Nanoporous metal, fabricated via the selective dissolution of an alloy (i.e., dealloying), can be filled with another metal via electrodeposition to create unique, functional structures unattainable via just dealloying. In this work, by controlling the charge of Ni deposition, we finetune the porosity and the pore width of nanoporous copper. At a sufficiently low rate, the deposition proceeds uniformly under interface control, until the porosity approaches a percolation threshold, which also governs the smallest attainable pore width. Via microscopic characterizations, we determine that we can tune down the porosity from 57.5 % to 15.8 % and the pore width from 89 nm to 34 nm. A tuned structure that retains the structural bi-continuity rejects 80 % KCl from a 1 mM solution, a function not available in the pristine structure but enabled by the narrowed pores.

Metallic glasses (MGs), as distinctive amorphous metallic alloys, exhibit high-density undercoordinated sites and elevated Gibbs free energy, rendering them highly promising candidates for electrocatalysis. However, MGs inevitably undergo aging or structural relaxation over time, which inevitably triggers the degradation of their intrinsic catalytic properties. Consequently, reversing the aging effect of fully relaxed MGs to recover and even boost their catalytic performance has long remained a formidable and unresolved challenge in the field, given that conventional strategies are ineffective in reactivating the relaxed atomic configurations and restoring the high-energy state of MGs. Herein, we report an innovative energy modulation strategy-Ultrasonic Vibration Loading (UV loading). This strategy not only retrieves the energy of fully relaxed MGs but also induces the formation of a biphase structure with coexisting amorphous and crystalline phases, where the synergistic coupling of the crystalline phase's superior electrical conductivity and the amorphous phase's abundant unsaturated coordination sites optimizes the hydrogen adsorption Gibbs free energy to be closer to 0 eV, thereby remarkably enhancing their catalytic performance. The general applicability of this approach is validated by the superior hydrogen evolution reaction (HER) activity of Pt-based MGs and Pd-based MGs in alkaline electrolytes. Our findings underscore the unique merits of UV loading in tailoring the surface energy and catalytic performance of MGs and provide a versatile paradigm for surface energy modulation of advanced electrocatalysts.

Balancing stability and activity of the hydrogen evolution reaction (HER) electrocatalysis remains challenging for advanced electrolysis technologies. This work introduces a synergistic design strategy to tackle the challenge with in situ surface restructuring. Fe-based double perovskite is developed with an optimal electronic structure for HER catalysis, delivering an overpotential of 325 mV in 0.1 m KOH and 184 mV in 1 m KOH at 10 mA/cm2, among the best reported. Additionally, the catalyst exhibited remarkable self-improving stability, with specific activity increasing 1.98 times at 300 mV overpotential after 20 h, due to the restructuring of an amorphous layer confirmed with transmission electron microscopy. To demonstrate practical utility, the catalyst was integrated into an active flow membraneless electrolyzer (AFME), a promising technology that is currently limited by instability. The device demonstrated outstanding operational stability for 1000 h at 50 mA/cm2, with a minimal decay rate of 0.25 mV/h, establishing a new benchmark for membraneless systems. This work not only presents a powerful strategy for designing self-improving catalysts but also validates its practical efficacy in next generation electrolyzer technologies, paving the way for cost-effective green hydrogen production.

Active-flow membraneless electrolyzers (AFMEs) offer inexpensive alkaline water electrolysis but challenge the stability of catalytic electrodes with the rapid electrolyte flow. Here, we fabricate hierarchical nanoporous nickel from nickel foam via steps of electrodeposition and dealloying. This binder-free architecture provides a highly accessible active surface area for both hydrogen and oxygen evolution reactions and a mechanical stability superior to particle-binder pastes. We further use finite element modelling to guide the electrode design for uniform reaction distribution and low polarization. The electrode operates stably in an AFME at a current density of 50 mA cm(-2) and an electrolyte flow rate of 200 mL min(-1) for 120 h, demonstrating an effective design of active and durable porous electrodes for water electrolysis.

