ObjectiveWith the rapid development of the electric vehicle industry, lithium-ion batteries have garnered significant attention as the core energy storage system. Currently, limitations in cathode materials—such as cost and energy density—have become key factors hindering further improvements in lithium-ion battery performance. Among these, high-nickel materials, due to their high specific capacity, excellent rate capability, and cycle stability, have emerged as one of the most promising cathode material systems. However, as nickel content increases, structural degradation during cycling becomes a more severe issue for high-nickel cathode materials. Particularly at a high cut-off voltage of 4.6 V, the material undergoes deep delithiation and inevitably experiences irreversible phase transitions from the hexagonal phase (H1) to the monoclinic phase (M), then back to the hexagonal phase (H2) and finally to the hexagonal phase (H3). The H2-H3 phase transition is often accompanied by severe contraction along the c-axis, resulting in significant anisotropic lattice strain. This uneven volume change leads to stress accumulation within and between particles. When the stress exceeds the material's fracture toughness, cracks form along grain boundaries or within the crystal. The formation of microcracks not only compromises the mechanical integrity of the particles but also provides pathways for electrolyte intrusion, leading to more severe interfacial side reactions. Under high voltage, highly active Ni⁴⁺ at the surface acts as a catalyst, causing severe decomposition of the electrolyte. Furthermore, the release of lattice oxygen further accelerates the surface structural reorganization of the layered phase into the rock salt phase, resulting in the formation of a thicker CEI layer. This mechanism—where irreversible phase transitions drive lattice strain, which in turn induces microcrack propagation, thereby exacerbating interfacial side reactions and structural degradation, and ultimately leading to capacity decay—severely hampers the application of high-energy-density, high-nickel cathode materials. Therefore, synergistically optimizing material design by addressing both bulk structure and interfacial chemistry to mitigate failure is key to developing next-generation high-specific-capacity, long-cycle high-nickel cathode materials.MethodsThe precursors were prepared using the hydroxide coprecipitation method, and Zr-doped high-nickel cathode materials were synthesized via a high-temperature solid-state reaction. The specific procedure is as follows: The hydroxide precursor Ni₀.₈₉Co₀.₀₅Mn₀.₀₅Al₀.₀₁(OH)₂ was uniformly mixed with lithium hydroxide at a molar ratio of 1.03:1 (lithium salt ratio), and then sintered for 15 hours at 760 °C under an oxygen atmosphere to obtain a cathode material named NCMA. During the mixing process, nano-ZrO₂ was added, successfully introducing Zr ion doping at a mass fraction of 0.2%, resulting in a material named NCMA-Zr. The crystal structures of all samples were characterized by X-ray diffraction (XRD) using a Bruker D8 Advance instrument with Cu Kα radiation, with a diffraction range of 2θ between 10° and 80°. The collected XRD data were analyzed using the FULLPROF Rietveld refinement program. The morphology, microstructure, and elemental distribution of the materials were examined using a scanning electron microscope (SEM, ZEISS Sigma 300), a transmission electron microscope (TEM, FEI Tecnai G2 F20), and an energy-dispersive X-ray spectrometer (EDS). The surface chemical composition of the samples was investigated using X-ray photoelectron spectroscopy (XPS, Thermo Scientific K-Alpha, USA). lectrochemical performance was tested using the Newway Battery Program within a voltage window of 2.7~4.3 V or 2.7~4.6 V (1 C = 180 mA/g) at a test temperature of 30°C or the higher temperature of 45 °C The kinetic performance of the electrodes was evaluated using the constant-current intermittent titration (GITT) technique, which involves supplying a current of 0.1C for 10 minutes followed by a 60-minute rest period. Electrochemical impedance spectroscopy (EIS) measurements were performed on a PARSTAT 2273 electrochemical workstation over a frequency range of 100 kHz to 0.1 Hz.Results and DiscussionsThe results demonstrate that the strong Zr-O bonds introduced by Zr doping effectively stabilize the crystal structure during cycling, mitigate particle cracking caused by lattice strain, thereby suppressing interfacial side reactions and enhancing the material's cycling stability. NCMA-Zr exhibits a discharge specific capacity of 194.06 mAh/g with negligible capacity decay after 100 cycles at 30 °C,1 C, and 4.3 V. Under more demanding conditions at a high voltage of 4.6 V, the modified materials still exhibit outstanding performance, maintaining a capacity retention rate of 87.20% after 100 cycles, significantly outperforming the unmodified material. Furthermore, at 4.3 V and 5 C, NCMA-Zr achieves a high discharge specific capacity of 181.24 mAh/g, with a capacity retention rate of 95.31% after 200 cycles. This work provides a new viable technical route for developing next-generation high-nickel cathode materials that combine high energy density with long-cycle performance.ConclusionsIn response to the above challenges, this study aims to address the capacity degradation in the high-nickel material LiNi₀.₈₉Co₀.₀₅Mn₀.₀₅Al₀.₀₁O₂ (NCMA) caused by structural degradation during long-term cycling through crystal structure modification, while also enhancing its electrochemical stability under harsh conditions such as high temperature and high voltage. Zr doping was introduced into the material via a high-temperature solid-state method. The strong Zr-O bond energy effectively stabilizes the crystal lattice framework, suppressing grain cracking and interfacial side reactions during cycling, thereby enhancing the structural and interfacial stability of the material. Through a combination of characterization techniques—including X-ray diffraction, electron microscopy, and X-ray photoelectron spectroscopy—along with electrochemical testing, we systematically investigated the effects of doping on crystal structure, microstructure, surface chemistry, and electrochemical performance. We focused on exploring the structural stability mechanisms of Zr-doped materials under severe conditions such as a wide voltage window (4.3~4.6 V), high rates (5 C), and high temperatures (45 °C), aiming to reveal the regulatory mechanisms by which Zr doping suppresses the irreversibility of phase transitions, slows microcrack propagation, and mitigates interfacial side reactions. This work provides new technical routes and methods for developing next-generation lithium-ion battery cathode materials that combine high energy density with long-term cycling stability.

