Metal–organic frameworks (MOFs) have potential application prospects in the electrochemical energy storage and conversion area on account of their high specific surface area, high porosity, tunable pore size, and structural diversity when compared to traditional porous materials. In order to expand the application scope of MOFs, thermal decomposition can be carried out via calcination treatment in order to convert them into porous metal oxide materials. In this review, we summarize the synthetic methods of MOF-derived transition metal oxide (TMO) composites and their applications in lithium-ion batteries (LIBs) as anodes. A variety of TMOs and composites with different structures and morphologies derived from MOFs based on several types of ligands, including 1,4-benzenedicarboxylic acid (H₂BDC), 1,3,5-benzenetricarboxylic acid (H₃BTC), 2-methylimidazole, ferricyanide, and other unusual organic linkers, have been discussed. Finally, current challenges and possible solutions of MOF-derived anode materials have been proposed.

Conspicuously, metal–organic frameworks (MOFs) serve as homogenously and periodically atom‐dispersed self‐sacrificial template for in situ engineering of hierarchical porous carbon‐encapsulated micro/nanoheterostructure materials, integrating the merits of micro/nanostructure to high‐volumetric energy storage. Copper phosphide represents a promising candidate due to its compact material density compared to commercial graphite. Herein, micro/nanostructured Cu₃P/Cu encapsulated by carbon‐nanotube‐assembled hierarchical octahedral carbonaceous matrix (Cu₃P/Cu@CNHO) is constructed by an in situ MOF‐derived engineering for novel anode material in LIBs, which achieves an extraordinary cycling stability (a well‐maintained gravimetric/volumetric capacity of 463.2 mAh g⁻¹/1878.4 mAh cm⁻³ at 1 A g⁻¹ up to 1600 cycles) and distinguished rate capability (an ameliorated capacity of 317.7 mAh g⁻¹ even at 10 A g⁻¹), together with unprecedented heat‐resistant capability (an elevated temperature of 50 °C for 1000 cycles maintaining 434.7 mAh g⁻¹ at 0.5 A g⁻¹). The superior electrochemical performance of Cu₃P/Cu@CNHO is credited to the large specific surface area, conductive carbon matrix and metallic copper dopants, synergistic effects of the intrinsic Cu₃P/Cu heterostructure, and well‐defined micro/nanostructure, facilitating a boosted electrochemical conductivity and accelerated diffusion kinetics.

Lithium-ion batteries (LIBs) have dominated the portable electronic and electrochemical energy markets since their commercialisation, whose high cost and lithium scarcity have prompted the development of other alkali-ion batteries (AIBs) including sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). Owing to larger ion sizes of Na⁺ and K⁺ compared with Li⁺, nanocomposites with excellent crystallinity orientation and well-developed porosity show unprecedented potential for advanced lithium/sodium/potassium storage. With enticing open rigid framework structures, Prussian blue analogues (PBAs) remain promising self-sacrificial templates for the preparation of various nanocomposites, whose appeal originates from the well-retained porous structures and exceptional electrochemical activities after thermal decomposition. This review focuses on the recent progress of PBA-derived nanocomposites from their fabrication, lithium/sodium/potassium storage mechanism, and applications in AIBs (LIBs, SIBs, and PIBs). To distinguish various PBA derivatives, the working mechanism and applications of PBA-templated metal oxides, metal chalcogenides, metal phosphides, and other nanocomposites are systematically evaluated, facilitating the establishment of a structure–activity correlation for these materials. Based on the fruitful achievements of PBA-derived nanocomposites, perspectives for their future development are envisioned, aiming to narrow down the gap between laboratory study and industrial reality.