Physics

ABSTRACT The long‐standing role of fibers as basic structural components has given way to a new paradigm of smart fibers that integrate environmental sensing with programmable responses. Despite recent progress in materials chemistry and device engineering, fabrication choices are often guided by cost and convenience at the expense of advanced capabilities. This review reframes manufacturing as a central design axis that governs not only morphological properties but also molecular orientation, hierarchical organization, and interfacial properties, all of which determine performance. In this review, we first discuss the design principles of activation triggers and response mechanisms, highlighting how they interplay with the unique geometry of fibers. We then provide a detailed comparison of manufacturing strategies, including continuous single fiber spinning, non‐woven deposition, and direct synthesis, emphasizing their distinct trade‐offs in scalability, resolution, and material compatibility. We further examine post‐processing and multiscale integration as steps that preserve, refine, and extend fiber‐level properties into system‐level functions. Finally, we discuss emerging directions toward fiber electronics and intelligent systems that merge physical in‐fiber processing with data‐driven interpretation. Together, these principles establish a task‐dependent framework that aligns design, manufacturing, and function, advancing smart fibers from isolated demonstrations to integrated next‐generation devices.

ABSTRACT Strong enhancement of magnetization is highly desirable for increasing device efficiency, improving temperature stability, enhancing sensitivity, and enabling device miniaturization. Here, we demonstrate a 2.6−4.7 times higher room temperature ferrimagnetic moment (730−770 emu cc −1 ) compared to 170−260 emu cc −1 in as‐grown CoFe 2 O 4 films, achieved by site‐specifically intercalating hydrogen ions near the Fe 3+ in tetrahedral sites. While the spin moments of the Fe 3 + at octahedral and tetrahedral sites cancel each other out in as‐grown films, X‐ray spectroscopy of hydrogenated films reveals that both Fe 3+ and Co 2+ at octahedral sites can contribute to the enhanced total magnetic moment. This robust enhancement in insulating CoFe 2 O 4 , exhibiting high reproducibility over ≈10 cycles and long‐term stability over ≈10 d, suggests that hydrogenic‐ferrimagnetic coupling holds great promise for ultralow power electronics operating at high frequencies.

ABSTRACT Anode‐free lithium metal batteries (AF‐LMBs) offer high energy density systems and simplified design through the complete elimination of excess lithium. However, their practical development is hindered by sluggish lithium‐ion (Li + ) transport and uneven lithium deposition at the anode interface. Here, we introduce a nanoconfined ion‐regulator based on a high‐entropy metal–organic framework (HE‐MOF). The simulation results demonstrate that the multi‐metal channels provide heterogeneous local coordination environments, broadening the distribution of Li + binding sites, facilitating Li + migration, suppressing local ion retention, and regulating interfacial electrolyte decomposition, ultimately leading to the formation of a thin LiF‐rich SEI layer. As a result, the Li||HE‐MOF/C half‐cell delivers an initial Coulombic efficiency of 97.74% at 0.5 mA cm −2 , the HE‐MOF/C@Li symmetric cell exhibits stable cycling for over 10000 h at 60 mA cm −2 /1 mAh cm −2 , and the anode‐free HE‐MOF/C||NCM‐811 full cell remains stable for 2300 cycles with a capacity decay rate per cycle of 0.026%. This work provides a proof‐of‐concept high‐entropy MOF interfacial strategy for regulating Li deposition in AF‐LMBs.

ABSTRACT Wood is used as a high‐performance structural material in advanced buildings owing to its high mechanical strength, sustainability, and environmental friendliness. However, to overcome the intrinsic size limitation of natural wood, developing green adhesives with high strength, self‐healing, recyclability, and low cost to replace polluting petroleum‐based products has become the key objective for the next stage in wood adhesives research. Inspired by the multiscale structure of gecko toe pads, this work develops a biomimetic self‐healing adhesive featuring dual mechanisms of phase separation and mechanical interlocking. By introducing sodium acetate trihydrate (SAT) into a poly(vinyl alcohol) (PVA)/wood powder (W) adhesive, phase separation occurs to promote the formation of a dense hydrogen‐bonding network and a mechanically interlocked microstructure, which makes the green, sustainable PVA/W/SAT adhesive with high shear strength (5 MPa). Benefiting from SAT's excellent phase‐change capability, the material achieves phase‐change‐induced self‐healing at crack interfaces. The combination of superior mechanical performance, self‐healing functionality, and environmental friendliness makes the PVA/W/SAT adhesive a promising candidate for transforming waste wood into high‐performance planks, significantly reducing the carbon footprint of structural materials.

