Zeolitic-imidazolate framework (ZIF)-derived Fe-N/C materials represent the most promising type of noble-metal-free oxygen reduction reaction (ORR) electrocatalysts for proton exchange membrane fuel cells (PEMFCs) and Zn-air batteries (ZABs), yet their performance is fundamentally limited by the low intrinsic activity of symmetric Fe-N4 sites and slow mass transport in micropore-dominated carbon architectures. We herein develop a two-dimensional hierarchically meso-/microporous Fe-N/C material (Fe-NOCl/C) with multiple structural asymmetries of Fe active sites through molten-salt-assisted strategy to overcome the dilemma. Specifically, atomic Fe centers are coordinated in an asymmetric Fe-N3O1Cl1 configuration, with in-plane N3O1 and axial Cl1 coordination, accompanied by abundant neighboring vacancies. Theoretical calculations demonstrate that the geometrically asymmetric Fe-N3O1Cl1 sites, together with neighboring vacancies, induce pronounced electronic delocalization and asymmetric charge redistribution at the Fe center, thereby optimizing O2 adsorption/activation, lowering the rate-determining free-energy barrier, and accelerating ORR kinetics relative to conventional symmetric Fe-N4 sites. Coupled with rapid mass transport enabled by the hierarchical porous architecture, Fe-NOCl/C delivers outstanding ORR activity (E1/2 = 0.823 V in acid and 0.924 V in alkali) and high PEMFC and ZAB power densities of 632 and 237 mW cm−2, respectively. These results mark an important advance in the development of high-performance electrocatalysts and provide fundamental insights into catalytic mechanisms for electrochemical energy conversion.

Photocatalytic nitrogen (N2) fixation provides a cost-effective, environmentally friendly, and efficient method for producing ammonia (NH3), which is utilized in agriculture, energy storage, and the production of zero-carbon fuels for transportation. Recently, porous framework materials (PFMs), including metal organic frameworks (MOFs), porous coordination polymers (PCPs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and zeolites as well as molecular clusters/polyoxometalates (POMs), have emerged as promising materials for the photofixation of N2, attributed to high surface areas, configurable structures, and unique active sites, which aid N≡N triple bond activation and facilitate efficient electron transfer. The synthesis methods, design strategies focusing on electronic/surface modulation, and photocatalytic N2-fixation performance of PFMs and POMs are summarized. Additionally, the reaction mechanism, charge-carrier kinetics, and thermodynamics, particularly those elucidated by advanced characterization techniques, are emphasized. Challenges and future directions emphasizing the integration of renewable energy sources, advances in catalyst stability, and scalability are also discussed. This review aims to design and develop advanced organic-inorganic materials for N2 photofixation, to facilitate the practical implementation of photocatalytic NH3 synthesis.

Electrocatalysts rarely operate as their as-synthesized phases: under anodic bias, surface reconstruction creates new active states and, critically, new interfacial electrostatics. Yet built-in electric fields (BIEFs) in heterojunction catalysts are still typically treated as static descriptors, disconnected from reconstruction kinetics. Here we demonstrate an electrochemical reconstruction-enabled amplification of interfacial electric fields, yielding a non-equilibrium Mott-Schottky junction that accelerates the emergence of the true oxygen-evolution active phase. A hierarchical hollow AgCo-PBA@NiCo-LDH precursor is designed to host an initial n-n junction. During electrochemical activation, the AgCo-PBA selectively reduces to metallic Ag, converting the interface into an Ag/NiCo-LDH Mott-Schottky heterojunction with a markedly strengthened BIEF, directly quantified by Kelvin probe force microscopy and corroborated by zeta-potential analysis. The amplified field drives interfacial charge redistribution, promotes Ni2+ -> Ni3+ oxidation, and accelerates the formation of NiOOH, identified by in-situ Raman spectroscopy as the catalytically competent phase. As a result, the reconstructed Ag@NiCo-LDH (R-Ag@NiCo-LDH) delivers an overpotential of 271 mV at 30 mA cm(-2), a Tafel slope of 59.25 mV dec(-1), and robust durability (>110 h at 50 mA cm(-2)). Comparative studies with a non-reconstructed control sample directly evidence that the electrochemical transformation, not merely the presence of metallic Ag, is crucial for BIEF enhancement. Density functional theory calculations further indicate that field-enhanced electronic coupling shifts the Ni d-states toward the Fermi level, optimizes adsorption of OER intermediates, and lowers the rate-determining barrier. This work establishes reconstruction-coupled electric-field engineering as a general strategy to move beyond static heterojunction design for non-precious OER catalysis.