Solid-state phase transformations (SSPTs) during dealloying dictate the evolution of nanoporous architectures, yet their atomic-scale mechanisms remain elusive due to the dominance of classical surface-diffusion models. Here, by combining vapor-phase dealloying with aberration-corrected transmission electron microscopy, we directly uncover a nonconservative SSPT pathway in a Co-Zn alloy, governed by bulk diffusion rather than interfacial kinetics. Real-time tracking reveals a transformation cascade: initial Zn sublimation triggers the formation of a metastable Zn-deficient intermediate (gamma-CoZn-vac), a derivative of the parent gamma-CoZn lattice, followed by atomic column merging and lattice relaxation into alpha-Co. We further mapped Zn bulk-diffusion trajectories driven by chemical potential gradients and identified crystal planes selectively prone to reconfiguration. This work challenges the long-held assumption that dealloying relies solely on surface dynamics, establishing bulk atomic diffusion as a universal driver for nonconservative phase transformations. Our findings may provide the theoretical framework for designing functional nanoporous materials through vacancy-mediated engineering.

Metallic glasses (MGs) often suffer from sluggish hydrogen evolution reaction5 (HER) kinetics in neutral and alkaline media, with their catalytic performance predominantly confined to acidic environments. Herein, we reported a novel thermoplastic forming technique to fabricate a self-supported partially crystallized nanoporous Pt56.2Ni5.2Cu16.8P21.8 metallic glass (C-NPMG). The C-NPMG catalyst delivers ultralow overpotentials of 18.0 mV (0.5 M H2SO4), 42.2 mV (1 M KOH), and 88.0 mV (1 M phosphate-buffered saline (PBS)) at a current density of 10 mA cm−2, outperforming most state-of-the-art non-noble MGs and Pt-based benchmarks across all pH conditions. Notably, it maintains negligible performance decay for over 1000 h in alkaline electrolytes, showcasing superior stability. Experimental and computational analyses reveal that the enhanced HER activity arises from three synergistic effects: (1) the high-specific-surface-area nanoporous architecture that maximizes active site exposure; (2) the formation of crystallite-amorphous interfaces during partial crystallization, which lowers the energy barrier for H2 desorption; (3) the hierarchical super-hydrophilic and super-hydrophobic wettability of the C-NPMG, which optimizes mass transport and prevents electrolyte-induced corrosion. This work establishes a novel design paradigm for developing high-performance, pH-universal HER electrocatalysts by integrating structural nano-engineering and crystallite-amorphous phase synergy in metallic glass systems to overcome the trade-offs between performance and stability in electrochemical water splitting.

Metal foils that alloy with lithium have attracted renewed interest as the issue of continuous solid-electrolyte interphase (SEI) growth can be effectively addressed with solid-state electrolytes (SSEs). However, an impractically high pressure is required to maintain the contact between the foils and inorganic SSEs. Here, we show that a soft polymer solid electrolyte can also alleviate the issue of SEI growth for an Al foil anode at a practically low pressure. Unlike liquid electrolytes, the polymer PVDF-HFP does not infiltrate pits and pores formed during Al lithiation, leading to a more uniform reaction and insignificant SEI growth deep in the anode, as shown by microstructural and compositional analyses of both the surface and the cross section of the anode. It thereby significantly boosts the Coulombic efficiency and the cycling stability of the Al foil anode compared to its liquid counterpart. The work unveils a new path to stabilize alloy anodes for safe, inexpensive solid-state batteries.