ABSTRACT Inducing localized mineralized lesions offers a promising drug‐free strategy for tumor suppression, yet calcium‐phosphate systems are limited by slow crystallization, high ion requirements, and poor organelle specificity. Here, we develop a silicene‐derived nanoplatform that serves as an “inorganic silicic acid reservoir”, enabling controlled, organelle‐specific biosilicification for cancer therapy. Silicene nanosheets are sequentially engineered with tannic acid and PEI‐anchored triphenylphosphonium (TPTS), conferring high colloidal stability, efficient endosomal escape, and selective mitochondrial targeting. Within the oxidative mitochondrial milieu, TPTS undergoes programmed hydrolysis to release Si(OH) 4 , which condenses in situ to form silica directly on mitochondrial membranes. The resulting confined mineral deposits disrupt membrane potential, impede metabolite trafficking, and precipitate a catastrophic energetic collapse that drives apoptosis. This platform delivers two major advances: (1) Intracellular mineralization redefinition—precursors shift from intrinsic labile physiological ions to exogenous bio‐orthogonal nano‐reservoir, enabling sustained, site‐specific silicic acid release; (2) High therapeutic potency – organelle‐level precise therapy surpasses conventional high‐dose‐dependent cellular‐scale mineralization, achieving 81.79% tumor inhibition in ectopic models and 65.81% even in the more challenging orthotopic TNBC models, without inducing systemic toxicity. Together, these results establish a generalizable paradigm for spatially programmed mineralization therapy and position silicene as a versatile foundation for next‐generation organelle‐targeted cancer interventions.

ABSTRACT The commercialization of organic photovoltaics (OPVs) is hampered by the trade‐off between high power conversion efficiency (PCE) and processability, particularly in thick‐film and large‐area fabrication. Herein, three halogenated diphenyl ether additives with similar structures but distinct physical properties, 1‐bromo‐2‐phenoxybenzene ( o ‐BPB), 1‐bromo‐4‐phenoxybenzene ( p ‐BPB), and 4,4′‐oxybis (bromobenzene) (BDPE), are selected to regulate the film‐forming process of the PTQ10: m‐ TEH system. Studies reveal that BDPE exhibits the lowest electrostatic potential (ESP), maximum electron delocalization, and highest decomposition temperature, enabling its retention in the drying film. Through dibromo‐induced negative ESP and π–π complementarity with m ‐TEH, BDPE forms directional noncovalent interactions that delay acceptor nucleation, suppress oversize phase separation, and promote ordered molecular stacking. This ESP‐driven interaction simultaneously optimizes the vertical phase distribution, enhances crystallinity, reduces energy loss, extends exciton diffusion lifetime, and accelerates charge transport while suppressing recombination. Benefiting from these synergistic effects, the BDPE‐based PTQ10: m ‐TEH device achieves a PCE of 19.80%, delivers a short‐circuit current density of 30.49 mA cm −2 at 500 nm thickness. BDPE also shows universality in various binary systems (20.11% PCE for D18:L8‐BO) and good processability in large‐area modules. This work provides an efficient strategy for low‐cost thick‐film OPVs, offering new theoretical and engineering pathways for their up‐scale production.

