Metal-organic frameworks (MOFs) have recently emerged as ideal electrode materials and precursors for electrochemical energy storage and conversion (EESC) owing to their large specific surface areas, highly tunable porosities, abundant active sites, and diversified choices of metal nodes and organic linkers. Both MOF-based and MOF-derived materials in powder form have been widely investigated in relation to their synthesis methods, structure and morphology controls, and performance advantages in targeted applications. However, to engage them for energy applications, both binders and additives would be required to form postprocessed electrodes, fundamentally eliminating some of the active sites and thus degrading the superior effects of the MOF-based/derived materials. The advancement of freestanding electrodes provides a new promising platform for MOF-based/derived materials in EESC thanks to their apparent merits, including fast electron/charge transmission and seamless contact between active materials and current collectors. Benefiting from the synergistic effect of freestanding structures and MOF-based/derived materials, outstanding electrochemical performance in EESC can be achieved, stimulating the increasing enthusiasm in recent years. This review provides a timely and comprehensive overview on the structural features and fabrication techniques of freestanding MOF-based/derived electrodes. Then, the latest advances in freestanding MOF-based/derived electrodes are summarized from electrochemical energy storage devices to electrocatalysis. Finally, insights into the currently faced challenges and further perspectives on these feasible solutions of freestanding MOF-based/derived electrodes for EESC are discussed, aiming at providing a new set of guidance to promote their further development in scale-up production and commercial applications.

Rechargeable batteries of high energy density and overall performance are becoming a critically important technology in the rapidly changing society of the twenty-first century. While lithium-ion batteries have so far been the dominant choice, numerous emerging applications call for higher capacity, better safety and lower costs while maintaining sufficient cyclability. The design space for potentially better alternatives is extremely large, with numerous new chemistries and architectures being simultaneously explored. These include other insertion ions (e.g. sodium and numerous multivalent ions), conversion electrode materials (e.g. silicon, metallic anodes, halides and chalcogens) and aqueous and solid electrolytes. However, each of these potential “beyond lithium-ion” alternatives faces numerous challenges that often lead to very poor cyclability, especially at the commercial cell level, while lithium-ion batteries continue to improve in performance and decrease in cost. This review examines fundamental principles to rationalise these numerous developments, and in each case, a brief overview is given on the advantages, advances, remaining challenges preventing cell-level implementation and the state-of-the-art of the solutions to these challenges. Finally, research and development results obtained in academia are compared to emerging commercial examples, as a commentary on the current and near-future viability of these “beyond lithium-ion” alternatives.

All‐solid‐state zinc–air batteries are characterized as low cost and have high energy density, providing wearable devices with an ideal power source. However, the sluggish oxygen reduction and evolution reactions in air cathodes are obstacles to its flexible and rechargeable application. Herein, a strategy called MOF‐on‐MOF (MOF, metal‐organic framework) is presented for the structural design of air cathodes, which creatively develops an efficient oxygen catalyst comprising hierarchical Co₃O₄ nanoparticles anchored in nitrogen‐doped carbon nano‐micro arrays on flexible carbon cloth (Co₃O₄@N‐CNMAs/CC). This hierarchical and free‐standing structure design guarantees high catalyst loading on air cathodes with multiple electrocatalytic activity sites, undoubtedly boosting reaction kinetics, and energy density of an all‐solid‐state zinc–air battery. The integrated Co₃O₄@N‐CNMAs/CC cathode in an all‐solid‐state zinc–air battery exhibits a high open circuit potential of 1.461 V, a high capacity of 815 mAh g⁻¹ Zn at 1 mA cm⁻², a high energy density of 1010 Wh kg⁻¹ Zn, excellent cycling stability as well as outstanding mechanical flexibility, significantly outperforming the Pt/C‐based cathode. This work opens a new door for the practical applications of rechargeable zinc–air batteries in wearable electronic devices.