The integration of surface-regular micro/nanostructured electrodes within a limited footprint area is promising to enhance the electrochemical performance of planar micro-supercapacitors (P-MSCs), while developing simple yet efficient manufacturing methods for such electrodes remains a challenge. Here, we propose a universal strategy combining femtosecond laser plasma lithography with spatial light modulation (SLM-FPL), fabricating well-ordered sub-wavelength micro/nanostructured electrodes of interdigital P-MSCs (SEP-MSCs) on graphene oxide (GO) films. Achieving 500/50 µm finger widths/spacings and 680 nm internal grating periods, this method enables device densities >25 units inch−2 with processing efficiency orders of magnitude higher than conventional laser direct writing. Further performance optimizations via wettability modification, electric field engineering, and hybrid composites (GO-MXene/COF) yield outstanding specific capacitance ( 41.4 F cm−3) and cycling stability (93

ABSTRACT Sustainable aqueous zinc‐ion batteries (AZIBs) have emerged as promising next‐generation energy storage solutions, aligning with global initiatives to mitigate climate change and promote low‐carbon transitions. Their appeal stems from the utilization of earth‐abundant materials and aqueous electrolytes, which minimize reliance on scarce metals and alleviate the safety and environmental risks associated with organic‐solvent‐based systems. This review systematically evaluates the sustainability of AZIBs throughout their entire life cycle, encompassing material selection, cell manufacturing, operational use, and end‐of‐life recycling, while providing a forward‐looking perspective on their advancement. However, critical hurdles to industrialization persist, including zinc dendrite growth, cathode dissolution, and restricted cycle life. To realize genuine sustainability, future research must prioritize green material innovations, such as bio‐based binders, functional separators, and eco‐friendly electrolytes, while implementing dry electrode fabrication and other low‐impact manufacturing techniques. Adopting a comprehensive life‐cycle approach guided by circular economy principles is vital for fostering synergistic optimization across design, production, use, and recycling, ultimately achieving a “cradle‐to‐cradle” system. Furthermore, supportive policies, cross‐sector collaboration, and international standardization are essential to bridge the gap between laboratory research and large‐scale application. Through systematic, multi‐faceted innovation, sustainable AZIBs are well‐positioned to drive the global energy transition.

As a sustainable cathode material for sodium-ion batteries, Na4MnFe(PO4)3 (NMFP) is prized for high theoretical operating voltage and cost-effectiveness. However, its practical electrochemical activity is notoriously poor, contradicting theoretical predictions. Here, we reveal that this inactivity stems primarily from Mott localization, driven by strong electron correlations within the high-spin 3d5 electronic configuration (t2g 3eg 2) of Mn2+ and Fe3+. This symmetric, half-filled state leads to pronounced charge localization, severely suppressing the intrinsic redox activity. To address this limitation, we devised a symmetry-breaking reconstruction strategy which reorganizes the spin ordering to promote electron delocalization and activates multiple redox couples (Mn4+/Mn3+, Mn3+/Mn2+, and Fe3+/Fe2+). More critically, induce a novel "Na2 dp Na1" migration path for Na+, with a remarkably lower energy barrier than those of conventional paths (0.39 vs. 0.98 eV). Consequently, the engineered Na4Mn0.5Fe0.5Cr0.5Ti0.5(PO4)3 delivers 138.84 mAh g-1 at 0.1C, which represents a 12.74-fold breakthrough over the pristine NMFP (10.9 mAh g-1). Our findings elucidate symmetry-breaking as a critical route for activating Mott-localized states in polyanionic frameworks and establish a new paradigm for designing redox-active and sustainable cathode materials.

Aqueous zinc-iodine batteries(Zn-I2Bs)emerge as promising candidates for grid-scale energy storage due to their inherent safety,low cost,and environmental benignity.However,their practical deployment is hindered by critical challenges,including severe self-discharge driven by coupled polyiodide shutting and hydrogen evolution reaction(HER),limited practical energy density constrained by low voltage plateaus and predominantly two-electron iodine redox,sluggish reaction kinetics from complex iodine species interconversion,and zinc anode instability(dendrites,corrosion,passivation).This work provides a comprehensive analysis of Zn-I2B mechanisms,debating the interplay between iodine's layered structure favoring intercalation and its multivalency enabling conversion reactions,particularly pathways for electron redox beyond I-/I2.Strategies to mitigate these challenges are critically reviewed:anchoring iodine species within tailored host materials(e.g.,functionalized carbons,COFs,perovskites)to suppress shuttling;electrolyte engineering(e.g.,DES,additives)to sequester free I-and modulate solvation;functional separators/membranes for ion sieving;catalytic materials(transition metal/nonmetal-based)to accelerate kinetics;and anode protection/modification(interfacial layers,hydrogel electrolytes,nonmetallic anodes)to enhance reversibility.The review synthesizes recent advances,identifies persistent bottlenecks,and outlines future research directions essential for realizing the commercial potential of high-performance Zn-I2Bs.

