Yaokang Lv

Polymer cathodes featuring versatile designable redox‐active motifs and structural anti‐dissolution in aqueous electrolytes have attracted interest for advancing zinc‐organic batteries. However, their implementation is hindered by insulating electronic properties and sluggish ion transport, both arising from twisted molecule chains with poor structural planarity, which limits active‐site accessibility and capacity delivery. Here we design planar macromolecular semiconductors (PMSs) by fusing a four‐electron pyrene‐4,5,9,10‐tetraone acceptor and a two‐electron tetraminobenzoquinone donator into long‐range conjugated polymeric skeletons through intermolecular π – π interactions. The highly π ‐extended planarity endows PMSs with a semiconducting property (7.64 × 10 ⁻⁷ S cm ⁻¹ ) that promotes efficient electron delocalization, and yields the highest ion diffusion coefficient (6.52 × 10 ⁻⁷ cm ² s ⁻¹ ) among reported organic cathodes. Leveraging synergistic fast electron‐ion transport kinetics, the long‐range stacking of molecular planes minimizes conformational disorder, enabling near‐complete utilization (98.4%) of redox‐active quinone−phenazine motifs with an ultralow activation energy (0.19 eV). Consequently, Zn||PMSs battery liberates high capacities (442/263 mAh g ⁻¹ at 0.2/100 A g ⁻¹ ), alongside a long lifespan (60,000 cycles). Besides, PMSs cathode enables a 348 mAh zinc pouch cell with a high mass loading (20 mg cm ⁻² ) to operate stably for 1000 cycles. This work provides a promising direction to design planar organic semiconductors for boosting electron‐ion migration kinetics toward better zinc batteries.

Hexaazatrinaphthylene self-fused multi-N-heterocycles enable multielectron Mg ²⁺ redox reactions and structural insolubility in aqueous electrolytes, achieving excellent capacity (375 mAh g ⁻¹ ) and life (20 000 cycles) in magnesium-ion batteries.

Organic anodes for calcium‐ion batteries (CIBs) generally rely on extended conjugated structures to host high‐density redox couples for enhanced capacity. However, this design often lowers frontier molecular orbital energies, resulting in undesirably high redox potentials (> −0.6 V) that compromise cell voltages. Here we propose a dichalcogenide electronegativity engineering by introducing a family of diphenyl dichalcogen compounds (Ph‐2S, Ph‐2Se, and Ph‐2Te) featuring dual sulfide, selenide, telluride motifs, as high‐performance CIB anodes. The decreasing electronegativity along dichalcogenide bonds (S─S > Se─Se > Te─Te) progressively elevates the lowest unoccupied molecular orbital energy from −2.80 (Ph‐2S) to −2.50 (Ph‐2Se) and −2.00 eV (Ph‐2Te), shifting the redox potentials to increasingly negative values of −0.76, −0.82, and −0.84 V, respectively. Moreover, Ph‐2Te shows the strongest redox activity to start four‐electron Te‐conversion with 98% utilization (vs. 65% of Ph‐2Se and 31% of Ph‐2S). Consequently, Ph‐2Te anode liberates the highest capacity of 257 mAh g ⁻¹ , outperforming Ph‐2S (152 mAh g ⁻¹ ) and Ph‐2Se (223 mAh g ⁻¹ ). Notably, Ph‐2Te anode enables state‐of‐the‐art CIBs with a high redox voltage (1.2 V), an active‐material‐pair level energy density (68 Wh kg ⁻¹ ), and a long lifespan (5000 cycles). This work establishes dichalcogenide engineering as a promising strategy toward low‐redox‐potential organic anodes for advanced CIBs.

Organic anodes for calcium‐ion batteries (CIBs) generally rely on extended conjugated structures to host high‐density redox couples for enhanced capacity. However, this design often lowers frontier molecular orbital energies, resulting in undesirably high redox potentials (> −0.6 V) that compromise cell voltages. Here we propose a dichalcogenide electronegativity engineering by introducing a family of diphenyl dichalcogen compounds (Ph‐2S, Ph‐2Se, and Ph‐2Te) featuring dual sulfide, selenide, telluride motifs, as high‐performance CIB anodes. The decreasing electronegativity along dichalcogenide bonds (S─S > Se─Se > Te─Te) progressively elevates the lowest unoccupied molecular orbital energy from −2.80 (Ph‐2S) to −2.50 (Ph‐2Se) and −2.00 eV (Ph‐2Te), shifting the redox potentials to increasingly negative values of −0.76, −0.82, and −0.84 V, respectively. Moreover, Ph‐2Te shows the strongest redox activity to start four‐electron Te‐conversion with 98% utilization (vs. 65% of Ph‐2Se and 31% of Ph‐2S). Consequently, Ph‐2Te anode liberates the highest capacity of 257 mAh g ⁻¹ , outperforming Ph‐2S (152 mAh g ⁻¹ ) and Ph‐2Se (223 mAh g ⁻¹ ). Notably, Ph‐2Te anode enables state‐of‐the‐art CIBs with a high redox voltage (1.2 V), an active‐material‐pair level energy density (68 Wh kg ⁻¹ ), and a long lifespan (5000 cycles). This work establishes dichalcogenide engineering as a promising strategy toward low‐redox‐potential organic anodes for advanced CIBs.