The catalytic conversion of lithium polysulfides (LiPSs) is crucial for realizing high-energy-density lithium-sulfur batteries. Herein, we propose a molecular cooperate engineering strategy to construct a hierarchical catalytic reaction chain for addressing the complex sulfur phase transitions and sluggish 16-electron reaction kinetics. A covalent organic framework with a D-A1-A2 electronic structure was developed to generate a built-in electric field (BIEF) via establishing intramolecular charge transfer (ICT) between bipolar functional groups. Theoretical calculations and in situ characterizations confirm that primary and auxiliary functional groups of COF can synergistically enable selective LiPSs capture while the BIEF-facilitated electron transfer accelerates redox reactions of LiPSs, conferring reduced conversion energy barriers and mitigated shuttle effect. Moreover, the anchoring of the & horbar;NO2 group and hence the effect of the & horbar;CF3 group induce directional Li+ deposition, ensuring the favored Li plating with epitaxial layered growth and suppressed dendrite formation. As a result, the Li symmetric cell demonstrates an ultra-long lifespan (>16 000 h at 5 mAh cm(-2)) while Li-S batteries can achieve exceptional cycling stability (0.039% capacity decay per cycle over 1000 cycles). Meanwhile, the pouch cells deliver a high energy density of 395.6 Wh kg(-1) with 90.2% capacity retention over cycling. This work presents a generalizable strategy for advancing multi-electron redox systems.

ABSTRACT Proton exchange membrane fuel cells (PEMFCs) offer a clean pathway for electricity generation. However, their widespread adoption is hindered by the high cost and insufficient durability of platinum (Pt)‐based cathode catalysts. Although non‐precious metal single‐atom catalysts (SACs) have emerged as promising alternatives, their activity and stability still lag behind practical requirements. An effective strategy to bridge this gap is the construction of hybrid catalysts that couple Pt nanoparticles (NPs) with SACs. This approach simultaneously addresses cost and durability challenges; however, the fundamental mechanisms behind the synergistic enhancement remain unclear, impeding rational design. This review systematically summarizes recent advances in Pt‐based NPs/clusters combined with non‐platinum single‐atom site catalysts/hybrid catalysts (Pt/M@SACs), focusing on how the integration of SACs enhances the sintering resistance, durability, poisoning tolerance, and intrinsic activity of Pt sites. This review focuses on elucidating the underlying mechanisms, including charge transfer, modulation of intermediate adsorption, and alteration of reaction pathways. Finally, we provide perspectives on future research directions, aiming to guide the rational design of next‐generation, high‐performance, and low‐Pt fuel cell catalysts.

The oxygen evolution reaction (OER) is the kinetic bottleneck in both alkaline and acidic water electrolysis, and its intrinsically complex four-electron/proton-coupled pathway often constrains efficiency and durability. Conventional catalyst optimization through composition, morphology, and defects engineering largely relies on static structures and is ultimately constrained by the fixed electronic and spin configurations pre-set before the reaction. Herein, we establish a novel dynamic control engineering paradigm, wherein magnetic, electric, strain, and thermal physical fields act as a transformative regulatory handle to overcome the inherent limitations of static catalyst design. By analyzing field-matter interactions, we reveal how these fields dynamically modulate spin/charge distribution, induce lattice distortion, and in-situ tune reaction energetics under operando conditions, enabling reaction pathway switching and real-time catalytic performance enhancement. Unlike prior reviews that address individual fields in isolation, our work uniquely provides an integrated comparative and synergistic perspective, establishing a unified framework that correlates design principles, catalyst architectures and device configurations across magnetic, electric, strain, and thermal fields. We critically examine the interplay of coexisting effects and articulate a “materials-field-reactor” co-design vision for practical integration. This review not only redefines physical fields as active design elements rather than passive external aids but also charts a clear roadmap from mechanistic understanding to practical energy accounted electrolyzers, ultimately defining a new frontier for next-generation OER catalysts in sustainable hydrogen production.