Almost all commercial lithium-ion batteries (LIBs) with LiCoO2 (LCO) as cathode material are cycled from 3.0 to 4.2 V and their actual specific capacity just ranges from 140 to 160 mA h g-1, which is much lower than the theoretical specific capacity of LCO of 274 mA h g-1. To further improve the actual specific capacity of LCO, elevating the upper limit of its working voltage is necessary. However, as the upper limit of its working voltage is elevated to 4.5 V or higher, the LCO crystal will undergo severe irreversible phase transition, and the oxidization decomposition of electrolyte on the cathode's surface will exacerbate, which will severely reduce the cycling lifespan of batteries, hindering the actual application of high voltage LCO. In this work, we find that 3,5-difluorophenylboronic acid pinacol ester (35-DAPE) is an effective cathode electrolyte interphase (CEI)-forming additive, which can form a robust and stable CEI layer rich in fluorophenyl-groups and B-F/B-O bonds on the surface of LCO cathode, inhibiting the dissolution of cobalt ions and maintain the structural stability of LCO crystal over cycles. The graphite||LCO pouch cells in a voltage range of 3.0-4.5 V with 35-DAPE display a capacity retention rate of 91.1 % after 150 cycles at room temperature, compared to that of 2.4 % in baseline electrolyte. Besides, rate performance at room temperature and discharging performance at low temperatures of graphite||LCO pouch cells can also be observed with an improvement after the introduction of 35-DAPE. In addition, this work has explained the decomposition mechanism of 35-DAPE and how its products improve the electrochemical performance of graphite||LCO pouch cells in detail, which not only advances the actual application of fluorophenylboronic acid pinacol ester additive in high voltage LIBs but also provides valuable insights for the design of functional electrolyte additives. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Biomass-derived hard carbons represent promising low-cost anode materials for sodium-ion batteries. However, their complex preparation processes and high carbonization temperatures (>1300 degrees C) incur significant energy consumption and cost, hindering sustainable production. This work presents an environmentally benign strategy utilizing low-cost waste cotton fibers to produce high-performance hard carbon anodes with a low carbonization temperature of 900 degrees C. The innovation involves the integration of a dry ball-milling pretreatment, which facilitates the phase transformation from cellulose I to cellulose II. Comprehensive microscopic and spectroscopic analyses confirm that this phase transformation promotes the formation of a microcrystalline carbon layer with enlarged interlayer spacing during subsequent low-temperature carbonization. Moreover, the electrochemical test demonstrates the ball milling-pretreatment driven hard carbon anode delivers higher reversible capacity of 270.00 mAh g(-1) compared to 166.76 mAh g(-1) for the non-ball milling samples and a high initial Coulombic efficiency of 85.34 %. It also exhibits excellent rate capability and long-term cycling stability, retaining a specific capacity of 193.85 mAh g(-1) under a high current density of 2 A g(-1) after 1300 charge-discharge cycles. Kinetic analysis further reveals that the enhanced sodium storage stems predominantly from an insertion mechanism within the engineered microcrystalline carbon layer induced by ball milling. This work establishes a cost-effective and energy-efficient pathway for transforming textile waste into high-value anode materials, advancing the sustainable development of sodium-ion battery.

Nanopores evolve in dealloying to dictate alloy corrosion while enabling the creation of functional metallic nanomaterials. Yet, the nanoscale dynamics of the porosity evolution have long eluded experimental characterizations. With aberration-corrected transmission electron microscopy, we reveal the evolution of nanoporous Co from the vapor phase dealloying (VPD) of γ-CoZn across scales. The in situ characterization confirms key aspects of the dealloying mechanism based on macroscopic characterizations and simulations, including dissolution by repeated step flow and vacancy-cluster nucleation as well as ligament and pore bifurcation. It also separates the step flow kinetics from that of VPD, revealing that a bond energy difference between the alloy constituents can determine the dealloying kinetics and affect the morphology. The findings refine the classic dealloying theory for potentially new fabrications.

Lithium (Li) plating can significantly degrade lithium-ion battery (LIB) performance, posing safety risks. Detecting and monitoring Li plating, especially in its onset stage, is challenging due to its complex and unpredictable nature. This study introduces an ultrasonic spectroscopy method for in situ early detection of mild Li plating and monitoring its development within commercial LIBs. A wave model predicts the ultrasonic spectrum from a multi-layer and saturated porous battery structure. Controlled experiments are conducted at both room and low temperatures. At room temperature, the ultrasonic amplitude generally increases during battery charging. However, at low temperature, the transmission amplitude at the resonance frequency shows a clear decrease during the same charging process. The opposite trend of amplitude change enables highly sensitive and reliable detection of early-stage Li plating with minimal interference from factors such as state-of-charge (SOC) variations. The method is further evaluated by tracking Li plating growth during real-world fast-charging scenarios.

Aqueous zinc-ion batteries (ZIBs) are desirable for large-scale energy storage due to their high energy density, cost-effectiveness, and eco-friendliness. However, the enhancement of their durability under impact remains a major challenge since traditional liquid electrolytes are prone to leakage when subjected to severe shocks or impacts. In this study, a novel shear-thickening electrolyte was reported by integrating starch with Zn(CF3SO3)2 electrolyte. Under normal conditions, this electrolyte behaves like a conventional liquid electrolyte with excellent ionic conductivity, low viscosity, and high fluidity. While upon exposure to external force stimuli, the liquid electrolyte can change to a solid. Moreover, the starch molecules have strong interactions with Zn2+, promoting the epitaxial electroplating of Zn on the anode and effectively suppressing dendrite formation. The ZIBs fabricated based on this shear-thickening electrolyte possess good electrochemical performance and stability, with a capacity retention rate of 96.5% after 3000 cycles at 2 A g-1. More interestingly, the assembled AlVO/CC-50%/Zn flexible battery demonstrates high capacity retention after bending at angles of up to 90 degrees. This shear- thickening electrolyte prevents the battery from damage caused by external force, thereby significantly boosting the impact resistance and the flexible properties of ZIBs.