ABSTRACT Developing highly selective ion‐exchange membranes to suppress active‐species crossover remains a critical challenge in aqueous redox flow batteries (ARFBs). Unfortunately, their practical performance is often compromised by hydration‐induced membrane swelling, giving rise to non‐selective water channels that facilitate catholyte‐anolyte crossover. Herein, we show that geometric topology is a previously overlooked but decisive parameter governing membrane microstructure, hydration behavior, and ion selectivity. Using a coarse‐grained molecular dynamics framework, we reveal a geometry‐driven phase‐separation mechanism under membrane hydration. Isotropic 0D geometric motifs remain uniformly dispersed and promote the formation of highly interconnected yet spatially confined hydration networks, whereas anisotropic one‐ and 2D geometric motifs exhibit a strong propensity to bundle and aggregate, inducing phase separation and interfacial voids that promote non‐selective transport. Guided by this principle, a membrane incorporating 0D geometric motifs simultaneously achieves high cationic conductivity and strong polysulfide rejection, enabling stable operation of a polysulfide‐based aqueous redox flow battery for over 700 h with Coulombic efficiencies exceeding ∼99.5% and peak power densities of ∼138 mW cm − 2 , dramatically outperforming conventional commercial membranes and demonstrating the effectiveness of the geometry‐guided membrane design principle in advancing future membrane engineering.

ABSTRACT High rate capability of cathodes in lithium‐ion batteries (LIBs) is essential for fast rechargeability of electric vehicles. Herein, we report that coating the cathode side of the separator with a layer of nanoporous carbon significantly improves the rate capability of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC) and LiFePO 4 (LFP) cathode materials, where NMC and LFP deliver 121 mAhg −1 and 125 mAhg −1 at 2 Ag −1 (∼12 C), respectively. To elucidate the underlying mechanism, we investigate the interfacial behavior and charge transfer kinetics using the distribution of relaxation times (DRT) from electrochemical impedance spectroscopy. Our DRT results show an increased relaxation time for mass transport and indicate a more populated charge storage in the diffuse layer of the electrical double layer (EDL). Simulations on ion transport behavior using a size‐modified Poisson–Nernst–Plank equation reveal that the nanopore‐confined EDLs produce an exclusion effect that increases Li‐ion transport resistance in over‐confined pores. These results support the experimentally observed increase in performance for coatings with expanded pore sizes and further indicate that the carbon layer enhances both (de)lithiation processes by promoting a more uniform and consistent gradient of Li‐ions in the EDL.

ABSTRACT Visualizing mechanical force distribution through mechanoluminescent foams allows real‐time optical monitoring of human motion for energy, sensing, and safety applications. However, conventional polymer‐based mechanoluminescent composites often suffer from inefficient stress transmission in thick structures due to their high elasticity, resulting in surface‐confined emission and weak luminescence in the global regions. In this study, Al 2 O 3 is introduced as a simple additive that performs dual functional roles in both structural and electrical aspects. During fabrication, surface‐adsorbed species on Al 2 O 3 , such as oxygen and moisture, induce spontaneous bubble formation, generating a sponge‐like porous architecture that enhances force dispersion and consequently improves mechanoluminescent performance in the global region of the foam. Moreover, the intrinsically strong positive triboelectricity of Al 2 O 3 strengthened the interfacial triboelectric field, leading to highly bright emission even with a low loading ratio of ML particles. When applied to shoe soles, the foam enables not only full‐area signal monitoring but also spatially resolved detection of dynamic loading during human motion. This study reveals the dual structural and triboelectric enhancements induced by a simple additive and highlights its potential for realizing practical self‐luminous platforms in smart footwear, healthcare monitoring, and wearable stress sensing.

ABSTRACT The development of all‐solid‐state batteries (ASSBs) is critical for overcoming the safety and performance limitations of conventional lithium‐ion batteries with liquid electrolytes. Solid polymer electrolytes (SPEs) offer promising processability and interfacial contact but suffer from low room‐temperature ionic conductivity. Liquid crystal electrolytes (LCEs) have emerged as a solution, leveraging their self‐assembling mesophases to create ordered ion transport channels that enhance conductivity. However, translating the molecular advantages of LCEs into high‐performance devices requires advanced manufacturing techniques capable of precise structural control. This work introduces a novel 3D‐printed, ultra‐thin (20 µm) composite LCE membrane engineered for high dielectric constant ( ε r ′ ∼ 40) and ionic conductivity (~10 −3 S cm −1 ). The membrane is composed of a polymer matrix (PVDF), a polymer network formed by the reaction of liquid crystal (LC) monomer RM257 and thiol monomers, and the high‐dielectric small molecule LC 4‐cyano‐4′‐pentylbiphenyl (5CB). When integrated into ASSBs with a lithium metal anode and LiCoO 2 cathode, the printed LCE membrane enables outstanding long‐term cycling stability (retaining a capacity of 76.6% over 3000 cycles). This study demonstrates that combining molecular design with additive manufacturing provides a powerful strategy for developing high‐performance, durable, and safe ASSBs.

