport rate of the composite. When compared with SiO x @C anodes, SiO x /Co@C-600 composites showed higher initial CE, superior cyclic stability and good rate performance. In particular, the successful matching of the anode with the lithium iron phosphate (LFP) cathode in full cell systems validated the possibility of its practical application. This work provides important insights into the application of Si-based materials in lithium-ion battery electrode materials and the development of high energy density batteries. [ABSTRACT FROM AUTHOR]

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]