The practical application of sulfur-based batteries is significantly limited by sluggish reaction kinetics and structural collapse. Herein, a copper-modified sulfurized polyaniline (CuSPANI) cathode with distinctive d-p-π multi-orbital coupling is constructed through Cu heteroatom introduction. This coupling, arising from hybridization between Cu d orbitals and sulfurized polyaniline (SPANI) p/π orbitals, enables triple electronic modulation: reducing energy barriers to enhance kinetics, expanding electron delocalization to improve conductivity, and activating horizontal Cu d orbitals to strengthen structural stability. Consequently, the aqueous CuSPANI battery delivers a high reversible capacity of 834.75 mAh gs−1 at 3 C and exceptional cycling stability (61.2% capacity retention after 60,000 cycles at 15 C). Moreover, the designed flexible quasi-solid-state pouch cell achieves a 1.25 V output and maintains stable power under deformation, highlighting its potential for wearable energy storage. This work provides new insight into designing high-performance sulfurized polymers via orbital hybridization.

Manganese hexacyanoferrate (MnHCF), also known as Prussian white cathode material, has become a popular choice for sodium-ion batteries due to its high output voltage, low cost, and high theoretical specific capacity. However, MnHCF synthesized via conventional methods exhibits a cubic phase, presenting issues such as CN vacancies, crystalline water, poor conductivity, and complex phase transitions during charge-discharge cycles. These factors lead to low capacity utilization and poor cycle life, limiting its application in sodium-ion batteries. The performance of Prussian white cathode material is closely related to its structure. In this study, MnHCF with monoclinic phase characteristics was synthesized by introducing nitrogen as the reaction atmosphere. After 200 cycles at 5C, its capacity retention rate was 75%, showing more excellent cycle performance and rate performance compared with the cubic phase. Additionally, this work investigates structural changes during moderate discharge cycles. Crucially, in situ EIS and cyclic voltammetry at varying scan rates characterize the evolving kinetic processes throughout charge-discharge cycles. This study presents an effective synthesis strategy, which is helpful for the design and optimization of Prussian blue analog sodium-ion batteries.

ABSTRACT Aqueous dual‐ion batteries (DIBs) are becoming one of the most compelling choices for large‐scale stationary energy storage owing to the excellent safety performance, high power density, and cost‐effectiveness. However, their low output voltage leads to insufficient energy density. Here, we design a highly reversible pH‐neutral Ag↔Ag 2 SO 4 electrochemistry and construct a novel Zn‐based conversion‐type aqueous anion–cation shuttle DIB. A dendrite‐free Zn anode with functional graphite layer is prepared to improve cycle life. Benefitting from the synchronous effect of Zn 2+ /SO 4 2− dual charge carries and dendrite‐free anode, the DIB delivers a high output voltage of 1.41 V, volumetric energy density of 3295.4 Wh L −1 at 0.5 A g −1 , and 95.9% capacity retention over 300 cycles at 1 A g −1 , superior to most reported DIBs. As a proof of concept, we fabricate a quasi‐solid‐state aqueous DIB with remarkable mechanical strength, flexibility, and impressive temperature resistance. With working temperature decreasing from 20 to −10°C, it shows only a very low‐capacity loss (8.4%) and negligible polarization change (0.05 V). This work overcomes the bottleneck of low output voltage in aqueous DIBs and offers a promising pathway for the development of future aqueous batteries with high energy density.

Aqueous proton batteries (APBs) are increasingly recognized as promising energy storage devices owing to their high safety, environmental friendliness, and fast kinetics. Copper hexacyanoferrate (CuHCF), with its open framework structure and interconnected proton transport channels, is regarded as a promising cathode material for APBs. However, its practical application is hindered by limited active sites and structural distortion induced by the Jahn-Teller effect. To address these issues, this study employs a Co2+ doping strategy to successfully synthesize a CuCoHCF-1 material with high specific capacity and excellent structural stability. The incorporation of Co2+ optimizes the local coordination environment by forming stronger Co-N bonds, effectively suppressing lattice distortion. Meanwhile, it modulates the intramolecular charge distribution, activating more Fe sites for redox reactions. Benefiting from the synergistic enhancement of structural stability and electrochemical activity, the CuCoHCF-1 cathode exhibits superior rate performance, a high specific discharge capacity (84.4 mAh & centerdot;g-1 at 0.1 A & centerdot;g-1), and remarkable cycling stability (93.1% capacity retention after 40,000 cycles at 5 A & centerdot;g-1). This study provides an effective strategy for designing high-performance cathode materials for APBs through multifunctional cation doping.