Lithium‑sulfur (LiS) batteries are highly promising for next-generation high-energy-density energy storage, but their commercialization is severely hindered by the lithium polysulfides (LiPSs) shuttle effect, sluggish sulfur redox reactions, and poor interfacial charge transport. Herein, we rationally construct a heterostructured Co3O4/CoSe2 composite anchored on reduced graphene oxide (rGO) as a multifunctional interlayer for modifying polypropylene (PP) separators, creating a synergistic adsorption–catalysis–transport triple-functional interface to overcome these bottlenecks. The Co3O4 component provides strong chemical adsorption to LiPSs, while CoSe2 lowers the energy barrier for LiPSs conversion and accelerates sulfur redox reactions. Meanwhile, the conductive rGO framework facilitates electron transport and may contribute to hindering LiPSs diffusion. In situ Raman spectroscopy revealed separator-dependent LiPS accumulation at the separator–anode interface during cycling, revealing an altered spatial distribution and reaction pathway of polysulfides. DFT calculations further confirm enhanced adsorption energies and a substantially reduced Gibbs free energy barrier for the rate-determining LiPSs conversion step on the Co3O4/CoSe2@rGO surface. Owing to these advantages, the LiS battery with the modified separator exhibits excellent long-term stability with a low capacity decay rate of 0.05% per cycle over 1400 cycles at 2C, and reliable performance under extreme conditions (5 °C, 60 °C, and high sulfur loading of 5.16 mg cm−2). The pouch cell delivers an initial capacity of 1319.7 mAh g−1 at 0.1C, providing proof-of-concept validation for the scalability of this separator engineering approach. This work offers a systematic optimization framework for multifunctional separators and provides mechanistic insights that may inform the development of high-performance LiS batteries.

Increasing the upper cut-off voltage of O3-type layered LiCoO2 cathodes is a promising strategy to enhance their specific energy density, attracting significant recent attention. However, this approach induces severe surface reconstruction and poor cycling performance as a result of oxygen loss. To overcome this limitation, we propose a novel synthesis strategy that employs a metastable O2-type LiCoO2 framework combined with a minor Li-defective T2-type Li1-xCoO2 phase, which is transformed via thermal treatment into a stable O3-type LiCoO2 capable of high-voltage operation up to 4.6 V. Surprisingly, this thermal treatment results in the formation of a thin, uniform spinel LiCo2O4 layer on the O3-type LiCoO2 surface. This Li-ion conductive surface layer not only facilitates Li-ion transport but also inhibits structural collapse along the c-axis during high-voltage cycling. Furthermore, it effectively mitigates oxygen loss from the LiCoO2 cathode during long-term cycling. Consequently, the modified O3-type LiCoO2 cathode exhibits a high-capacity retention of 88% at 1 C over 200 cycles (3.0-4.6 V), substantially outperforming its unmodified counterpart (39%). This strategy of converting Li-poor metastable phases into a thermodynamically stable layered structure with a self-formed protective surface layer opens a new avenue for developing high-capacity, stable layered cathodes for advanced lithium-ion batteries.