The rapid proliferation of wearable, portable, and foldable electronics has exposed critical limitations in conventional energy storage technologies, particularly in terms of mechanical adaptability and miniaturization. Addressing these challenges necessitates the development of energy storage systems that are not only electrochemically robust but also mechanically flexible and scalable. MXenes, an emerging class of two-dimensional transition metal carbides, nitrides, and carbonitrides, have emerged as compelling candidates for flexible energy storage applications owing to their distinctive structural and physicochemical attributes (electrical conductivity, tunable surface chemistries, and intrinsic mechanical flexibility). This review critically examines recent advances in the synthesis and structural modulation of MXenes tailored for flexible energy storage systems. Emphasis is placed on their integration with complementary materials, such as carbon nanostructures (e.g., nanotubes and nanofibers), transition metal oxides (e.g., V2O3, VO2, and TiO2), and porous matrices. The discussion encompasses a broad spectrum of device chemistries, ranging from diverse flexible battery applications to supercapacitors, and highlights the mechanistic roles of MXenes in charge transport, ion diffusion, and mechanical resilience. Key challenges, including structural degradation under strain, interfacial stability, and scalable processing, are identified. Alongside strategic design principles to guide the future development of mechanically compliant and high-end Mxene based flexible energy technologies are highlighted.

Marine wearable technology is of critical importance for ocean exploration and development. However, antiswelling, underwater adhesion, luminescence, and stable marine environmental sensing capabilities within a single system remain a core challenge in this field. Herein, a multifunctional marine wearable smart skin is designed based on an ionogel with the synergistic effects of hydrophilic-hydrophobic, cation-π, and π-π interactions, as well as lanthanide metal-ligand coordination. Benefiting from its dense polymeric network and hydrophobic nature, the ionogel shows excellent antiswelling performance and can effectively displace the water layer at the bonding interface. The synergistic effects of multiple noncovalent interactions with various materials further endow the ionogel with superior, reversible, and stable underwater adhesion toward distinct substrates. These two properties guarantee long-term stable sensing. Additionally, the introduction of lanthanide complexes enables the ionogel to emit multicolor fluorescence in an aquatic environment. Notably, the salt-adaptive conductivity of the ionogel shields the signal-to-noise ratio from seawater. Eventually, via conformal attaching to the human or robotic body, this marine-adaptable ionogel-based wearable skin can provide not only precise digital signals corresponding to human movements and robotic grasping behaviors, which is further extended to underwater communication, but also bright visual information in dark marine conditions, which is expected to achieve potential functions such as display and warning. These findings provide a promising route for the development of advanced marine wearable platforms with outstanding integrated performance.

Sodium-ion batteries (SIBs) are a promising alternative to lithium-ion batteries due to the abundance and costeffectiveness of sodium resources. Na3MnTi(PO4)3, as a representative polyanionic cathode material, shows great potential but suffers from poor electronic conductivity and structural instability induced by the Jahn-Teller effect, leading to limited cycle life. To overcome these challenges, a boronation mixed-layer coating was designed, which not only enhances electronic conductivity through the carbonaceous framework creation but also improves the interfacial stability. Meanwhile, the formation of metal/B-O bonds in the boronation coating effectively suppresses the Jahn-Teller effect, inhibits the migration and dissolution of transition metal ions, mitigates adverse phase transitions, and tolerates volume changes during cycling. These synergistic effects significantly improve the electrochemical performance and structural durability of the material. As for demonstration, the asdeveloped Na3MnTi(PO4)3/C@NixB electrode delivers superior capacities of 153.2, 108.7, and 105.2 mAh g- 1 at 0.2C, 1C, and 5C after 50, 2000, and 1000 cycles, respectively, outperforming single-layer carbon-coated counterparts. Furthermore, the straightforward synthesis of boronation coating highlights its potential for scalable industrial application.

The strategy of enhancing biocatalytic activity through the modification of natural cells with nanomaterials has overcome the intrinsic catalytic bottlenecks of bacteria, making significant contributions to energy production and pollution treatment. However, chemically engineered biocatalyst systems remain in their early stages of development. Herein, we report a simple and straightforward strategy for constructing an efficient biocatalyst by incorporating carbon quantum dots (CDs) into Escherichia coli (E. coli) to enhance the oxygen reduction reaction (ORR) at the cathode of microbial fuel cells (MFCs). The introduction of CDs significantly accelerates extracellular electron transfer and metabolic activity, markedly increases intracellular adenosine triphosphate (ATP) levels, and promotes substrate utilization. Furthermore, the engineered E. coli exhibits enhanced surface adhesion and increased electronegativity. Electrochemical measurements demonstrate superior ORR activity, delivering a maximum current density of 3.1 mA·cm−2 and an onset potential of 0.67 V, outperforming many previously reported biocatalysts. When applied in an MFC system, the modified biocatalyst achieves a maximum power density of 325 μW·cm−2, placing it among the highest-performing systems reported to date. This work provides a facile and cost-effective approach for improving MFC performance and offers a promising design strategy for next-generation biohybrid catalysts.

