Self-template fabrication of multi-scaled ZnFe2O4 microspheres and their excellent lithium-ion storage properties

•Multi-scaled structure of ZnFe2O4 microspheres have been synthesized via facile solvothermal methods with various annealing processes.•As anodes for lithium-ion batteries, all those as-synthesized ZnFe2O4 electrodes exhibited excellent electrochemical stabilities.•DFT calculations have been adopted to understand the Li+ insertion mechanism of ZnFe2O4 during the discharge process. [Display omitted] Self-template multi-scaled structure of ZnFe2O4 (ZFO) microspheres were synthesized through a solvothermal method, subsequently accompanied by various annealing processes. Specifically, hollow microspheres ZFO samples with modifiable internal structures (ranging from solid, core-in-hollow wall and double wall hollow) were synthesized differently through a mutual cooperation of inward-outward ripening mechanism by an anisotropic heating process during the calcination process. As active anodes for lithium-ion batteries (LIBs), that as-synthesized ZFO electrodes exhibited outstanding electrochemical properties and cyclic stabilities. Importantly, density functionally theoretical calculations have been investigated so as to understand the intermediate structures and electrochemical mechanisms of as-synthesized electrodes in the initial discharge process.