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Lithium-sulfur batteries (LSBs) have attracted intensive attention as a promising next-generation energy storage system, due to the high energy density and low cost of sulfur cathodes. Despite the substantial progress...

Calcium ion batteries (CIBs) are pursued as potentially low‐cost and safe alternatives to current Li‐ion batteries due to the high abundance of calcium element. However, the large and divalent nature of Ca2+ leads to strong interaction with intercalation hosts, sluggish ion diffusion kinetics and low power output. Herein, a small molecular organic anode is reported, tetracarboxylic diimide (PTCDI), involving carbonyl enolization (CO↔CO−) in aqueous electrolytes, which bypasses the diffusion difficulties in intercalation‐type electrodes and avoid capacity sacrifice for polymer organic electrodes, thus manifesting rapid and high Ca storage capacities. In an aqueous Ca‐ion cell, the PTCDI presents a reversible capacity of 112 mAh g−1, a high‐capacity retention of 80% after 1000 cycles and a high‐power capability at 5 A g−1, which rival the state‐of‐the‐art anode materials in CIBs. Experiments and simulations reveal that Ca ions are diffusing along the a axis tunnel to enolize carbonyl groups without being entrapped in the aromatic carbon layers. The feasibility of PTCDI anodes in practical CIBs is demonstrated by coupling with cost‐effective Prussian blue analogous cathodes and CaCl2 aqueous electrolyte. The appreciable Ca storage performance of small molecular crystals will spur the development of green organic CIBs.

Multivalent metal batteries (MMBs) have been considered potentially high‐energy and low‐cost alternatives to commercial Li‐ion batteries, thus attracting tremendous research interest for energy‐storage applications. However, the plating and stripping of multivalent metals (i.e., Zn, Ca, Mg) suffer from low Coulombic efficiencies and short cycle life, which are largely rooted in the unstable solid electrolyte interphase. Apart from exploring new electrolytes or artificial layers for robust interphases, fundamental works on deciphering interfacial chemistry have also been conducted. This work is dedicated to summarizing the state‐of‐the‐art advances in understanding the interphases for multivalent metal anodes revealed by transmission electron microscopy (TEM) methods. Operando and cryogenic TEM with high spatial and temporal resolutions realize the dynamic visualization of the vulnerable chemical structures in interphase layers. Following a scrutinization of the interphases on different metal anodes, we elucidate their features for appealing multivalent metal anodes. Finally, perspectives are proposed for the remaining issues on analyzing and regulating interphases for practical MMBs.