Aqueous metal-selenium batteries (AMSeBs) have emerged as promising candidates for safe, cost-effective, and high-energy-density energy storage, yet their development is hindered by challenges spanning electrode stability, reaction reversibility, and electrolyte compatibility. This review systematically explores the thermodynamic and electrochemical landscape of AMSeBs, integrating theoretical analysis with experimental advances to establish a rational design framework. First, by evaluating key parameters, including electrode potentials, volume change rates, solubility of metal selenides, and energy metrics, we identify promising systems such as Zn-Se and Cu-Se, along with unexplored candidates like Fe-Se and Ga-Se. Second, selenium-based cathodes are categorized into three types, elemental Se & SexSy composites, organic selenides, and transition metal selenides, with emphasis on multi-electron transfer mechanisms, particularly the six-electron Se4+/Se2- redox pathway, which offers a route to overcome capacity limitations. Third, strategies for stabilizing metal anodes, expanding the electrochemical stability window of aqueous electrolytes, and mitigating shuttle effects are critically discussed. Finally, we outline future directions, including interface engineering, artificial intelligence-assisted material screening, and flexible device integration, providing a roadmap toward high-performance AMSeBs for next-generation energy storage applications.

Aqueous batteries can be deemed as a prospective alternative for reliable, economically feasible, and scalable energy storage systems. However, the inadequate output voltage and insufficient energy density limit their large-scale applications. For solving these problems, significant efforts have been made to broaden the electrochemical stability window of aqueous electrolytes. As an essential battery component, the electrolyte profoundly influences the electrochemical behavior and window of aqueous batteries. This article summarizes key strategies and latest progress in electrolyte design, with the central goal of widening the electrochemical stability window of aqueous batteries for the development of high-performance and high-voltage systems. We begin by discussing concentrated electrolytes, including water-in-salt and hydrate-melt systems, which modulate water activity and facilitate the formation of protective interphases. We then outline the use of multifunctional electrolyte additives that kinetically suppress water splitting by disrupting the hydrogen-bond network, isolating electrode contact, or tailoring ion solvation structures. Furthermore, pH-decoupling electrolytes, which thermodynamically extend the ESW by physically separating acidic and alkaline environments, are introduced. Finally, this review explores other promising strategies and provides a forward-looking perspective on the design of next-generation high-voltage aqueous batteries, highlighting pathways toward breaking the 4 V barrier.

The practical application of sulfur-based batteries remains challenged by the sluggish charge transfer kinetics and structural instability of sulfur cathodes, largely attributed to the absence of efficient electron transport pathways and robust electrode architecture. Herein, we present an in situ electron bridge construction strategy by introducing a transition metal to tailor the electronic properties and reinforce the structure of sulfurized polyacrylonitrile (SPAN) cathode. The dynamic d-p orbital hybridization between copper and SPAN within the electron bridge promotes bandgap closure, shifting the electronic character from a semiconducting state toward a metallic state, thereby establishing high-speed electron transfer channels and accelerating redox kinetics. Simultaneously, the self-assembled copper-modified SPAN (CuSPAN), driven by in situ thermodynamically-favorable process, intrinsically reinforces the cathode structure, conferring exceptional long-term operational stability. As a result, the aqueous CuSPAN-based battery achieves a high reversible capacity of 760 mAh g-1 at 3 C and outstanding cyclic stability with 79.2% capacity retention over 50 000 cycles at 15 C, superior to previously reported aqueous sulfur batteries. To verify the practicality, a flexible pouch cell is built based on the CuSPAN cathode, Zn anode, and gel electrolytes, delivering a stable operating voltage (1.2 V), high energy density (950 Wh kg-1), and remarkable cycling stability even under various harsh conditions.