While bifunctional electrocatalysts enabling both oxygen reduction (ORR) and oxygen evolution (OER) reactions are recognized as pivotal chemical steps for next-generation energy devices, their practical implementation persists as a formidable scientific challenge. In this study, hetero-structured catalyst (CrFeCoNiCu/Mn3O4/MnO/ NC) was successfully synthesized in situ containing both high-entropy alloy and spinel manganese-based oxide by a simple heat treatment process while two control samples (CrFeCoNiCu/Mn3O4/NC and CrFeCoNiCu/NC) were also prepared. It exhibited excellent catalytic performance and stability for both ORR and OER compared with commercial Pt/C and RuO2 catalysts. The superior bifunctional performance was further observed with the overpotential gaps (Delta Egap) of the three electrodes being 0.634 V, 0.655 V, and 0.698 V, respectively, which were lower than those of the combination of RuO2 and Pt/C at 0.723 V. The enhanced catalytic performance was subsequently corroborated by density-functional theory (DFT). This study proposes an alternative method for the synthesis and design of high-performance bifunctional electrocatalysts.

The advancement of lithium metal batteries toward their theoretical energy density potential remains constrained by safety and performance issues inherent to liquid electrolytes. Quasi‐solid‐state electrolytes (QSSEs) based on poly‐1,3‐dioxolane (poly‐DOL) represent a promising development, yet challenges in achieving satisfactory Coulombic efficiency and long‐term stability have impeded their practical implementation. While lithium nitrate addition can enhance efficiency, its incorporation results in prohibitively slow polymerization rates spanning several months. In this work, high‐polymerization‐enthalpy 1,1,1‐trifluoro‐2,3‐epoxypropane is introduced as a co‐polymerization promoter, successfully integrating lithium nitrate into poly‐DOL‐based QSSEs. The resulting electrolyte demonstrates exceptional performance with 2.23 mS cm −1 of ionic conductivity at 25 °C, a Coulombic efficiency of 99.34% in Li|Cu cells, and stable lithium metal interfaces sustained through 1300 h of symmetric cell cycling. This co‐polymerization approach also suppresses poly‐DOL crystallization, enabling Li|LiFePO 4 cells to maintain stability beyond 2000 cycles at 1C. Scale‐up validation in a ≈1 Ah Li|NCM811 pouch cell achieves 94.4% capacity retention over 60 cycles. This strategy establishes a new pathway for developing high‐performance, in situ polymerized quasi‐solid‐state batteries for practical energy storage applications.

Alkaline zinc (Zn) batteries offer the potential for safe and cost-effective energy storage; however, their cycle life is limited by issues, such as hydrogen evolution, ZnO passivation, and shape changes. While increased alkalinity can help address hydrogen evolution and passivation, Ca(OH)2 has proven to be the most effective additive for mitigating shape changes. Nevertheless, its low solubility restricts both its consistency and its practical application. In this study, we demonstrate that hydroxoaluminate ions (Al(OH)4-) provide a promising, soluble alternative. Kinetic analysis indicates that hydroxoaluminate accelerates interfacial ZnO formation, thereby suppressing shape changes, as confirmed by microstructural characterization. This approach extends the cycle life of a Zn-powder anode to over 370 cycles at a 20% depth of discharge in a Zn||NiOOH battery.

Aqueous deep eutectic electrolytes (DEEs) offer great potential for low‐cost zinc‐ion batteries but often have limited performance. Discovering new electrolytes is therefore crucial, yet time‐consuming and resource‐intensive. In response, this work presents a Large Language Model (LLM)‐based multi‐agent network that proposes DEE compositions for zinc‐ion batteries. By analyzing academic papers from the DEE field, the network identifies innovative, inexpensive, and sustainable Lewis bases to pair with Zn(BF 4 ) 2 ·xH 2 O. A Zn(BF 4 ) 2 ·xH 2 O‐ethylene carbonate (EC) system demonstrates high conductivity (10.6 mS cm −1 ) and a wide electrochemical stability window (2.37 V). The optimized electrolyte enables stable zinc stripping/plating, achieves outstanding rate performance (81 mAh g −1 at 5 A g −1 ), and supports 4000 cycles in Zn||polyaniline cells at 3 A g −1 . Spectroscopic analyses and simulations reveal that EC coordinates to Zn 2+ , mitigating water‐induced corrosion, while a fluorine‐rich hybrid organic/inorganic solid electrolyte interphase enhances stability. This work showcases a pioneering LLM‐driven approach to electrolyte development, establishing a new paradigm in materials research.