ABSTRACT Halide perovskites exhibit exceptional optoelectronic properties, yet their intrinsic chemical fragility and ionic nature pose fundamental challenges for high‐resolution patterning and nanoscale integration. Here we report a reversible, all‐optical structural modulation strategy that enables chemistry‐free, sub‐diffraction patterning of halide perovskite thin films through light‐driven crystallization‐decomposition dynamics. Localized femtosecond laser excitation induces controlled crystallization and an orthorhombic‐to‐cubic phase transition in CsPbBr 3 thin films, markedly enhancing crystallinity and optoelectronic response. In contrast, ultraviolet illumination promotes defect formation and partial decomposition into CsBr and PbBr 2 , reversibly suppressing crystallinity and photocurrent. This optically driven crystallization‐decomposition cycle is repeatable over multiple iterations with more than 85% photocurrent recovery, establishing a robust platform for reversible material‐state control. Leveraging the nonlinear competition between laser‐induced crystallization and UV‐induced inhibition, we further demonstrate resist‐free, sub‐diffraction nanolithography with feature sizes down to 93.5 nm, well beyond the conventional optical diffraction limit. This work reveals a light‐programmable structural degree of freedom in halide perovskites and provides a general materials framework for reconfigurable perovskite architectures, adaptive photonics, and dynamic optoelectronic systems.

ABSTRACT Biophotonic healthcare devices have been widely investigated for photochemical tissue bonding (PTB), photobiomodulation (PBM), photodynamic therapy (PDT), and photothermal therapy (PTT). However, their clinical applications remain limited due to the short light penetration depth and the incompliant light source, including externally powered light‐emitting diodes (LEDs). Here, we present a stretchable photonic patch embedded with biocompatible room light‐ and sunlight‐activatable luminescent particles (RSLPs) in an elastomeric matrix. This patch enables ambient light‐activatable phototherapy without an external light source by absorbing broadband ambient light and converting it into red luminescence. The emission promotes PTB, fibroblast proliferation, and M1/M2 macrophage polarization for tissue regeneration, activating photosensitizers to induce collagen crosslinking and wound sealing. The conformal patch maintains optical performance even under movement, enabling continuous phototherapy during daily life activity. Remarkably, after PTB‐driven sealing, wound healing is accelerated in both linear and circular wounds, mediated by PBM‐induced tissue regeneration. A further clinical study on normal human facial skins demonstrates that a single PBM treatment with the patch acutely improves viscoelastic recovery and attenuates superficial erythema. This ambient light‐activatable biophotonic patch platform would pave a big avenue toward PTB, PBM, and various biomedical applications.

ABSTRACT Nature has long inspired the design of reversible smart adhesives; however, achieving both high adhesion strength and switchability remains a significant challenge, particularly for emerging applications (e.g., soft robotics and wearable electronics). Herein, we introduce switchable phase‐locking‐mediated adhesives (SPAs) that leverage high‐density hydrogen bonds to deliver ultrahigh adhesion (up to 15 MPa). The underlying mechanism involves dynamic phase‐locking mediation that harmonizes interfacial adhesion with bulk cohesion through interfacial mechanical locking and strain‐induced phase separation. This strategy optimizes performance across the complete adhesion lifecycle, including spreading, adhering, and debonding via temperature/force‐mediated phase‐locking. Through detailed molecular analysis of the SPA system, we uncover the mechanistic basis of ultrahigh adhesion and establish design guidelines applicable to future smart adhesive development.

