Safety concerns about organic media-based batteries are the key public arguments against their widespread usage. Aqueous batteries (ABs), based on water which is environmentally benign, provide a promising alternative for safe, cost-effective, and scalable energy storage, with high power density and tolerance against mishandling. Research interests and achievements in ABs have surged globally in the past 5 years. However, their large-scale application is plagued by the limited output voltage and inadequate energy density. We present the challenges in AB fundamental research, focusing on the design of advanced materials and practical applications of whole devices. Potential interactions of the challenges in different AB systems are established. A critical appraisal of recent advances in ABs is presented for addressing the key issues, with special emphasis on the connection between advanced materials and emerging electrochemistry. Last, we provide a roadmap starting with material design and ending with the commercialization of next-generation reliable ABs.

Noble metals manifest themselves with unique electronic structures and irreplaceable activity toward a wide range of catalytic applications but are unfortunately restricted by limited choice of geometric structures spanning single atoms, clusters, nanoparticles, and bulk crystals. Herein, we propose how to overcome this limitation by integrating noble metal atoms into the lattice of transition metal oxides to create a new type of hybrid structure. This study shows that iridium single atoms can be accommodated into the cationic sites of cobalt spinel oxide with short-range order and an identical spatial correlation as the host lattice. The resultant Ir0.06Co2.94O4 catalyst exhibits much higher electrocatalytic activity than the parent oxide by 2 orders of magnitude toward the challenging oxygen evolution reaction under acidic conditions. Because of the strong interaction between iridium and cobalt oxide support, the Ir0.06Co2.94O4 catalyst shows significantly improved corrosion resistance under acidic conditions and oxidative potentials. This work eliminates the “close-packing” limitation of noble metals and offers promising opportunity to create analogues with desired topologies for various catalytic applications.

Single-atom catalysts (SACs) include a promising family of electrocatalysts with unique geometric structures. Beyond conventional ones with fully isolated metal sites, an emerging class of catalysts with the adjacent metal single atoms exhibiting intersite metal-metal interactions appear in recent years and can be denoted as correlated SACs (C-SACs). This type of catalysts provides more opportunities to achieve substantial structural modification and performance enhancement toward a wider range of electrocatalytic applications. On the basis of a clear identification of metal-metal interactions, this review critically examines the recent research progress in C-SACs. It shows that the control of metal-metal interactions enables regulation of atomic structure, local coordination, and electronic properties of metal single atoms, which facilitate the modulation of electrocatalytic behavior of C-SACs. Last, we outline directions for future work in the design and development of C-SACs, which is indispensable for creating high-performing new SAC architectures.

Sulfur is an important electrode material in metal−sulfur batteries. It is usually coupled with metal anodes and undergoes electrochemical reduction to form metal sulfides. Herein, we demonstrate, for the first time, the reversible sulfur oxidation process in AlCl3/carbamide ionic liquid, where sulfur is electrochemically oxidized by AlCl4− to form AlSCl7. The sulfur oxidation is: 1) highly reversible with an efficiency of ~94%; and 2) workable within a wide range of high potentials. As a result, the Al−S battery based on sulfur oxidation can be cycled steadily around ~1.8 V, which is the highest operation voltage in Al−S batteries. The study of sulfur oxidation process benefits the understanding of sulfur chemistry and provides a valuable inspiration for the design of other high-voltage metal−sulfur batteries, not limited to Al−S configurations.

Metal sulfides electrodeposition in sulfur cathodes mitigates the shuttle effect of polysulfides to achieve high Coulombic efficiency in secondary metal-sulfur batteries. However, fundamental understanding of metal sulfides electrodeposition and kinetics mechanism remains limited. Here using room-temperature sodium-sulfur cells as a model system, we report a Mo5N6 cathode material that enables efficient Na2S electrodeposition to achieve an initial discharge capacity of 512 mAh g−1 at a specific current of 1 675 mA g−1, and a final discharge capacity of 186 mAh g−1 after 10,000 cycles. Combined analyses from synchrotron-based spectroscopic characterizations, electrochemical kinetics measurements and density functional theory computations confirm that the high d-band position results in a low Na2S2 dissociation free energy for Mo5N6. This promotes Na2S electrodeposition, and thereby favours long-term cell cycling performance.