The large-scale applications of anion exchange membrane water electrolysis (AEMWEs) and zinc-air batteries (ZABs) are observably limited by the lack of highly active, multifunctional, and industrially applicable electrocatalysts. In this work, we report a solvent-free rapid pyrolysis strategy that successfully prepares a composite material of Pt8V-V2O3 heterostructure supported on nitrogen-doped porous carbon (Pt8V-V2O3@NPC). In alkaline hydrogen evolution reactions, the mass activity of Pt8V-V2O3@NPC reaches 10.6 times that of commercial Pt/C, while the half-wave potential for the oxygen reduction reaction is 0.89 V. The assembled ZABs demonstrate stable cycling performance over 5550 cycles at a current density of 5.0 mA cm-2, with negligible voltage decay. Likewise, AEMWEs incorporating this material exhibit stable operation for over 500 h at a current density of 1000 mA cm-2, with a voltage decay rate of only 0.14 mV h-1. Combined X-ray absorption fine structure spectroscopy and theoretical studies demonstrate that the interfacial electron transfer from V2O3 to Pt8V optimizes the d-band center of Pt8V-V2O3. This study proposes an interface electronic bridging strategy for the design of multifunctional electrocatalysts, which may provide support for the development of practical clean energy technologies.

ABSTRACT As a sustainable cathode material for sodium‐ion batteries, Na 4 MnFe(PO 4 ) 3 (NMFP) is prized for high theoretical operating voltage and cost‐effectiveness. However, its practical electrochemical activity is notoriously poor, contradicting theoretical predictions. Here, we reveal that this inactivity stems primarily from Mott localization, driven by strong electron correlations within the high‐spin 3d 5 electronic configuration (t 2g 3 e g 2 ) of Mn 2+ and Fe 3+ . This symmetric, half‐filled state leads to pronounced charge localization, severely suppressing the intrinsic redox activity. To address this limitation, we devised a symmetry‐breaking reconstruction strategy which reorganizes the spin ordering to promote electron delocalization and activates multiple redox couples (Mn 4+ /Mn 3+ , Mn 3+ /Mn 2+ , and Fe 3+ /Fe 2+ ). More critically, induce a novel “Na2 dp Na1” migration path for Na + , with a remarkably lower energy barrier than those of conventional paths (0.39 vs. 0.98 eV). Consequently, the engineered Na 4 Mn 0.5 Fe 0.5 Cr 0.5 Ti 0.5 (PO 4 ) 3 delivers 138.84 mAh g −1 at 0.1C, which represents a 12.74‐fold breakthrough over the pristine NMFP (10.9 mAh g −1 ). Our findings elucidate symmetry‐breaking as a critical route for activating Mott‐localized states in polyanionic frameworks and establish a new paradigm for designing redox‐active and sustainable cathode materials.

As global demand for safe, sustainable, and low-cost energy storage grows, aqueous zinc-iodine batteries (AZIBs) emerge as promising candidates. However, their practical application is hindered by complex side reactions, including polyiodide shuttling, the hydrogen evolution reaction (HER), and electrolyte acidification. Conventional glass fiber separators fail to mitigate these interfacial issues and pose significant environmental burdens due to high carbon emissions and non-degradability. This study introduces a bio-based separator derived from Aspergillus niger mycelium. Its 3D interconnected network and polar-rich surface (-OH, -NH2) facilitate chemical polyiodide anchoring, water adsorption, and local pH buffering. Operating through a "water-confining-promoted-desolvation" mechanism, the separator suppresses the shuttle effect and HER while stabilizing zinc deposition. AZIBs using this separator exhibit excellent capacity retention over 10 000 cycles at 1.0 A g-1, achieving an energy density of 208.77 Wh kg-1 and maintaining 153.32 mAh g-1 at -25°C. Life-cycle assessment shows a 99.4% reduction in carbon emissions compared to glass fiber, with full biodegradability within 50 days. This work offers a sustainable paradigm for high-performance separators, advancing AZIBs toward environmental compatibility.

