The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in‐depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal‐ion batteries, lithium–sulfur batteries, and metal–air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and future development prospects are forecast, and the electrode materials are further optimized through defect engineering to promote the development of the battery industry.

Covalent organic frameworks (COFs) are excellent platforms with tailored functionalities in photocatalysis. There are still challenges in increasing the photochemical performance of COFs. Therefore, we designed and prepared a series of COFs for photocatalytic hydrogen generation. Varying different ratios of βketoenamine to imine moieties in the linkages could differ the ordered structure, visible light harvesting, and bandgap. Overall, βketoenamine-linked COFs exhibited much better photocatalytic activity than those COFs having both β-ketoenamine and imine moieties on account of a nonquenched excited state and more favorable HOMO level in the photoinduced oxidation reaction from the former. Specifically, after in situ growth of β-ketoenamine-linked COFs onto NH 2 −Ti 3 C 2 T x MXene via covalent connection, the heterohybrid showed an obvious improvement in photocatalytic H 2 evolution because of strong covalent coupling, electrical conductivity, and efficient charge transfer. This integrated linkage evolution and covalent hybridization approach advances the development of COF-based photocatalysts.

The commercialization of fuel cells, such as proton exchange membrane fuel cells and direct methanol/formic acid fuel cells, is hampered by their poor stability, high cost, fuel crossover, and the sluggish kinetics of platinum (Pt) and Pt‐based electrocatalysts for both the cathodic oxygen reduction reaction (ORR) and the anodic hydrogen oxidation reaction (HOR) or small molecule oxidation reaction (SMOR). Thus far, the exploitation of active and stable electrocatalysts has been the most promising strategy to improve the performance of fuel cells. Accordingly, increasing attention is being devoted to modulating the surface/interface electronic structure of electrocatalysts and optimizing the adsorption energy of intermediate species by defect engineering to enhance their catalytic performance. Defect engineering is introduced in terms of defect definition, classification, characterization, construction, and understanding. Subsequently, the latest advances in defective electrocatalysts for ORR and HOR/SMOR in fuel cells are scientifically and systematically summarized. Furthermore, the structure–activity relationships between defect engineering and electrocatalytic ability are further illustrated by coupling experimental results and theoretical calculations. With a deeper understanding of these complex relationships, the integration of defective electrocatalysts into single fuel‐cell systems is also discussed. Finally, the potential challenges and prospects of defective electrocatalysts are further proposed, covering controllable preparation, in situ characterization, and commercial applications.

Developing high-performance batteries relies on material breakthroughs. During the past few years, various in situ characterization tools have been developed and have become indispensible in studying and the eventual optimization of battery materials. However, soft X-ray spectroscopy, one of the most sensitive probes of electronic states, has been mainly limited to ex situ experiments for battery research. Here we achieve in situ and operando soft X-ray absorption spectroscopy of lithium-ion battery cathodes. Taking advantage of the elemental, chemical and surface sensitivities of soft X-rays, we discover distinct lithium-ion and electron dynamics in Li(Co1/3Ni1/3Mn1/3)O2 and LiFePO4 cathodes in polymer electrolytes. The contrast between the two systems and the relaxation effect in LiFePO4 is attributed to a phase transformation mechanism, and the mesoscale morphology and charge conductivity of the electrodes. These discoveries demonstrate feasibility and power of in situ soft X-ray spectroscopy for studying integrated and dynamic effects in batteries.

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