Manipulating the selectivity-determining step in the hydrogenation of nitrogen-containing intermediates is critical to achieving high ammonia selectivity in electrocatalytic nitrate reduction. Here, we propose a molecular interface engineering strategy that functionalized with thiol-anchored aromatic ligands to regulate the interfacial binding affinity and activation of key nitrogen-containing intermediates on silver nanocube surfaces. By systematically varying the electronic properties of the substituents, we identify 4-(methylthio)benzaldehyde as the most effective ligand, increasing the ammonia Faradaic efficiency from 50.8% to 98.9% and achieving a yield rate of 14,366.1 μg h-1 cmgeo-2 at -0.63 V versus reversible hydrogen electrode. In situ electrochemical characterizations combined with theoretical simulations further reveal that 4-(methylthio)benzaldehyde modification promotes the activation of weakly hydrogen-bonded water molecules and accelerates the hydrogenation of *HNO intermediates. This targeted modulation of interfacial binding affinity offers an effective strategy for selectivity control in electrocatalytic nitrate reduction. The enhanced performance is further validated in a membrane electrode assembly electrolyser, underscoring the practical viability of this molecular design strategy for selective nitrate conversion.

Dehydration-induced phase engineering reconfigures kinetic pathways of mixed phosphate cathodes to enable sustainable and low-temperature sodium-ion batteries.

Introducing ES into 1 H ,1 H ,5 H -perfluoropentyl-1,1,2,2-tetrafluoroethyl (OTE)-based electrolyte creates SO⋯C–F interactions that weaken the fluorine effect, reduce anion aggregation, and promote loose solvation and fast kinetics.

The nickel-based layered oxide cathode material can achieve ultra-high capacity by increasing the nickel content to 90% and raising the cut-off voltage to 4.6 V. However, the residual strain generated during calcination exacerbates structural degradation of the ultra-high-nickel cathode. Herein, we report a stepwise tempering treatment approach that incorporates Co, B, and Al into the LiNi0.96Mn0.04O2 (NM96) cathode material to inhibit the reduction transition from Ni3+ to Ni2+ and mitigate the non-uniform phase transition during calcination, effectively alleviating residual strain (0.37% to 0.14%) and facilitating the formation of a stable cationic phase (similar to 3 nm) on the active surface, thereby successfully reducing lattice oxygen loss and suppressing structural degradation. The modified material (NM96@Co-B+Al) exhibits an exceptionally high reversible capacity of 248 mAh g(-1) and a remarkable specific energy density of 957 Wh kg(-1), while maintaining 86.5% capacity retention after 100 cycles at 4.6 V, 1 C. This work highlights the important role of inhibiting residual strain in improving the structural stability of layered materials.

In the fabrication of microelectronic devices, polyimide (PI) is often patterned through plasma etching. However, the relationship between its etching behavior and the precursor processing technology has not been systematically revealed. In this paper, PMDA-ODA type PI was selected as the research object. For the first time, the effects of two film-forming processes, freeze drying (FD) and thermal drying (TD), on the microstructure of PI films and their O2 plasma etching behavior were systematically compared. By means of scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and water contact angle testing, the intrinsic differences between the two types of films and the performance evolution rules during the etching process were clarified. The results show that the surface of the FD-PI film exhibits discrete pore structure, while the TD-PI film is characterized by a dense and non-porous structure. This structural difference leads to more significant surface morphology evolution and chemical composition changes in FD-PI during the etching process. After plasma treatment, polar oxygen-containing groups such as O=C-O were successfully introduced onto the surfaces of both types of films. The content of these groups showed regular changes with the etching time, and the wettability of the films processed by the two different technologies was characterized by a dynamic water contact angle measuring instrument. This study reveals the internal mechanism by which the drying process affects the plasma etching behavior of PI films by regulating their initial microstructure, providing important theoretical basis and process guidance for the precision processing of high-performance PI films for advanced electronic devices.