Covalent organic frameworks (COFs) have emerged as competitive battery materials by solving the solubility and/or kinetics limitations of small molecules and polymers, while offering structure‐function merits over inorganics. However, a tricky trade‐off remains between active‐site density and accessibility. Here we describe a trade‐off‐breaking design of sulfur‐modulated COF superstructures (TD‐COFS) via synergistic geometric‐electronic structure engineering. Flower‐shaped TD‐COFS is constructed by intermolecular H‐bonding and π‐π stacking self‐assembly of tricarbonyl‐benzothiazole motifs, maximizing exposure of well‐organized multi‐protophilic active sites and π‐electron delocalization routes. Electron‐rich S‐heterocyclic benzothiazole (replacing N‐containing bipyridine, TM‐COFS) increases the electronegativity of TD‐COFS and reduces the redox barrier (S < N), enabling synchronous optimization of molecular charge distribution and electronic bandgap (−0.75/1.82 vs. −0.52/2.47 eV of TM‐COFS). Furthermore, sulfur modulation boosts proton‐transfer redox activity with a low activation energy (0.23 eV), and achieves full accessibility of highly dense protophilic sites in TD‐COFS (99.3% vs. 0.34 eV/84.7% of TM‐COFS), liberating high capacity (356 mAh g ⁻¹ ) and cycling stability (70 000 cycles). Besides, the assembled soft‐packed all‐organic proton batteries deliver state‐of‐the‐art capacity (161 mAh g ⁻¹ ), energy density (81 Wh kg ⁻¹ _cell ), and life (3000 cycles). This work broadens the design philosophy of structured‐tailored COFs with highly dense and accessible protophilic sites for better proton batteries.

Covalent organic frameworks (COFs) have emerged as competitive battery materials by solving the solubility and/or kinetics limitations of small molecules and polymers, while offering structure‐function merits over inorganics. However, a tricky trade‐off remains between active‐site density and accessibility. Here we describe a trade‐off‐breaking design of sulfur‐modulated COF superstructures (TD‐COFS) via synergistic geometric‐electronic structure engineering. Flower‐shaped TD‐COFS is constructed by intermolecular H‐bonding and π‐π stacking self‐assembly of tricarbonyl‐benzothiazole motifs, maximizing exposure of well‐organized multi‐protophilic active sites and π‐electron delocalization routes. Electron‐rich S‐heterocyclic benzothiazole (replacing N‐containing bipyridine, TM‐COFS) increases the electronegativity of TD‐COFS and reduces the redox barrier (S < N), enabling synchronous optimization of molecular charge distribution and electronic bandgap (−0.75/1.82 vs. −0.52/2.47 eV of TM‐COFS). Furthermore, sulfur modulation boosts proton‐transfer redox activity with a low activation energy (0.23 eV), and achieves full accessibility of highly dense protophilic sites in TD‐COFS (99.3% vs. 0.34 eV/84.7% of TM‐COFS), liberating high capacity (356 mAh g ⁻¹ ) and cycling stability (70 000 cycles). Besides, the assembled soft‐packed all‐organic proton batteries deliver state‐of‐the‐art capacity (161 mAh g ⁻¹ ), energy density (81 Wh kg ⁻¹ _cell ), and life (3000 cycles). This work broadens the design philosophy of structured‐tailored COFs with highly dense and accessible protophilic sites for better proton batteries.

A nonplanar tertiary-N extended nitrobenzene enables an insoluble and low-energy-barrier nitroarene small molecule cathode, achieving a state-of-the-art cycling life of 180 000 cycles in aqueous batteries.

The evolution of electrochromic materials and technologies has opened innovative avenues for smart devices. However, their civilian adoption remains constrained by high material costs and energy-intensive fabrication processes. Recent research has shifted toward integrated electrochromic systems that combine energy storage with visualization capabilities. Among these, electrochromic supercapacitors (ECSCs) suffer from relatively low energy density, constraining their storage capacity, whereas electrochromic zinc-ion batteries (ECZIBs) demonstrate superior energy density, making them more promising for smart energy storage applications. This review systematically examines the fundamental structure, key performance parameters, and essential materials of ECZIBs, with particular focus on recent progress in the design of cathode, anode, and electrolyte materials. We summarize the major bottlenecks currently impeding performance enhancement and practical deployment, discuss potential strategies to overcome these challenges, and provide an outlook on future development trends in ECZIBs. We hope this concise review will offer valuable guidance and inspire further research, ultimately fostering new breakthroughs in this emerging field.

Polymer anodes solve the solubility issue of small molecules while offering structure-function merits compared with inorganics for superior ammonium-ion batteries (AIBs), but current research focuses either on rigid polymers for rapid ion transport or flexible ones for high active-site utilization. Here, we design polymeric heptazine-biguanide frameworks (HBFs) via integrating planar three-electron meleme and rotated four-electron chlorhexidine linkers, which harness the advantages of rigid heptazine and flexible biguanide while alleviating their respective shortcomings. Heptazines afford fast electron delocalization, and biguanide chains reduce steric hindrances, leading to ultrahigh utilization of imine sites (99.6%) and ultralow activation energy (0.15 electron volts) in HBFs. Septuple hydrogen-bonded NH ₄ ⁺ coordination per heptazine-biguanide module enables a record capacity (314 milliampere hours per gram) and an exceptional rate capability (60 amperes per gram) among reported polymer anodes. The structural merits of HBFs also enable state-of-the-art all-polymer AIBs with unprecedented energy density (100.6 watt-hours per kilogram of cell) and long life (120,000 cycles). This work gives a previously unidentified paradigm for designing rigid-flexible organic materials toward better AIBs.

This review systematically summarizes the advancements of versatile inorganic cathode materials for aqueous zinc-ion batteries, and outlines the current challenges and development roadmaps towards next-generation advanced energy storage.