The gas-electrolyte-electrode triple-phase interfaces (TPIs) critically govern the kinetics of the electrochemical CO2 reduction reaction (CO2RR) by regulating concerted proton-electron transfer processes. However, sluggish mass transfer and the unbalanced adsorption of key intermediates within the local microenvironment of TPI remain major obstacles to efficient multicarbon product formation. Here, we report a dual-interface strategy featuring amphiphilic and biphasic architectures to decouple mass-charge transfer, achieved through in-situ electrochemical activation of a polydimethylsiloxane (PDMS)-modified Cu-BTC electrode. The hydrophilic/hydrophobic interface promotes the synergistic mass transfer of CO2 and protons within the TPI microenvironment, whereas the amorphous/crystalline interface modulates the electronic structure of catalytic active sites to optimize the adsorption kinetics of key intermediates. Such decoupling-mediation accelerated C2H4 Faradaic efficiency (FE) exceeding 86% at -0.9 V (vs. reversible hydrogen electrode, RHE), over 2.5 times higher than that of the control groups. This work highlights the potential of dual-interface decoupling engineering to simultaneously optimize CO2 mass transport pathways and intermediate adsorption kinetics, thereby enabling highly efficient electrosynthesis of C2H4.

Electrolyte additive engineering is regarded as an effective strategy for dual-interface optimization in four-electron aqueous zinc-iodine batteries (AZIBs). However, realizing durable Ah-level AZIBs with industrial-grade parameters (≥10 mg cm-2 I2 cathode mass loading, ≥5 mAh cm-2 Zn anode areal capacity) remains a significant hurdle. Here, we compare various nitrogen-containing cationic ligands to evaluate their synergistic regulation on iodine immobilization and Zn nucleation. This screening successfully establishes N-methylimidazolium chloride (MImCl) as a premier electrolyte additive for stabilizing dual-interface coordination. Upon discharging, the adsorption of MIm+ on the I2 cathode enables electrostatic binding with polyiodides and ICl2-. This interaction not only suppresses the polyiodide shuttle but also shields the I+ species from hydrolysis, promoting a robust and reversible four-electron I-/I0/I+ redox chemistry at elevated I2 mass loading. On the Zn anode, MIm+ preferentially adsorbs onto its surface during charging, accelerating Zn2+ deposition kinetics for dendrite suppression while passivating parasitic reactions, realizing uniform large-capacity Zn plating/stripping. As a result, the engineered 1.4 Ah four-electron Zn||I2 pouch cells achieve an excellent cyclability of 800 cycles and an ultrahigh cathode-mass-specific energy density of 455 Wh kg-1, surpassing most aqueous Zn-based systems in the Ah-class regime.

Improving the sluggish ion/electron kinetics of niobium-based oxides is of great significance for the development of extremely fast-charging batteries. Herein, we propose an elemental halogen engineering strategy to tune the oxygen vacancy gradient, thereby tailoring the electronic structure. The Br-TNO-350 exhibited remarkable lithium-ion storage capabilities along with outstanding cycling stability. At 10C, the initial discharge capacity reached 164.71 mAh g−1, and was sustained at 143.26 mAh g−1 after 1000 cycles, reflecting a capacity retention of 86.98%. Even under low-temperature conditions (−10 °C), Br-TNO-350 maintained an average capacity of 73.52 mAh g−1 after 500 cycles at 5C. The improvement can be attributed to the expansion of layer spacing and the creation of oxygen vacancies after doping with Br, which facilitates the transfer of ions and electrons. This research presents a promising strategy to enhance the electrochemical performance of TiNb₂O₇ and provides valuable insights for the development of fast-charging batteries with long cycling life.