ABSTRACT Aqueous zinc‐ion batteries are promising for large‐scale energy storage due to their safety and cost‐effectiveness. The industrial application of zinc metal anodes is impeded by challenges, including dendrite growth, hydrogen evolution reaction, and interfacial passivation. Current research, though abundant in strategies, lacks a unified scientific framework, leading to fragmented progress. This review examines strategies for managing the chemical environment at the interface. The failure of zinc anodes is due to thermodynamic instability, which is evident through side reactions, and kinetic heterogeneity, as demonstrated by the random growth of dendrites. This article provides a systematic review of the fundamental mechanisms of strategies across three principal dimensions: ion flux regulation, interfacial chemistry modulation, and nucleation/growth control. Examples include ion flow regulation for uniform Zn 2+ transport and electric field uniformity, interface chemistry regulation to minimize water activity and side reactions, artificial solid electrolyte interphase construction, solvation structure reconstruction, and regulation of nucleation and growth for dense deposition through heterogeneous nucleation and interfacial energy optimization. This review highlights antagonistic effects in multi‐strategy synergy and critiques the materials‐first trap, along with the misleading nature of unrealistic experimental conditions. Finally, it offers an overview of essential avenues for practical application.

Developing highly efficient and stable non-precious-metal bifunctional oxygen electrocatalysts remains a primary bottleneck for the widespread application of rechargeable zinc-air batteries (RZABs). While transition-metal phosphides (TMPs) are promising candidates, their efficacy is fundamentally constrained by the mutually exclusive adsorption-energy requirements of oxygen intermediates during the oxygen reduction and evolution reactions (ORR/OER). Herein, an innovative Zn-induced electron-bridge strategy is proposed to construct strongly coupled heterointerfaces with atomic-scale precision. In this design, Zn species act dually as structure-directing agents and electronic modulators. Comprehensive experimental and theoretical analyses demonstrate that Zn incorporation strategically optimizes the d band centers of the Fe/Ni active sites, alleviating the excessively strong adsorption of oxygenated intermediates. Furthermore, it establishes interatomic cross-interfacial electron-transfer channels that synergistically accelerate reaction kinetics. Consequently, the engineered Zn-FeNiP nanocomposite, confined within a three-dimensional (3D) N, P-codoped carbon matrix (Zn-FeNiP@3DNPC), delivers outstanding bifunctional performance with a narrow potential gap (ΔE) of 0.63 V, featuring a high ORR half-wave potential of 0.85 V and a low OER potential of 1.48 V at 10 mA cm−2. When integrated into an RZAB, the air cathode delivers a high peak power density of 162.8 mW cm−2 and exceptional ultralong cycling stability over 1600 h. This work establishes a generalizable method based on precise electronic-structure engineering via interfacial electron bridging for designing robust electrocatalysts.

ABSTRACT Aqueous Zn–S batteries (AZSBs) have garnered significant attention owing to their high energy density and low cost. However, their practical application is hindered by the limited electrochemical reversibility of sulfur cathode and the interfacial instability of zinc anode. Here, we developed a functionalized co‐solvent electrolyte incorporating aprotic polar tetramethylurea (TMU) and potassium iodide (KI) as synergistic additives, where TMU regulates the Zn 2+ coordination environment and cooperates with iodide species to construct an electrolyte‐derived, interface‐confined, and coordination‐mediated dynamic ion bridge pathway. This pathway couples TMU‐regulated Zn 2+ transport with I 3 − /I − ‐mediated charge transfer at the sulfur cathode interface, thereby reducing the kinetic barriers for Zn 2+ transport and ZnS conversion. Meanwhile, the TMU/KI‐regulated interfacial environment homogenizes Zn 2+ flux at the anode, promotes uniform Zn plating/stripping, and suppresses parasitic reactions. Through the synergistic regulation of the ion bridge, the AZSB delivers a high specific capacity of 759 mAh g −1 at 5 A g −1 and maintains over 71.2% capacity retention after 1000 cycles. This work proposes a promising electrolyte design strategy for energetic AZSBs via synergistic regulation, offering a promising route toward next‐generation sustainable energy storage systems.

