Spatially Guided Assembly of Polyoxometalate Superlattices and Their Derivatives as High-Power Sodium-Ion Battery Anodes.

The use of polyoxometalate clusters (POMs) with multitudinous structures and surface properties as building blocks has sparked the development of cluster-assembled materials with many prospective applications. In comparison to classic molecules and assembly processes, control over the steric interactions and linkage of large POMs to achieve superlattices with multiple levels of organization remains a great challenge. This work presents a universal approach to modulate the spatial coordination behavior and configurations, and achieves a class of cluster superlattice architectures formed by linear alignment and two-dimensional arrangement of POM units. The formation mechanism is explained as a stepwise co-assembly pathway in which POMs can intervene and dictate a typical stripping-restacking combination mode with the lamellar mediator. These cluster superlattices with long-range POMs ordering impart distinct merits to their derivatives by sulfuration, for which we demonstrate the substantially promoted power and cycling life of these POM derivatives applied as sodium-ion battery anodes.