Sodium iron fluorophosphate (Na2FePO4F, NFPF) is considered a promising candidate for sodium-ion batteries (SIBs) cathode materials due to low cost and abundant resources, but its practical application is limited by sluggish kinetics and low energy efficiency. An orbital-level electronic structure modulation strategy by constructing NFPF-Na3V2(PO4)2F3 (NVPF) heterojunction was proposed to reconstruct electron-ion synergistic transport channels for performance enhancement. Density functional theory (DFT) reveals that interfacial Fe-V 3d orbital coupling can enhance electron delocalization through upshifting of the d x 2 -y 2 orbital, which synergistically enhances electron delocalization across the heterointerface and boosts electronic conductivity by 20-fold. Synchrotron radiation, X-ray absorption spectroscopy, and DFT further confirm that the interfacial local electric field optimizes Na+ diffusion path by modulating its coordination environment and forming new electronic pathways at the interface. Analysis of the distribution of relaxation times also illustrates the faster reaction kinetics. The NFPF-NVPF cathode delivers a specific capacity of 120.9 mAh g-1 at 0.2 C (113.6 mAh g-1 for NFPF) and exhibits a high capacity retention of 81.7% compared to 60.9% for NFPF and 75.9% for the mixing composites. This study offers a novel approach for multi-objective optimization of "electron conduction-ion diffusion-structural stability."

Decoupling key intermediates’ adsorption via asymmetric 3d‐5d‐orbital hybridization overcomes the intrinsic scaling relation bottleneck, enabling rational design of high‐performance, durable multifunctional electrocatalysts for anion exchange membrane water electrolyzers (AEMWEs) and Zn–air batteries (ZABs). Here, we reveal that asymmetric 3d‐5d‐orbital hybridization, engineered through the synergy of lattice strain and defect structures in a nitrogen‐doped carbon‐supported PtCo alloy (PtCo@NPC), effectively decouples these adsorption energies of key intermediates. PtCo@NPC demonstrates exceptional multifunctional electrocatalytic performance for the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction in alkaline media. Density functional theory calculations suggest that electronic structure modulation tunes the adsorption characteristics of intermediates, while X‐ray absorption fine structure spectroscopy confirms the corresponding changes in the electronic states of surface Pt and Co atoms. When deployed in devices, PtCo@NPC enables AEMWEs to operate stably for 522 h at 1000 mA cm −2 with a voltage decay rate of only 0.103 mV h −1 and empowers ZABs to achieve a long cycle life of over 2520 cycles at 5.0 mA cm −2 . This study highlights electronic‐structure modulation as a powerful strategy for advanced energy technologies.

Developing efficient and stable bifunctional oxygen catalysts is essential for addressing the trade‐off between reduction and oxidation reactions in rechargeable zinc–air batteries (ZABs). In this work, a novel composite regulation‐enhanced strategy is proposed to prepare a heterogeneous composite catalyst, FeCoNiCuMn@NC/NiFeCe LDH, exhibiting exceptional bifunctional activity. The catalyst achieves a half‐wave potential of 0.905 V for the oxygen reduction reaction and a 266 mV overpotential at 10 mA cm −2 for oxygen evolution reactions. Experimental and theoretical analyses reveal that the heterogeneous interface between FeCoNiCuMn@NC and NiFeCe LDH effectively optimizes the electronic structure of materials by shifting the d‐band center closer to the Fermi level. This optimization not only enhances the continuous distribution of electronic density but also improves the adsorption and desorption processes of intermediates, thereby effectively overcoming the trade‐off between catalyst activity and stability. When applied in rechargeable ZABs, the catalyst demonstrates remarkable cycling stability over 750 h and a peak power density of 268.5 mW·cm −2 . This study lead to a breakthrough in bifunctional oxygen catalyst design, significantly advancing rechargeable ZABs and inspiring new strategies for diverse energy storage and conversion systems.

