Dongliang Chao

Ligand ablation of aldehyde-functionalized ZIF-90 creates asymmetric CaN ₃ O sites on mesoporous carbon. Ca 4p polarization promotes side-on dual-iodine adsorption, lowering reaction barriers and accelerating iodine conversion in Zn–I ₂ batteries.

Aqueous manganese batteries based on MnO ₂ electrodeposition-dissolution process offer a compelling route to safe, low-cost and scalable energy storage. Despite their merits of high specific capacity and voltage, the hindrance towards practical implementation is the parasitic reaction and accumulation of dead manganese, leading to poor reversibility and low energy efficiency. Here, we identify the lattice-oxygen topology as the structural origin of Mn ³⁺ -driven parasitic reaction during weakly acidic MnO ₂ dissolution. By synthesizing a series of MnO ₂ polymorphs with a controllable transition from pyramidal (O _py ) to planar oxygen (O _pl ) topology, we reveal that the rapid O _py dissolution accounts for the formation of MnOOH intermediates (i.e., Mn ³⁺ ), but MnOOH is suppressed on O _pl -dominated pathways owing to the larger lattice distortion. Guided by this mechanism, a facile and cost-effective approach is applied to realize dual-regulation of oxygen topology, namely, activating O _pl dissolution and simultaneously passivating O _py sites through strengthened Mn-O bonding. As a result of the suppressed Mn ³⁺ disproportionation side reaction, the Mn-Cu cell retains 100% capacity over 5800 cycles with an energy efficiency of 83% and Coulombic efficiency close to 99.99%. This study unlocks the potential of aqueous manganese oxide batteries for highly durable and sustainable energy storage.

High‐valence iodine redox chemistry in aqueous batteries is fundamentally constrained by the requirement of highly concentrated halide environments, which stabilize reactive iodine cations but inevitably induce electrolyte corrosion and sluggish interfacial kinetics. In this study, we demonstrate an interfacial halide enrichment strategy that circumvents this long‐standing concentration dependence in four‐electron zinc‐iodine batteries. By introducing only 0.1 M bromo‐pyrrolidinium salt into the electrolyte, a localized halide‐rich microenvironment is spontaneously reconstructed at the cathode interface, enabling reversible I ^– /I ₂ /I ⁺ conversion without relying on bulk hyper‐concentrated halides. Spectroscopic analyses and theoretical calculations reveal that the pyrrolidinium cations preferentially anchor at the charged interface through complementary electrostatic and soft interactions with iodine/polyhalide species, thereby promoting interfacial Br ^– enrichment and stabilizing metastable IBr ₂ ^– intermediates. Meanwhile, ethylene glycol (EG)‐mediated solvation regulation and interfacial water exclusion further suppress iodine hydrolysis and parasitic reactions. As a result, the dilute‐halide electrolyte system achieves a reversible capacity of 413.3 mAh g ⁻¹ at 0.4 A g ⁻¹ and maintains 88.2% capacity retention after 5000 cycles at 2 A g ⁻¹ , while simultaneously improving zinc anode reversibility. This work establishes an interfacial halide enrichment paradigm for regulating high‐valence halogen chemistry beyond conventional electrolyte concentration limitations.

High‐valence iodine redox chemistry in aqueous batteries is fundamentally constrained by the requirement of highly concentrated halide environments, which stabilize reactive iodine cations but inevitably induce electrolyte corrosion and sluggish interfacial kinetics. In this study, we demonstrate an interfacial halide enrichment strategy that circumvents this long‐standing concentration dependence in four‐electron zinc‐iodine batteries. By introducing only 0.1 M bromo‐pyrrolidinium salt into the electrolyte, a localized halide‐rich microenvironment is spontaneously reconstructed at the cathode interface, enabling reversible I ^– /I ₂ /I ⁺ conversion without relying on bulk hyper‐concentrated halides. Spectroscopic analyses and theoretical calculations reveal that the pyrrolidinium cations preferentially anchor at the charged interface through complementary electrostatic and soft interactions with iodine/polyhalide species, thereby promoting interfacial Br ^– enrichment and stabilizing metastable IBr ₂ ^– intermediates. Meanwhile, ethylene glycol (EG)‐mediated solvation regulation and interfacial water exclusion further suppress iodine hydrolysis and parasitic reactions. As a result, the dilute‐halide electrolyte system achieves a reversible capacity of 413.3 mAh g ⁻¹ at 0.4 A g ⁻¹ and maintains 88.2% capacity retention after 5000 cycles at 2 A g ⁻¹ , while simultaneously improving zinc anode reversibility. This work establishes an interfacial halide enrichment paradigm for regulating high‐valence halogen chemistry beyond conventional electrolyte concentration limitations.