Given their inherent advantages in safety, low cost, and environmental benefits, aqueous proton batteries (APBs) have emerged as a highly promising new energy storage system. Prussian blue analogues (PBAs) are considered excellent cathode materials for APBs due to their simple preparation, open three-dimensional framework, and abundant redox sites. However, they still suffer from issues such as unstable lattice structures and poor cycling performance. To address this, a Cu-Fe-based Turnbull's blue analogue (denoted as TBACu) was synthesized via a facile co-precipitation method, demonstrating superior long-cycle cycling stability. This outstanding performance stems from two primary factors: First, the abundant crystalline water incorporated during synthesis forms a continuous hydrogen-bond network within the crystal structure, facilitating rapid proton transport via the Grotthuss mechanism. Second, the incorporation of Cu greatly enhances the stability of the lattice framework, ensuring highly reversible proton insertion/extraction during cycling. As a result, TBA-Cu exhibits an outstanding specific capacity of 73.2 mAh g-1 at 0.1 A g-1 and demonstrates exceptional cycling robustness, with 83% capacity retention even after 50,000 cycles at 5 A g-1. This work provides valuable insights for the design of high-performance and long-life Prussian blue-based cathode materials for proton batteries.

Zinc-ion batteries (ZIBs), as sustainable energy storage systems, possess the advantages of high capacity, low cost, and environmental friendliness, and have thus attracted extensive attention. However, ZIBs still face challenges such as electrode corrosion, passivation, and uncontrollable side reactions during practical operation. Gel electrolytes (GEs) combine the high ionic conductivity of liquid electrolytes with the high safety and structural stability of solid-state electrolytes, effectively addressing many challenges encountered by both cathodes and anodes. Meanwhile, through tailoring the composition and crosslinking mode of the gel network, GEs can endow batteries with wide-temperature adaptability, wearability, implantability, and smart responsiveness, thereby significantly enhancing their practical performance. On this basis, this review first systematically summarizes the composition and preparation methods of GEs. Subsequently, from the perspective of modification mechanisms, it provides an in-depth analysis of the modification strategies and mechanisms by which GEs regulate anode stability, suppress cathode dissolution, and improve ion transport performance. It further highlights the remarkable electrochemical performance of GEs in diverse application environments. Finally, current challenges and future directions for the development of GEs are summarized and prospected. By comprehensively reviewing high-performance GEs for ZIBs, this review aims to provide valuable references for the future development and design of advanced GEs as well as the commercial application of ZIBs.

Developing highly efficient and durable non-precious metal electrocatalysts for oxygen reduction reaction (ORR) remains a critical challenge for the practical application of zinc-air batteries (ZABs). Herein, we successfully synthesized a robust N, P-codoped Fe-N-C catalyst featuring a unique 0D/1D intertwined architecture through a phosphorus-induced heteroatom-modulation strategy. By utilizing FePc-encapsulated ZIF-8 as a precursor, the in-situ growth of 1D carbon nanotubes from 0D carbon dodecahedrons was achieved, constructing a 3D hierarchical conductive network. Experimental and mechanistic analyses reveal that P-doping serves as the key morphology director. It not only induces the formation of structural-stable 1D nanotubes to enhance electron transfer but also modulates the electronic density of Fe centers to elevate electro-oxidation resistance. Consequently, the optimized catalyst exhibits a superior half-wave potential (E1/2) of 0.884 V (vs. RHE) in alkaline media. Remarkably, the as-assembled ZAB achieves an exceptional stability of over 1300 h, demonstrating the superior structural integrity and durability of the 0D/1D network. This research offers a strategic design for engineering high-performance and stable Fe-N-C catalysts through synergistic 0D/1D architecture construction.

Heterostructured composites have emerged as pivotal platforms for multifunctional electrocatalysis, where in-situ synthesis strategies prove critical in constructing atomically precise interfaces. However, precisely engineering such interfaces with favorable electronic structures and optimized adsorption energetics remains a significant challenge. To address this, we report a dynamic phase-reconstruction strategy by a bonded phosphorus source strategy enabling the spontaneous formation of Co-Co2P heterointerfaces within a three-dimensional N, P-codoped carbon architecture (Co-Co2P@HNPC), engineered through molecular self-assembly of histidine-phytic acid supramolecular complexes with cobalt ions. The metallic Co-Co bonds and Co-P coordination reveals charge redistribution at heterointerfaces through strengthened Co-N-C bonding networks. DFT result demonstrates that the reconfigured heterointerface synergistically optimizes d-band center positioning via p-d orbital hybridization, concurrently lowering the Gibbs free energy barriers for both ORR and OER. The optimized catalyst achieves low overpotentials (ηOER = 1.63 V @10 mA cm−2; E1/2 = 0.83 V) and exceptional rechargeable Zn-air battery performance, with a lifespan exceeding 1200 h and a peak power density of 201 mW cm−2. This study introduces a dynamic phosphidation engineering strategy, utilizing chemical anchoring of P-precursors, providing new insights for designing effective heterointerface electrocatalysts.