Lithium-metal batteries (LMBs) stand as promising next-generation energy storage systems by virtue of their ultrahigh energy density, yet conventional liquid electrolytes suffer from intrinsic flaws including flammability, lithium dendrite growth and concentration polarization induced by dual-ion conduction. Gel polymer electrolytes (GPEs) integrate the high ionic conductivity of liquid electrolytes and the superior safety of solid electrolytes, but remain challenged by the trade-off among ionic conductivity, lithium-ion transference number and interfacial stability. Herein, a single-ion-conducting gel polymer electrolyte coupled with an electrospun membrane (SIC-GPE-ESM) is designed via a synergistic strategy of anion covalent anchoring and separator structural engineering. A polymerizable anion-functionalized lithium salt (LiMTFSI) is synthesized to covalently immobilize anions into the PEGDA-ETPTA crosslinked network, and the electrostatic repulsion between MTFSI- and TFSI- affords an ultrahigh Li+ transference number (tLi+) of 0.94. A PVDF-PAN-PVDF triple-layer electrospun membrane is constructed to enable mechanical reinforcement, thermal stability and accelerated ion transport. SIC-GPE-ESM exhibits a room-temperature ionic conductivity of 2.47 mS cm- 1, a 5.48 V electrochemical stability window, 129.7% elongation at break and 953.02 MPa elastic modulus. LiFePO4/Li cells deliver 108 mAh g- 1 at 10C with 90.04% capacity retention after 1400 cycles at 1C, while NCM811/Li cells achieve 191.87 mAh g- 1 at 0.1C with 71.55% retention after 200 cycles at 1C. Post-cycling characterizations confirm stable inorganic-rich solid electrolyte interphase/cathode electrolyte interphase (SEI/CEI) layers that effectively suppress lithium dendrite growth and transition metal dissolution. This work provides a robust strategy for constructing highconductivity single-ion gel electrolytes toward high-voltage LMBs.

Lithium-ion batteries have been widely deployed in the electric vehicle sector, as well as in other application areas. This widespread use has led to the accumulation of large quantities of diverse spent batteries, particularly lithium iron phosphate (LFP), and the recycling of spent batteries is increasingly imperative. Considering the high economic value of the regenerated lithium manganese iron phosphate (LMFP) product and the coexistence of spent LFP and spent lithium manganate oxide|lithium manganese oxide, we propose a new one-step strategy with integrated leaching-sol-gel and subsequent annealing. Through this route, we can successfully prepare LMFP with high phase purity and structurally stable characteristics. The regenerated LMFP exhibits excellent electrochemical performance, delivering an initial discharge capacity of 162 mAh g(-1) at 0.1 C and retaining its capacity without observable degradation after 500 cycles at 1 C. This recycling strategy demonstrates high energy efficiency, economic feasibility, process simplicity, and scalability, highlighting its strong potential for practical application in lithium-ion battery recycling.

Olivine-type LiMn x Fe1-x PO4 (LMFP) is a promising high-voltage cathode for next-generation lithium-ion batteries; however, its commercialization is hindered by structural instability from Mn3+ Jahn-Teller distortion and sluggish ionic kinetics. Herein, we develop a novel gradient-insertion strategy to address these limitations simultaneously. Through a facile solid-state process, Mg2+ is incorporated into LMFP microspheres, creating a concentration profile. Structural characterization confirms the successful incorporation of Mg2+, predominantly occupying the transition-metal sites, without altering the primary structure or forming a coating layer. This targeted modification significantly improves electrochemical performance: the Mg-insertion cathode (LMFP-Mg) delivers a high capacity of 149.78 mAh g-1 at 0.1 C, with the Mn redox contribution increasing significantly from 40.3% to 53.2%. After 300 cycles at 1 C, LMFP-Mg retains 91.2% of its capacity, significantly outperforming pristine LMFP (80.5%). At a high rate of 5 C, LMFP-Mg demonstrates a 26.4% improvement in discharge capacity compared to LMFP. Mechanistic studies reveal that gradient Mg2+ insertion cooperatively stabilizes the bulk lattice, suppresses Mn3+ Jahn-Teller distortion, and enhances Li+ diffusion coefficient, while the Mg-rich surface mitigates transition-metal dissolution and interfacial side reactions. This work demonstrates that spatially controlled insertion is a promising strategy for designing high-energy-density, long-life olivine cathodes.