The rapid expansion of autonomous IoT networks and wearable electronics has intensified the demand for photo-rechargeable zinc-based batteries (PRZBBs). While realizing high overall energy conversion efficiency intrinsically relies on cathode materials capable of multi-electron transfer reactions, current literature largely treats the fundamental electrochemistry of aqueous zinc batteries and the macroscopic engineering of solar-integrated devices as isolated domains. This review bridges this critical gap, offering a unique positioning by establishing a unified analytical framework that directly links fundamental multi-electron redox mechanisms to the dynamic architectural requirements of PRZBBs. Moving beyond a conventional cataloging of material classes, we critically evaluate diverse cathode platforms, including transition metal oxides, Prussian blue analogues, organics, halogens, and sulfur. Our incremental contribution lies in decoupling how specific multi-step reaction kinetics, distinct voltage plateaus, and dominant charge carriers dictate solar cell coupling strategies, particularly concerning maximum power point matching and intermittent charging adaptability. Furthermore, we critically and systematically assess the practical bottlenecks of these chemistries, such as shuttle effects, kinetic limitations, and voltage hysteresis, that hinder scalable integration. Finally, we distill these insights into a prioritized, roadmap-oriented perspective, outlining the short- to long-term engineering and scientific milestones necessary to translate fundamental multi-electron zinc chemistry into next-generation, commercially viable self-powered technologies.

Sodium-ion batteries represent promising energy storage devices, yet their deployment is severely hampered by sluggish ion-transport kinetics and unstable electrode–electrolyte interfacial chemistry that deteriorate rate capability and cycling lifespan, particularly under high-loading electrode configurations. Here, we report a structural anode design comprising double-shelled TiO2 spheres assembled from cross-distributed 2 nm thick nanosheets and uniformly encapsulated by a graphene-like armor. This architecture enables predominantly surface-controlled sodium storage behavior with ultrafast reaction kinetics and exceptional stability, overcoming the long-standing trade-off between capacity, rate performance, and cycle life. The rationally designed electrode achieves a practically relevant areal capacity of 2.13 mAh cm–2 and outstanding rate capability (121 mAh g–1 at 100 C). Remarkably, it remains more than 90% of its capacity over 3,000 cycles at 5 C under a high mass loading of 10.5 mg cm–2, outperforming conventional anode structures. This work establishes a structural design strategy for advanced anodes applicable in practical high-power batteries.

This review presents a framework linking feedstock-aware considerations with regeneration strategies for spent LFP materials, combining targeted repair for traceable, homogeneous feedstocks with normalized processing for heterogeneous feedstocks.

Sulfur-based aqueous batteries for sustainable energy storage have the advantages of material abundance, low cost, and high theoretical capacity. While aqueous multivalent metal–sulfur electrochemistry is effective in suppressing sulfide dissolution due to its low solubility product constant, it is intrinsically limited by sluggish conversion kinetics. Here, we decouple sulfur-conversion kinetics from sulfur-species stabilization by introducing a kinetic promoter. Operando spectroscopy, electrochemical quartz crystal microbalance analysis, and density functional theory simulations reveal that the Li+ promoter preferentially targets long-chain sulfur species and lowers the redox barrier, while Mn2+ anchors sulfur species and immobilizes short-chain intermediates, steering the reaction from a dissolution route to a rapid, solid-state-dominated pathway. This cooperative mechanism induces the formation of a highly reversible ternary solid phase with an apparent average composition close to Li4Mn6S8, suppressing the accumulation of soluble polysulfide intermediates and enabling deep discharge at ultrahigh rates. Consequently, the SABs with kinetic promoter exhibit highly reversible sulfur redox chemistry with a capacity of 1012 mAh g–1 at 15 A g–1. We also demonstrate the strategy in Zn2+-S and Ni2+-S systems, illustrating its effectiveness in various multivalent aqueous sulfur batteries.