Developing cost-effective, efficient oxygen evolution reaction (OER) catalysts is critical for sustainable hydrogen production through water electrolysis. While noble metal-based catalysts like RuO2 and IrO2 show high activity, their widespread adoption is limited by cost. Fe-based perovskite oxides present a more abundant alternative but typically exhibit inferior OER activities. In this study, we achieved systematic dual-site modulation by incorporating Ba at the A-site and Ni at the B-site of NdFeO3-delta, transforming it into a double perovskite structure. The resulting Nd0.8Ba1.2Fe1.6Ni0.4O6-delta catalyst achieved an overpotential of 320 mV at 10 mA cm-2 in 0.1 M KOH, significantly lower than typical Fe-based perovskites and noble metals. Ab initio simulations revealed that A-site modulation reduces the band gap, which enhances electronic conductivity. Meanwhile, B-site Ni incorporation strengthens metal-oxygen covalency and decreases charge-transfer energy. The synergistic effects between enhanced electronic conductivity and metal-oxygen covalency led to a significantly reduced Tafel slope of 63.23 mV dec-1, compared to 114.85 mV dec-1 for single-site modified Nd0.8Ba1.2Fe2O6-delta and 154.34 mV dec-1 for unmodified NdFeO3-delta. This work provides a framework for understanding and improving performance in Fe-based perovskite OER catalysts through dual-site modulation, paving the way for more cost-effective and sustainable water electrolysis technologies.

The particle size of TiO 2 anodes is commonly believed to have a negative impact on their mechanical properties. As submicron‐sized TiO 2 exhibits low surface energy, which reduces yield strength and leads to mechanical fracture during the two‐phase lithium storage mechanism, it is excluded from traditional nonaqueous lithium‐ion batteries. In this study, we discovered that TiO 2 demonstrates an independent size effect in an aqueous environment, mitigating the mechanical fracture associated with submicron‐sized TiO 2 . Our studies reveal that water molecules strongly interact with submicron TiO 2 materials, increasing the surface energy in aqueous electrolytes in a unique manner. This enhancement makes submicron TiO 2 more resilient during the lithiation and de‐lithiation reactions. Additionally, the transition from nano to submicron TiO 2 facilitates the inhibition of hydrogen evolution reactions (HER) in aqueous batteries and enhances the performance of electrode coatings. Consequently, submicron TiO 2 exhibits superior electrochemical performance in aqueous batteries, with an Ah‐level pouch battery achieving an energy density of 66 Wh kg −1 (217 Wh L −1 ) and demonstrating excellent cycling stability of over 1200 cycles. Our work has successfully addressed the size limitations of the TiO 2 anodes, offering an innovative perspective on micro‐sized electrode materials previously considered unsuitable for battery use.

AbstractNanoporous metals, a class of free‐standing, high specific‐area materials, evolve from interface‐controlled self‐organization in a selective dissolution (e.g., dealloying). The process creates randomly oriented pores, in which slow mass transport has limited the functional applications of nanoporous metals. Here the control of the pore orientation is demonstrated with a dealloying analogy, reduction‐induced decomposition, achieved in flow cells. Via forced convection, the self‐organization is placed under the control of sufficiently rapid mass transport to suppress pore branching and align 100 nm‐wide ligaments and pores along the direction of reaction propagation, boosting the permeability by an order of magnitude while retaining the large surface area. The pore orientation can be further manipulated with a flow field for an orientation pattern akin to the expected fluid pattern, enabling a nanoporous silver electrode to deliver a peak power of 0.3 W cm−2 in a redox‐flow battery, outperforming commercial carbon electrodes.

Dealloying was initially investigated in the context of corrosion science, but it was later developed into a new method for preparing nanoporous metals with a variety of novel properties and applications. Over the past decade, significant progress has been made in this field. Dealloying is no longer limited to a corrosion process requiring aqueous solutions — other forms of dealloying methods and even phase transformations can also create nanoporous structures, even in materials that are traditionally considered “un-dealloyable.” Dealloyed nanoporous structure is not necessarily uniform and isotropic — heterogeneous nanoporous materials often demonstrate better mechanical or functional performance. Moreover, a nanoporous metal is not merely the final product of dealloying — it can also act as a precursor for the development of other novel nanomaterials that may not be easily fabricated using conventional metallurgical methods. This article provides a review of the latest research on the development of nontraditional dealloying methods, the novel porous or nanoporous materials and their exceptional properties, and the emerging new opportunities in this field.