Lithium metal batteries (LMBs) are hindered by dendrite growth and volume expansion. While 3D hosts offer solutions, uniform lithiophilicity often leads to surface-preferred deposition and internal space wastage. Herein, we report amorphous carbon-coated ferroferric oxide (Fe3O4@C) nanospheres designed with a radial lithiophilicity gradient. The strong lithiophilic Fe3O4/C core and weaker lithiophilic carbon shell create a thermodynamic driving force, guiding Li ions to penetrate the outer layer and achieve "bottom-up" or "inside-out" deposition. This gradient mechanism, coupled with the robust solid core and flexible shell, effectively suppresses Li dendrite growth and accommodates volume expansion through synergistic mechanical stress. As a result, the half-cell achieves a stable Coulombic efficiency of 97.17% at 1 mAh cm-2, while the symmetrical cell demonstrates long-term cycling stability over 2000 h. Furthermore, the LFP full-cell retains a 93.4% capacity after 150 cycles at 1 C. This work highlights the critical role of radial gradient lithiophilicity in ensuring uniform, deep-level Li deposition for practical LMBs.

The electrochemical performance of lithium-sulfur batteries is hindered by the shuttle effect of lithium polysulfides, the poor electrical conductivity of sulfur, and sluggish redox kinetics of sulfur species. By mimicking the high-efficiency mass transport, excellent nutriment capture capability, and rapid catalytic conversion properties of marine sponges, a multifunctional bicontinuous mesoporous carbonaceous sulfur host incorporated with Co single atoms (denoted as bimeso-CoNC) is constructed as a cathode material for Li-S batteries. The 3D interconnected mesochannels in bimeso-CoNC enhance the Li+ transport and sulfur loading, while the incorporated Co single atoms exhibit strong polysulfide adsorption and accelerate the kinetics of polysulfide conversion. Remarkably, the bimeso-CoNC/S-based cathode delivers a high capability of 570.0 mAh g-1 at 6 C, a high areal capacity of 11.6 mAh cm-2 at an ultrahigh sulfur loading of 13.5 mg cm-2, and remarkable long-term stability (over 1200 cycles with 0.039% capacity decay per cycle). The comprehensive performance ranks among the best of the reported carbon-based cathode materials for Li-S batteries. This study presents a pore engineering strategy to improve the loading and adsorption of sulfur as well as accelerate the sulfur redox kinetics in Li-S batteries, which remarkably suppresses the shuttling effect and thus enhances the performance of Li-S batteries.

The Mo-O-Ni anchoring bonds for hydrogen spillover are constructed by room temperature solid-state reduction. The optimized 12%-PMA@Ni with well-balanced Mo-O-Ni anchoring bonds achieves complete naphthalene hydrogenation to decalin within 2 h at 180 °C under 1 MPa H2. DFT reveals a reduced H2 activation barrier (0.31 eV) and strong naphthalene adsorption (-1.75 eV), enabling efficient hydrogen migration.

Ni-rich layered oxide cathodes LiNixCoyMn1-x-yO2 (NCM, x ≥ 0.8) suffer from concurrent structural instability, interfacial degradation caused by residual lithium, and sluggish Li+ diffusion kinetics, which severely limit their application in high-energy lithium-ion batteries. Although extensive efforts have been devoted to addressing these issues, strategies capable of concurrently regulating the bulk structure, surface chemistry, and Li+ diffusion kinetics in a simple and scalable manner remain limited. Herein, a simple Ti and Nb comodification strategy via secondary calcination is proposed to synergistically regulate bulk structure, surface chemistry, and Li+ transport in Ni-rich cathodes. The incorporation of high valence Ti and Nb induces controlled Li/Ni antisite defects, which enhance the lattice and thermal stability of the cathodes. Meanwhile, the comodification reduces surface residual lithium, suppresses interfacial side reactions, and introduces oxygen vacancies, thereby enhancing Li+ diffusion kinetics. Benefiting from this synergistic regulation, the modified cathode delivers a high rate capacity of 174 mAh g-1 at 5 C and retains 94% capacity after 100 cycles at 1 C. This work provides an effective strategy for constructing Ni-rich cathodes with high structural stability and excellent performance for next-generation high-energy LIBs.

