Formation mechanism of Mn x Co 3- x O 4 yolk-shell structures.

Formation of Mn x Co 3- x O 4 yolk-shell microspheres via a solvothermal reaction of hydrated cobalt and manganese nitrates in ethanol is investigated. Spinel nanocrystals of cobalt oxide or cobalt-rich ternary oxide preferentially develop in the system, while manganese-rich hydroxide form Mn(OH) 2 -type nanosheets. Instead of continuing to grow individually, the nanocrystallites and nanosheets aggregate into large microspheres due to their strong inter-particle interaction. When the proportion of Mn-rich nanosheets is high, therefore the overall density is low, dehydration of hydroxide nanosheets and a surface re-crystallisation lead to formation of a dense and rigid shell, which is separated from a solid or hollow core via a further Ostwald ripening process. The proposed formation mechanism of the yolk-shell structures based on electron microscopic studies would help us to develop yolk-shell structure based multifunctional materials.