ABSTRACT Symmetry perturbation of planar FeN 4 moieties in Fe─N─C single‐atom catalysts holds great promise for elevating oxygen reduction reaction (ORR) performance, yet atomically precise coordination engineering of thermodynamically stable configurations with efficient O 2 mass‐transport integration remains challenging. Herein, a nitrogen‐mediated thermal activation strategy is proposed to construct a sublayer‐engineered Fe‐N 5 single‐atom catalyst, termed FeN 5 ‐ANDCL, featuring an axially N‐bridged dual‐carbon‐layer architecture integrated into a hollow carbon framework. The elaborately engineered FeN 5 ‐ANDCL enables cross‐scale structural orchestration, wherein the atomic‐scale axial N‐bridged sublayer steers cross‐layer charge transfer and triggers Fe d z 2 ‐O 2 p orbitals rehybridization, thereby elevating electron occupancy of antibonding states to weaken *OH adsorption, while the hollow carbon framework ameliorates O 2 diffusion resistance and streamlines transport pathways to achieve efficient mass‐transport. The unique configuration endows FeN 5 ‐ANDCL with exceptional ORR activity, attaining a high half‐wave potential of 0.927 V vs. RHE in alkaline media. When deployed in zinc‐air batteries, it delivers a peak power density of 307.3 mW cm −2 and remarkable cycling stability sustained for 1400 h. Collectively, this work establishes sublayer engineering for precise coordination regulation of single‐atom catalysts and demonstrates a cross‐scale orchestration principle that couples local electronic‐structure optimization with macroscopic transport regulation for efficient electrocatalysis.

The dry-film technology offers significant advantages over conventional wet-coating methods for high-loading electrode manufacturing, thereby enhancing the energy density of lithium-ion batteries (LiBs). However, the insufficient particle adhesion and Li-ion conductivity of polytetrafluoroethylene (PTFE) binder not only compromises mechanical stability but also accelerates capacity degradation for thick cathodes. The Ni-rich cathode material, despite its high energy density, also suffers from inherent instability issues. To address the above problems, the lithium-conductive in-situ polymer, PL-Li, is used as a multifunctional additive for thick cathodes, which possesses i) a protective layer bonded to active materials and improves the stability of Ni-rich cathodes, ii) accelerated ionic/electronic transport efficiency of PTFE and continuous ion transport channels in thick cathodes, and iii) high elasticity to boost the mechanical robustness and benefit for the formation of thick cathodes with high mass loading of 90 mg cm-2 (similar to 20 mAh cm-2). With Ni96 cathodes and Si/C anodes, a 17.9 Ah pouch cell attains an energy density of 397 Wh kg-1, and maintains 88.1% capacity after 200 cycles at 1C. This strategy not only enables precise tuning of key components in dry-film technology but also improves the functionality of thick electrodes, making them more suitable for high-energy-density LiBs.

This work develops an exact analytical solution for a reduced-order P2D battery model to combine accuracy with low computational cost. The full-order P2D model's complexity, comprising coupled nonlinear algebraic and partial differential equations, is first reduced via volume averaging and polynomial approximations. This simplification yields a system of algebraic equations and linearly decoupled ordinary differential equations (ODEs). The exact solutions for these ODEs are obtained using Mathematica's DSolve command. Analytical expressions for key physical variables are then derived by substituting the ODE solutions into the algebraic relations. The ROM solution's accuracy is validated against the full-order P2D model (simulated in PyBaMM) across various operating conditions. Comparisons of discharge curves for terminal voltage and electrode surface concentrations show strong agreement, with errors below 4% for C-rates up to 4. The model's primary limitation is a slight inaccuracy in capturing the sharp voltage drop near the end of discharge. Finally, the ROM solution is used to study an NMC/graphite cell, where simulation and experimental results align well (error <1% over most of the domain, rising to 3%-4% near the terminal points). In this study, the active material utilization is considered up to 60% in the positive electrode and 50% in the negative electrode, while electrode porosity is considered up to 30%.

