Yolk-shell structured composite for fast and selective lithium ion sieving

Abstract

Yolk-shell structured C@Li4Ti5O12 microspheres composed of carbon core (ca. 500 nm) and sea urchin-like Li4Ti5O12 shell (ca. 400–500 nm) are formed by hydrothermally treating the core–shell structured C@TiO2 in the EtOH/H2O solution of LiOH and calcining it in N2 atmosphere. Yolk-shell structured TiO2-type lithium ion sieve is further transformed from C@Li4Ti5O12 through the acid treatment, which have a high specific surface area of 201.74 m2/g. The composite shows adsorption capacity towards Li+ proportional to the pH value in the range of 7–13. The adsorption reaches equilibrium within 2 h with a high equilibrium adsorption capacity of 28.46 mg/g under alkaline conditions, which is ca. 8 times the value of ordinary TiO2 lithium ion sieve with comparable size and surface area, demonstrating the enhanced adsorption is attributed to the generation of more accessible surficial voids by replacing internal part with light carbon core. The adsorption follows Freundlich and pseudo-second-order kinetic models with a high rate constant of 0.015 g/(mg·min). The selective adsorption to Li+ is verified in the presence of K+, Na+, Ca2+ and Mg2+.