ABSTRACT Although nanoparticle‐based PROTACs (nPROs) provide a modular strategy to improve the biological fate of PROTACs, their degradation performance was fundamentally limited by restricted intracellular diffusivity. Here, we introduced an unconventional solution: Imparting autonomous motility to nPROs to transform them from passive carriers into active protein‐seeking degraders. We engineered nano‐motoring PROTACs (nMPROs) through asymmetric modification of gold nanoparticles, displaying POI ligands and E3 recruiters on one hemisphere while anchoring catalase on the opposite hemisphere. Within the H 2 O 2 ‐rich tumor cell microenvironment, catalase‐generated oxygen fueled directional propulsion, enabling nMPROs to actively navigate the intracellular space rather than relying on random diffusion. This propulsion fundamentally enhanced intracellular target‐search efficiency: nMPROs function as “nanoscopic protein‐sweeping robots,” autonomously interrogating a larger intracellular landscape and capturing more sparsely distributed target proteins. As a result, nMPROs achieved a threefold increase in ERα degradation potency relative to static nPROs and enabled modular, ligand exchange–based degradation of PD‐L1, demonstrating platform generality. Overall, this work establishes a new mechanistic paradigm for enhancing targeted protein degradation of nPROs and lays the foundation for generalizable next‐generation PROTAC nanoplatforms.

ABSTRACT Regulation of metal–oxygen (M–O) bonds and incorporation of sulfur are promising approaches for designing electrocatalysts for efficient hydrogen production from seawater. However, the durability of these catalysts is limited by the instability of M–O bonds under cathodic conditions and poisoning caused by the uncontrolled introduction of sulfur. In this study, a “killing two birds with one stone” strategy was developed for creating efficient hydrogen production electrocatalysts that involves anchoring PtNi nanoparticles on hydroxyl‐functionalized carbon nanotubes and modifying the surface with SO x species (S‐PtNi/CNTs) via a one‐pot hot‐injection‐combined wet‐chemical synthesis protocol. In this material, hydroxyl‐functionalized CNTs stabilize PtNi through M–O bonding, while SO x species tune the electronic structure of Pt and enhance M–O bond stability. Consequently, S‐PtNi/CNTs exhibits outstanding hydrogen production performance in alkaline seawater, delivering a 5.4‐fold increase in mass activity and a 21‐fold increase in specific activity compared to commercial Pt/C, along with remarkable stability over a 1000‐h operation period. Furthermore, S‐PtNi/CNTs significantly outperform commercial Pt/C in both a photovoltaic‐electrocatalysis electrolyzer and an anion‐exchange‐membrane water electrolysis system. The results of in situ spectroscopy and theoretical calculations confirm that SO x species stabilization of M–O bonds and improved chloride ions resistance are responsible for the superior performance of S‐PtNi/CNTs.

ABSTRACT Developing high‐performance nonlinear optical materials that simultaneously deliver large effective nonlinearity and device‐level integrability remains a longstanding challenge. Ferroelectric nematic liquid crystals (FNLC) have emerged as a promising platform owing to their intrinsic non‐centrosymmetry, theoretically predicted large second‐order nonlinearity, and solution processability on diverse substrates. However, realizing strong second‐harmonic generation (SHG) in FNLCs has been hindered by pronounced orientational disorder inherent to fluidic systems without lattice constraints. Here, this limitation is overcome through a surface‐anchoring strategy that induces highly ordered polar topological structures within self‐assembled FNLC droplets. The resulting architecture yields a giant effective SHG coefficient of 56.9 pm/V—an order of magnitude higher than previously reported FNLC systems—together with SHG efficiency surpassing that of benchmark LiNbO 3 films of comparable thickness. Moreover, the system exhibits broadband SHG response, while the engineered polar topology enables passive, field‐free spatial optical modulation with a contrast ratio of 330%. The combination of giant nonlinearity, outstanding SHG efficiency, broadband SHG response, spatial optical modulation, and solution processability establishes a new paradigm for integrated nonlinear photonic devices.