Solid-state lithium (Li) metal batteries are hindered by sluggish Li+ transport and anion-driven interfacial instabilities in polymer electrolytes. Herein, we develop a quasi-single-ion-conducting polymer electrolyte by embedding a crown ether-functionalized covalent organic framework (COF) into a fluorinated polymer matrix. Imine (C=N) linkages in the COF and polar fluorinated polymer domains cooperatively immobilize TFSI- via electrostatic adsorption and pore-defined confinement, while the imine sites and crown ether oxygens dynamically decouple Li+ from its counter-anion and provide exchangeable coordination nodes for rapid interlayer migration along ordered COF channels. As a result, the electrolyte delivers a high ionic conductivity of 1.15 × 10-3 S cm-1 with a high Li+ transference number of 0.91, establishing a continuous Li+-preferential transport network that homogenizes ion flux, promotes the formation of thin and compact interphases, and stabilizes Li anodes and high-voltage cathodes. This crown ether-COF design establishes a broadly applicable design paradigm for decoupling ion transport and interfacial chemistry, paving the way toward next-generation long-lifetime Li metal batteries.

Aqueous zinc-iodine batteries (AZIBs) are promising next-generation energy storage systems owing to their low-cost, high-energy density, and fast redox kinetics. However, their performance remains limited by sluggish iodine conversion, severe I-2 dissolution, and Zn corrosion. Here, zinc single atoms anchored on nitrogen-doped carbon (Zn-NC) serve as a signal atom catalyst to construct an anion-rich surface microenvironment, which lowers the energy barrier for I-2 redox and accelerates reaction kinetics. Meanwhile, Zn-NC enhances electrochemical activity, effectively adsorbs polyiodides, and suppresses the shuttle effect, collectively improving the rate performance and cycling stability. Electrochemical analyses reveal higher capacitive contributions, reduced polarization, and uniform Zn deposition. Consequently, Zn|I-2 cells deliver over 16000 cycles at 10 C, and pouch cells maintain >300 cycles with >8 mAh cm(-2) areal capacity at 54.7% Zn utilization.

Lithium-sulfur (Li-S) batteries have been regarded as a promising high-energy-density secondary battery system since their inception in the 1960s. However, poor long-term cycling performance and reversibility arose from the shuttle effect remains a challenge. Two-dimensional transition metal borides (MBenes) are ideal conductive frameworks due to their layered structure, excellent electrical conductivity, adjustable chemical surface and abundant active sites, which will effectively mitigate the lithium polysulfides (LiPSs) shuttling effect and simultaneously enhance the redox kinetics in Li-S batteries, thereby demonstrating substantial potential for practical applications. In this study, the Mo4/3B2-MoS2 composite was synthesized for the first time using an in-situ vulcanization strategy. By combining the strong chemical adsorption ability of MoS2 toward LiPSs with the high conductivity and electrocatalytic activity of Mo4/3B2 MBene, the shuttle effect is effectively suppressed, and the conversion kinetics are significantly accelerated. The tight interface formed in situ enhances both charge transfer and adsorption capacity, while the MBene skeleton effectively mitigates volume expansion, thereby maintaining electrode stability. Benefiting from the above synergistic mechanism, the Li-S batteries demonstrate an initial discharge capacity of 1311.4 mAh g-1 at 0.2 C, and maintain an ultra-low decay rate of 0.035% per cycle after 500 cycles at 1 C. This study presents an efficient in-situ synthesis strategy for the development of MBene-based composite catalysts, which enhances the immobilization and conversion of LiPSs through interface regulation and a synergistic catalytic mechanism, thereby promoting the advancement of highly reversible Li-S batteries.

Solid-state lithium (Li) metal batteries represent a leading candidate for next-generation high-energy-density energy storage, but their practical deployment is impeded by intrinsic concentration polarization and interfacial instability of conventional symmetric solid-state electrolytes. Herein, we report a solid asymmetric composite electrolyte by integrating single-ion-conducting zeolite molecular sieve layer into a hierarchical polymer framework via in-situ copolymerization encapsulation process, which constructs confined and directional quasisingle-ion transport pathways through three-dimensional supercage network layer enriched with functional acid sites, effectively suppressing anion migration and mitigating polarization. An electrode-electrolyte merging architecture with robust molecular bonding network is established, which can address the interfacial compatibility by filling the gaps and enhance mechanical integrity, resulting in a high ionic conductivity of 1.15 x 10-3 S cm-1 and stably cycling over 1000 h with dendrite-free structure. A high capacity retention of 85.1 % for 1500 cycles is achieved and corresponding pouch cells assembled with high-voltage cathodes demonstrate outstanding electrochemical and safety performance under extreme conditions. This work demonstrates a viable material design paradigm that integrates precise ion transport regulation with interfacial stabilization, offering a transformative pathway toward high-performance solid-state Li metal batteries.