Sn- -based metal oxides and composites have been widely investigated as candidate anodes for lithium-ion batteries. However, continuous capacity fade caused by serious volumetric expansion and crystal pulverization is often noticed during lithiation and alloying processes. In this study, we design a novel heterogeneous structural composite by constructing sandwich-structured graphene hollow spheres limited Mn2SnO4/SnO2 heterostructures (Mn2SnO4/SnO2@SG), of which infiltration of Mn source promotes the dissolution-redeposition of SnO2 in hollow-spherical graphene (SnO2@SG) and their in-situ transformation into Mn2SnO4; and the uniform distributed Mn2SnO4 and SnO2 nanoparticles are adjacent each other to form heterostructure within the sandwiched graphene hollow spheres. By comparing with the single metal oxide SnO2@SG material, the influence of the microstructure, chemical composition, element valence state and electrochemical properties of the heterostructured Mn2SnO4/SnO2@SG is investigated. The results show that the construction of Mn2SnO4/SnO2 heterostructure dramatically improves electronic/ionic transport kinetics and increases lithium storage reversibility, therefore leading to distinctly superior rate capability (823.8 mAh g(-1) at 5 C) and cycling capacity. An ultra-high discharge capacity of 1180.4 mA h g(-1) is maintained up to 100 cycles at 100 mA g(-1). The promising electrochemical performances can be attributed to the sandwiched-structure hollow graphene spherical skeleton and the formation of unique Mn2SnO4/SnO(2)heterostructures. (C) 2020 Elsevier Inc. All rights reserved.