ABSTRACT Operating LiNi x Co y Mn 1‐x‐y O 2 (NCM, x ≥ 0.92) cathodes at high temperature/voltages (≥4.3 V or 45°C) to achieve high capacity inevitably leads to accelerated capacity fade. Despite extensive research into cycling behaviour under various cut‐off voltage and phase degradations, the fundamental mechanisms governing internal phase transformations, lattice deformations, and internal stress generation remain poorly understood. By using HAADF–STEM characterization with DFT and MD simulations, we disclose a new chemo‐mechanical degradation rule: lattice bending leads to the formation of O1/LiNi 2 O 4 (Fd‐3m) and unstable intermediate transition phase Ni 3 O 4 (Cmmm), the bending and distortion of the lattice are the direct causes of internal stress. Unlike previous findings, both RS, Ni 3 O 4 /LiNi 2 O 4 and O1 phases were detected in various crack regions. Stress concentration from bending‐induced O1–LiNi 2 O 4 and LiNi 2 O 4 –Ni 3 O 4 –RS (Fm‐3m) phase transformations leads to intracrystalline cracking, impairing capacity retention. Lattice deformation can lead to the emergence of stress and the formation of micro‐cracks, even during the O3‐O1 phase transition. This work confirmed the relationship between phase transformation and stress in the in cracked areas and stress. Meanwhile, this research provides new insights into the degradation mechanism for lithium‐ion batteries, specifically paving the way for the design and optimization of high‐energy‐density.

ABSTRACT Scalable manufacturing of three‐dimensional (3D) micro‐/nano‐architectures with nanometric precision remains a pivotal challenge in photonics. Here, we introduce a parallel broad‐beam ion beam etching (IBE) technique that decouples this fundamental trade‐off, enabling the simultaneous and uniform transformation of two‐dimensional (2D) patterns into well‐defined 3D geometries across entire 4‐inch wafers. The IBE platform achieves angular uniformity exceeding 97% and reduces fabrication time by over two orders of magnitude compared to serial focused‐ion‐beam (FIB) methods. Leveraging this approach, we fabricate two distinct functional devices: a chiral 3D bending metasurface with a giant experimental circular dichroism of 0.8 in the mid‐infrared, and a collectively buckled plasmonic grating whose resonance is dynamically tunable over 150 nm in the visible spectrum via curvature control. This technology uniquely combines nanoscale precision with wafer‐scale throughput, enabling the construction of 3D metasurfaces via meta‐atom assembly and the global modulation of optical responses. Our work establishes a versatile platform that bridges the gap between design complexity and scalable manufacturing for next‐generation 3D integrated photonics.

ABSTRACT The miniaturization and integration of electronic/photonic devices demand precise control over light at the micro‐scale. However, achieving tailored optical anisotropy through intrinsic material design, rather than external components, remains a significant challenge. Herein, we report a general and programmable strategy for the growth of one‐dimensional organic crystals with precisely tunable asymmetric architectures via a spatially defined temperature gradient. By leveraging the competitive, facet‐dependent growth kinetics under a thermal bias, continuous and precise control over the structural asymmetry is achieved in single crystals, with a tunable morphological anisotropy ranging from 9% to 81%. The resulting asymmetric crystals exhibit a pronounced direction‐dependent optical response, yielding a photoluminescence intensity contrast ratio as high as 113.3, which scales directly with the degree of structural asymmetry. This work establishes a material‐based platform for applying direction‐dependent photonic properties directly into crystal morphology, paving the way for advanced organic photonic materials with built‐in anisotropy.

ABSTRACT Solid polymer electrolytes are promising for lithium metal batteries, yet achieving both high ionic conductivity and interfacial stability remains a major challenge. Here, we report a molecular rotor strategy that addresses this trade‐off by incorporating 3‐(1‐Pyridinio)‐1‐propanesulfonate zwitterions (PP‐Z) into a polyvinylidene difluoride electrolyte. This design establishes a dipole‐rotation‐assisted ion transport mechanism distinct from conventional polymer relaxation‐dependent conduction. Molecular dynamics simulations and experiments reveal that the anchored cationic group of PP‐Z serves as a pivot, while the mobile anionic end creates a dynamic coulombic field. This configuration facilitates rapid Li + migration through coordinated intrachain transport and interchain hopping, significantly enhancing ionic conductivity (5.1 × 10 −4 S cm −1 at 25°C and 1.5 × 10 −4 S cm −1 at 0°C) and the Li + transference number (0.52). The anionic terminals further participate in Li + solvation and promote formation of a LiF‐rich solid electrolyte interphase, enabling stable cycling for 1200 h in Li||Li cells at 0.3 mA cm −2 and > 500 cycles in Li||LiFePO 4 cells at 1C (25°C). Even at 0°C, the Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (1.8 mAh cm −2 ) pouch cell retains 85.1% capacity over 50 cycles while delivering 78.3% of its room‐temperature capacity initially.