The introduction of light energy in lithium-oxygen batteries is seen as a promising strategy. However, the limited absorption of light by the photoelectrode and the rapid recombination of photo-generated electron-hole pairs are knotty problems. Herein, dual-defect engineering is applied for preparation of Zn1-xCuxS cathode catalyst for photo-assisted Li-O2 batteries, in which Zn vacancy energy level promotes photon absorption, while the Cu doping facilitates the separation of carrier pairs. As a consequence, Zn1-xCuxS cathode exhibits great stability up to 163 cycles under illumination at 200 mA g- 1 with a fixed specific capacity of 600mAh g- 1, far exceed 46 cycles in darkness. Moreover, discharge product under illumination is film-like and fully decomposed during charging, while discharge product without illumination displays plate-like structure with restricted contact with cathode surface. This is attributed to defect-induced changes in the band structure and adsorption ability within cathode catalyst, which is confirmed via theoretical calculation. The strategy of dual-defect engineering is an effective approach for optimizing utilization of light and tuning Li2O2 formation, which holds great prospects in development of high-performance photo-assisted Li-O2 batteries.

Although lithium-ion batteries (LIBs) have achieved widespread adoption in the fields of communications and consumer electronics, aqueous batteries, due to their low cost and high safety, are also considered a promising technology for future sustainable energy storage. However, the high charge density of Ca2+ and Al3+ leads to a strong electrostatic interaction with the host material, which makes the selection of cathode materials for aqueous batteries an important challenge. In this paper, the interlayer spacing of the layered material VOPO4 has been expanded by the insertion of phenylamine, and it has been successfully applied in emerging aqueous calcium-/aluminum-ion batteries. After PA intercalation, the modified materials could realize an obvious specific capacity improvement. At a current density of 0.1 A g-1, it can reach an initial specific capacity of 147 mA h g-1 and maintain stable cycling performance for over 800 cycles. Compared with other similar counterparts, the specific capacity and cycle stability of VOPO4 after PA intercalation could show comprehensive advantages, which provides a novel orientation for the design of multivalent ion batteries within aqueous battery systems.

In proton exchange membrane water electrolysis (PEMWE), catalysts for acidic oxygen evolution reaction (OER) that demonstrate high current density and stability are essential. Herein, we synthesized La-doped RuO 2 (La-RuO 2 @TM) nanorod composite catalysts in situ on titanium mesh (TM) using a one-step low-temperature pyrolysis method. La-RuO 2 @TM displays excellent catalytic performance (1.533 V at 100 mA cm −2 ) and remarkable stability, showing no significant degradation in performance over 450 hours of operation. Density functional theory (DFT) calculations indicate that the formation of the La-O−Ru local structure modulates the adsorption strength of reaction intermediates, alleviates metal (Ru) leaching, and reduces oxygen loss, significantly enhancing the material‘s durability in acidic OER. The PEM electrolyzer utilizing La-RuO 2 @TM operates at 1.815 V with a current density of 1.0 A cm −2 , maintaining stable performance for 120 h at 60 °C. This study offers valuable insights for designing efficient and durable acidic OER catalysts.

The advancement of high-performance, safe, and cost-effective multivalent-ion batteries is pivotal for sustainable energy storage. Prussian blue analogs (PBAs), with their open framework and tunable redox-active sites, hold significant promise but face challenges in structural instability and sluggish ion diffusion. This review focuses on entropy production PBAs (EP-PBAs) for non-monovalent ion (Zn2+, Al3+, Mg2+, and Ca2+) battery systems. Incorporating multiple transition metals into PBAs leverages entropy production effects to stabilize crystal structures, enhance ion diffusion kinetics, and improve cycling stability. Synthesis methods such as coprecipitation, electrochemical deposition, and hydrothermal techniques are compared, with coprecipitation emerging as the most scalable approach. Entropy engineering mitigates lattice distortion, reduces defects, and suppresses phase transitions, enabling EP-PBAs to achieve high specific capacities and long-term stability. Challenges including interfacial instability and synthesis complexity are discussed, alongside future directions in material optimization, electrolyte compatibility, and scalable production. This work highlights the potential of entropy-stabilized PBAs as next-generation cathodes for multivalent-ion batteries, advancing sustainable energy storage technologies.

