To improve the energy conversion efficiency and durability of zinc–air batteries (ZABs) for large-scale implementations, here we propose an “air-breathing” strategy to significantly enlarge triple-interfaces with intensified mass transfer. By dip-coating the aerophilic perfluorochemical compounds (PFC) and amphiphilic ionomers into the self-supported electrodes, (1) the high solubility of O2 in the PFC nanoemulsions greatly increases triple-phase boundaries and facilitates the efficient supply/removal of O2 from the electrolyte; (2) the ionomers with hydrophobic and hydrophilic functionalities enable fast gas, water, and ion transport to the triple-phase boundaries; and (3) the self-supported electrode without binder ensures fast electron transfer while the firm integration prevents catalyst shedding. By applying this strategy, the ZABs show a high power density of 115 mW cm–2 and a narrow discharge/charge gap of 0.64 V at 10 mA cm–2 and a long-cycling durability (over 1000 h). This work provides a universal approach to promote gas-evolving reactions for electrochemical applications.

The establishment of abundant three‐phase interfaces with accelerated mass transfer in air cathodes is highly desirable for the development of high‐rate and long‐cycling rechargeable zinc–air batteries (ZABs). Covalent organic frameworks (COFs) exhibit tailored nanopore structures, facilitating the rational tuning of their specific properties. Here, by finely tuning the fluorinated nanopores of a COF, a novel air cathode for rechargeable ZABs is unprecedentedly designed and synthesized. COF nanosheets are decorated with fluorinated alkyl chains, which shows high affinity to oxygen (O2), in its nanopores (fluorinated COF). The fluorinated COF nanosheets are stacked into well‐defined O2‐transport channels, which are then assembled into aerophilic “nano‐islands” on the hydrophilic FeNi layered‐double‐hydroxide (FeNi LDH) electrocatalyst surface. Therefore, the mass‐transport “highway” for O2 and water is segregated on the nanoscale, which significantly enlarges the area of three‐phase boundaries and greatly promotes the mass‐transfer therein. ZABs based on the COF‐modified air cathode deliver a small charge/discharge voltage gap (0.64 V at 5 mA cm−2), a peak power density (118 mW cm−2), and a stable cyclability. This work provides a feasible approach for the design of the air cathodes for high‐performance ZABs, and will expand the new application of COFs.

In battery electrolyte design principles, tuning Li+ solvation structure is an effective way to connect electrolyte chemistry with interfacial chemistry. Although recent proposed solvation tuning strategies are able to improve battery cyclability, a comprehensive strategy for electrolyte design remains imperative. Here, we report a solvation tuning strategy by utilizing molecular steric effect to create a “bulky coordinating” structure. Based on this strategy, the designed electrolyte generates an inorganic-rich solid electrolyte interphase (SEI) and cathode–electrolyte interphase (CEI), leading to excellent compatibility with both Li metal anodes and high-voltage cathodes. Under an ultrahigh voltage of 4.6 V, Li/NMC811 full-cells (N/P = 2.0) hold an 84.1% capacity retention over 150 cycles and industrial Li/NMC811 pouch cells realize an energy density of 495 Wh kg–1. This study provides innovative insights into Li+ solvation tuning for electrolyte engineering and offers a promising path toward developing high-energy Li metal batteries.

Highly efficient, cis-selective, stable, recyclable and reusable heterogeneous single-site MOF-supported rhodium catalysts polymerize PA and its derivatives, producing cis-transoidal PPAs and their functional derivatives having a helical configuration or AIE properties.