The commercialization process of advanced zinc-air batteries (ZABs) mainly hinges on the efficiency of their bifunctional oxygen electrocatalysts. Among various candidates, FeCo alloy encapsulated in N-doped carbon material is a highly promising material. However, during the synthesis process, metal agglomeration and structural collapse often occur, which leads to insufficient active sites and poor stability. Herein, 3D hexagonallike FeCo alloy embedded N-doped carbon catalysts (FeCo-NC-2) are synthesized via an in-situ Fe incorporation strategy followed by one-step pyrolysis way. Fe doping effectively modulates the electronic structure of metal centers and acts as a structural promoter, inhibiting nanoparticle agglomeration and fostering a porous architecture with abundant metal-Nx sites. The resulting FeCo-NC-2 exhibits outstanding bifunctional performance, achieving a half-wave potential (E1/2) of 0.873 V for the oxygen reduction reaction (ORR) and an overpotential of 327 mV at 10 mA cm- 2 for the oxygen evolution reaction (OER), corresponding to a small potential gap (Delta E = Ej=10 - E1/2) of only 0.684 V. Assembled ZABs deliver a peak power density of 155 mW cm-2 and prominent cycle performance over 450 h, significantly outperforming noble-metal benchmarks. This study demonstrates the effectiveness of collaborative electronics and morphological engineering in developing high-performance electrocatalysts for sustainable energy applications.

To overcome the limitations of low activity of single-metal sites and suboptimal interface structures of porous carbon-derived electrocatalysts, a nitrogen-doped carbon-coated CuCo nanoparticle (CuxCoy−NC) catalyst was synthesized using a straightforward grinding method followed by high-temperature pyrolysis. The introduction of CuCo bimetallic sites plays a crucial role in enhancing the intrinsic catalytic activity by diversifying the active sites and optimizing the adsorption energy of oxygen intermediates. Particularly, when the Cu/Co mass ratio is 1:1, the formation of thin-walled carbon nanotubes effectively exposes the embedded metal active sites and refines the interface structure of the porous carbon matrix. As a result, the optimized CuxCoy−NC (1:1) catalyst demonstrates exceptional electrocatalytic performance for the oxygen reduction reaction. This enhancement enables the assembled zinc−air batteries to achieve an impressive discharge specific capacity of 812 mA·h/g at 25 mA/cm2.

Polyethylene oxide based all-solid-state lithium-sulfur batteries hold broad application prospects due to their low cost and high theoretical energy density. However, the shuttle effect of polysulfides and poor kinetics hinder their commercialization. Here, we employ a chemical reduction method to incorporate copper into lotus-podinspired biomass charcoal (BC-Cu), designing a novel three-dimensional honeycomb porous sulfur composite cathode. This refined cathode material design effectively confines polysulfides within the structure, significantly suppressing the shuttle effect. The introduction of copper accelerates the conversion process, while its unique porous structure provides fast migration pathways for charge carriers, ultimately enabling rapid reaction kinetics. Batteries containing BC-Cu exhibit the lowest charge transfer resistance, the highest discharge capacity, and the fastest ion diffusion rate. Notably, after 100 cycles at 0.5C, the battery retains a capacity of 1132.5 mAh g- 1, approximately seven times that of current commercial lithium-ion batteries. In addition, the performance enhancement mechanism after cathode modification is systematically investigated by means of polysulfide adsorption simulations, the galvanostatic intermittent titration technique, multi-scan cyclic voltammetry profiles, and in situ electrochemical impedance spectroscopy. This work opens a new avenue for designing highsafety, high-energy and low-cost battery systems.