Layered oxides, one of the most fascinating cathodes for sodium‐ion batteries (SIBs), have appropriate voltage window and feasible preparation process, however, cycling stability is the biggest challenge. Element doping is the most rational strategy to address this problem, but six‐coordinated octahedral radii and different radii in different valence states of these doping elements and the functions of these elements need to be taken into account. Hence, an example of P2/O3‐type Na 0.7 Mn 0.53 Ni 0.26 Fe 0.15 Mg 0.01 V 0.01 Co 0.01 Cu 0.01 Zn 0.01 Sn 0.01 O 2 (high‐entropy‐doped layered oxides, HEO) has been designed in consideration of moderate six‐coordinated octahedral radii and stabling the metal–oxygen bond. A reversible capacity of 126.9 mAh g −1 can be achieved. Even tested at 1000 mA g −1 , an improved rate performance of 72.9 mAh g −1 can be observed with a capacity retention rate of 66.5% after 1000 cycles. Potential‐based in situ electrochemical impedance spectroscopy measurements and corresponding distribution of relaxation time profiles prove the effect of multiple elemental combination. Concomitantly, in situ XRD results reveal the P2/O3 biphasic clamping reaction mechanism of HEO. Density functional theory results reveal that the multielement doping can modify the localization of electrons and enhance the structural stability. This work provides an idea of designing HEO cathode for SIBs by crystal structure modulation.

Pyrovanadates are considered a promising host material for the reversible intercalation of highly charged Ca2+ions due to their favorable layered structure and the presence of rich interstitial confined species.However,in calcium-ion battery(CIB)systems,the diffusion kinetics of the Ca2+ions are slower,and the electrostatic interactions are stronger(compared to Li+),which limits the effectiveness of pyrovanadate's structural advantages.In this study,we employ an allelic reconfiguration strategy to develop novel solid-solution phase pyrovanadate materials,specifically Zn3-xCux(OH)2V2O7·2H2O(x=0,1,1.5).By incorporating 'twin' isotopic Cu elements from the adjacent ds-block,we activate redox reactions at non-vanadium metal sites through the modulation of electronic properties.As a result,a pronounced plateau zone during the discharge/charge process is observed.Using theoretical simulations and X-ray absorption spectroscopy,we have clarified the mechanism by which the solid solution enhances the interlayered confinement of species such as lattice water and hydroxide radicals,improving structural stability and facilitating the diffusion of highly charged Ca2+ions.This approach effectively addresses the issue of layer shrinkage,which typically arises from the intense Coulombic interaction between the carrier and the host.When assembled with an active carbon anode,coin-cell CIB devices can operate steadily at a charge rate of 100 mA g-1 for over 1000 reversible cycles.This demonstrates the potential of innovative solid-solution design strategies to create Coulombic-force-resistant host materials for future multivalent metal-ion battery technologies,including CIB systems.

The growing accumulation of spent lithium-ion batteries (LIBs) presents pressing environmental and societal challenges, highlighting the urgent need to reimagine them as sustainable energy resources. Traditionally, the formation of Fe vacancies ( V"(Fe) ) in LiFePO4 (LFP) cathodes during extended cycling has been regarded as the chief culprit contributing to capacity degradation. However, this study uncovers their functional potential as beneficial structural defects for sodium-ion batteries, repurposing V-Fe(") from spent LFP batteries to engineer high-performance Na-Fe-P-O series cathode materials. These pre-existing vacancies trigger a self-adaptive lattice breathing mechanism that dynamically accommodates volume changes during rapid Na+ ion de-/intercalation, achieving 80% state-of-charge within 6 min and retaining 82.9% capacity after 4000 cycles at a high rate of 10 C. The proposed dual-loop upcycling model further enhances economic returns by 65% and reduces environmental footprint by 29%. This work pioneers a sustainable paradigm that transforms degradation mechanisms of LIBs into foundational design strategies for next-generation batteries.

3D accessible Mn‐based Prussian blue analogues (PBAs) framework shows great potential in serving as host for carriers. However, their inevitable Jahn–Teller distortion (JTD) induced by Mn 3+ ions bring uncertainty for structural and phase‐change robustness during carrier reversible intercalation, particularly for highly charged Al 3+ ions with strong Coulombic interaction. Herein, a cationic vacancy design on Mn sites (V Mn ) is proposed for high‐performance Al 3+ reversible storage. By virtue of low‐cost Na 2 EDTA molecules, the introduction of V Mn , the undesired JTD, and corresponding phase‐change can be well‐suppressed. As a result, the enhanced structural robustness of PBAs framework exhibits excellent long‐term cyclic stability and favorable intercalation energies for reversible Al 3+ ions storage. In addition, as‐assembled MoO 3 //V Mn ‐PBAs full cell batteries can operate in a wide temperature range from −15 to 50 °C, without any additives in aqueous electrolyte. This work highlights the comprehensive availability of cationic vacancy strategy and aqueous Al‐ion batteries within a wide range of ambinent temperature, further, providing novel sight for sustainable development for next‐generation energy storage technique.