Delicate Control of Multishelled Zn-Mn-O Hollow Microspheres as a High-Performance Anode for Lithium-Ion Batteries

Mixed/composite oxides of transition metals with hollow structures, especially multishelled hollow architecture, have promising potential for different applications, but their syntheses still remain a big challenge. Herein, a facile coordination polymer precursor method was developed to construct various multishelled Zn-Mn-O hollow microspheres, including ZnMnO₃, ZnMn₂O₄, and ZnMn₂O₄/Mn₂O₃. The composition of the hollow structures can be adjusted by controlling the composition of the coordination polymer precursors, which are easily obtained with Zn²⁺, Mn²⁺, and salicylic acid under solvothermal conditions. With a simple programmable heating process, the shell of the hollow structures can be adjusted and double-/triple-shelled ZnMnO₃, ZnMn₂O₄, and ZnMn₂O₄/Mn₂O₃ hollow microspheres have been controllably obtained. When the triple-shelled ZnMn₂O₄ hollow microspheres are used as anode materials for lithium-ion batteries, excellent activity and enhanced stability can be achieved. The triple-shelled hollow ZnMn₂O₄ exhibits a reversible capacity of 537 mA·h·g^-1 at 400 mA·g^-1 and a nearly 100% capacity retention after 150 cycles. This strategy is facile and scalable for the production of high-quality complex hollow nanostructures, with the possibility of extension to the preparation of other mixed metal oxides with complex structures.