Hollow/porous nanostructures derived from nanoscale metal–organic frameworks towards high performance anodes for lithium-ion batteries

Abstract

Lithium-ion batteries (LIBs), owing to their high energy density, light weight, and long cycle life, have shown considerable promise for storage devices. The successful utilization of LIBs depends strongly on the preparation of nanomaterials with outstanding lithium storage properties. Recent progress has demonstrated that hollow/porous nanostructured oxides are very attractive candidates for LIBs anodes due to their high storage capacities. Here, we aim to provide an overview of nanoscale metal–organic frameworks (NMOFs)-templated synthesis of hollow/porous nanostructured oxides and their LIBs applications. By choosing some typical NMOFs as examples, we present a comprehensive summary of synthetic procedures for nanostructured oxides, such as binary, ternary and composite oxides. Hollow/porous structures are readily obtained due to volume loss and release of internally generated gas molecules during the calcination of NMOFs in air. Interestingly, the NMOFs-derived hollow/porous structures possess several special features: pores generated from gas molecules release will connect to each other, which are distinct from “dead pores”; pore size often appears to be <10 nm; in terms of surface chemistry, the pore surface is hydrophobic. These structural features are believed to be the most critical factors that determine LIBs’ performance. Indeed, it has been shown that these NMOFs-derived hollow/porous oxides exhibit excellent electrochemical performance as anode materials for LIBs, including high storage capacity, good cycle stability, and so on. For example, a high charge capacity of 1465 mA h g⁻¹ at a rate of 300 mA g⁻¹ was observed after 50 cycles for NMOFs-derived Co₃O₄ porous nanocages, which corresponds to 94.09% of the initial capacity (1557 mA h g⁻¹), indicating excellent stability. The capacity of NMOFs-derived Co₃O₄ is higher than that of other Co₃O₄ nanostructures obtained by a conventional two-step route, including nanosheets (1450 mA h g⁻¹ at 50 mA g⁻¹), nanobelts (1400 mA h g⁻¹ at 40 mA g⁻¹) and nanoflowers (694 mA h g⁻¹ at 100 mA g⁻¹). The capacity is also better than Co₃O₄ octahedra obtained by a one-step hydrothermal method (946 mA h g⁻¹ at 100 mA g⁻¹). In this review, we will summarize the recent research advances on NMOFs-derived hollow/porous oxides as LIBs anodes. The enhanced lithium storage properties have been discussed in relation to their special structural parameters. Moreover, remarks on the current challenges and perspectives for future NMOFs applications are proposed. Through this systematic review, we aim to stress the importance of NMOFs templates for the fabrication of hollow/porous functional materials that would result in improved physicochemical properties and provide insights to guide future research for LIBs applications.