ABSTRACT The development of high‐performance anode materials is essential for next‐generation rechargeable batteries. Herein, a series of pyrene‐linked diketopyrrolopyrrole (DKP)‐based covalent organic frameworks (COFs) is reported through systematic side‐chain engineering using methyl and ether functionalities. A stepwise synthetic strategy employing unsubstituted, methylated, and ether‐functionalized DKP monomers enabled precise tuning of pore environments, ion coordination, and electrochemical behavior. Among these materials, the ether‐modified Py‐DKPOMe COF exhibited outstanding lithium storage performance, delivering an initial reversible capacity of 265 mA h g − 1 and retaining over 100 mA h g − 1 at an ultrafast 20C rate, with 60 mA h g − 1 maintained at 25C. Remarkably, it achieved 80% state of charge within 61.7 s and exhibited excellent long‐term cycling stability, while the high lithium‐ion diffusion coefficient (7.12 × 10 −10 cm 2 s −1 ) confirmed the rapid ion transport facilitated by the ether‐functionalized chains. Interestingly, density functional theory (DFT) and nudged elastic band (NEB) calculations revealed enhanced Li + adsorption affinity and reduced migration barriers in Py‐DKPOMe COF. In addition, Py‐DKPOMe COF also demonstrated promising sodium‐ion storage (138 mA h g − 1 ). Full‐cell tests with a Li‐rich LNMO cathode verified its practical applicability, highlighting molecular‐level COF design as a powerful strategy for fast, durable organic electrodes.

The sulfur redox mechanism in solid-state lithium–sulfur (Li–S) batteries remains unclear, as it has been reported to vary under different operating conditions due to sluggish reaction kinetics. Herein, we investigate sulfur reactions in solid-state batteries using solid electrolytes with high ionic conductivities to mitigate kinetic limitations. A solid-state Li–S cell employing Li 5.5 PS 4.5 Cl 1.5 exhibits an asymmetric voltage profile at 25 °C, with two voltage plateaus during discharge and poorly separated oxidation reactions during charge. Ex situ X-ray absorption spectroscopy (XAS) elucidates that these poorly separated oxidation reactions consist of overlapping conversion reactions, in contrast to the clearly distinguishable two-step conversion from S 8 to Li 2 S via Li 2 S x during discharge. In addition, operando impedance evolution, analyzed using a combined distribution of relaxation times (DRT) and distribution of phasances (DOP) model, reveals distinct relaxation processes during discharge and charge that arise from differences in the transport properties of the reaction products. This work demonstrates an intrinsic asymmetric sulfur redox mechanism in solid-state batteries that is difficult to resolve by conventional electrochemical measurements alone but can be clarified by combining XAS with impedance analysis using the DRT-DOP model.

ABSTRACT Machine learning (ML) is rapidly emerging as a powerful paradigm for decoding the complex physicochemical relationships that govern aqueous zinc‐based battery systems. By uncovering hidden correlations from high‐dimensional experimental and computational datasets, ML provides unprecedented opportunities to resolve ion transport, interfacial chemistry, and degradation behaviors that remain difficult to capture using conventional approaches alone. Herein, this review presents a comprehensive and mechanism‐oriented perspective on ML in zinc‐based energy storage, with feature engineering positioned as the central conceptual framework. Particular emphasis is placed on how physically meaningful descriptors are constructed and utilized across cathodes, zinc anodes, electrolytes, and electrode‐electrolyte interfaces, as well as on their distinct roles in dictating electrochemical performance. Recent advances are discussed in terms of how ML enables the identification of structure‐property relationships, accelerates materials optimization, and deepens mechanistic understanding of critical processes, including Zn 2+ transport, desolvation, interfacial evolution, and performance degradation. By organizing this evolving field through the dual lenses of device components and fundamental mechanisms, the intrinsic connection between data‐driven modeling with electrochemical theory is clarified. Finally, future directions toward data‐centric, physics‐informed, dynamic, and autonomous ML frameworks are highlighted, which are expected to drive zinc‐based energy storage from empirical trial‐and‐error development toward predictive and rational design.