Due to their open-framework structures and fast Na+ transport, Prussian blue analogues (PBAs) are promising cathode materials for sodium-ion batteries (SIBs). However, recycling them is hindered by environmental and economic concerns associated with low-value transition metals (TMs) and toxic cyanide ligands. Herein, we present a green, cost-effective, and broadly applicable upcycling strategy that directly converts spent PBAs into layered oxide cathodes via controlled thermal transformation along with a universal evolution behavior, as demonstrated by the successful synthesis of P2-type, biphasic P2/O3-type, and O3-type materials. Advanced structural characterizations reveal that the transformation from the three- dimensional PBA framework to twodimensional layered oxides involves lattice transformation, ligand decomposition, and the reorganization of TM octahedra into ordered TM-O layers. To understand the complex structural evolution of O3-type layered oxides during Na+ extraction, FAULTS simulations are employed to clarify the transformation mechanisms in NaNi1/ 3Fe1/3Mn1/3O2. Through compositional engineering and structural optimization, the modified cathode displays noticeably improved electrochemical performance, including fast Na+ diffusion, low voltage hysteresis, and exceptional cycling stability. The proposed upcycling pathway is technically feasible and offers methodological guidance for the circular development of SIB cathode materials.

Coming research trends will move toward high-energy-density Li-rich manganese layered (LMR) cathodes (>900 Wh kg-1). Nevertheless, their practical implementation is severely impeded by irreversible lattice oxygen release, progressive structural deterioration, pronounced capacity, and voltage decay. A critical unresolved issue arises from the absence of an effective atomic-scale design principle capable of stabilizing the interfacial structure and suppressing the layer-to-rock salt transformation, an instability pathway that is further aggravated in high-Ni LMR compositions. In this work, we establish an in situ atomic-level regulation strategy through La3+/W6+ codoping, which induces the formation of an interface-disordered phase while preserving the integrity of the layered framework. This strategy provides a direct resolution to this long-standing structural challenge by enabling controlled oxygen-vacancy generation and localized cation rearrangement at the near-surface region, thereby effectively suppressing detrimental phase transitions during electrochemical cycling and simultaneously enhancing Li+ transport kinetics. The introduction of robust La-O and W-O bonds further reinforces the interfacial oxygen framework and markedly improves thermal stability. As a consequence, the modified cathode demonstrates substantially enhanced electrochemical durability. Compared with the original sample, the capacity retention rate of LW-3 is 80.25%, which is significantly better than that of LMR (66.26%). Moreover, the results substantiate that high-Ni LMR compositions possess an intrinsic propensity toward layered-to-rock-salt transformation, which profoundly compromises structural and electrochemical stability. This work strengthens the structural integrity and mechanical resilience of LMR cathodes and offers a responsible strategy toward realizing high-energy, long-life Li-rich layered oxides suitable for next-generation energy storage technologies.

The tunnel-type oxide cathode material Na0.44MnO2 (NMO) and the sodium-based ferricyanide Na x Mn[Fe(CN)6]1-δ ·nH2O (FMHCF) are considered among the most promising cathode materials for sodium-ion batteries. However, the poor structural stability of FMHCF and the low sodium content in the NMO cathode limit their practical production and application. Guided by theoretical calculations, this work proposes an in situ growth strategy based on surface energy regulation mechanisms. The growth mechanism of the NMO-FMHCF intergrowth material was investigated by tracking its real-time morphological evolution at varying phase ratios and aging times. Furthermore, through electrochemical testing combined with theoretical calculations, we elucidate the synergistic enhancement effects of the NMO-FMHCF intergrowth structure in terms of structural stability, electrochemical performance, and sodium replenishment during the first cycle. The optimized intergrowth cathode material demonstrated significantly improved first-cycle charge-discharge efficiency, with a capacity retention rate of 70.46% after 950 cycles at 5C, indicating a promising new approach for designing high-performance sodium-ion battery cathode materials.

The commercial application of hard carbon (HC) anodes in sodium-ion batteries (SIBs) faces significant challenges, including poor rate capability and low initial Coulombic efficiency (ICE). Although current research primarily focuses on enhancing sodium storage capacity by increasing the number of closed pores, the slow filling kinetics associated with these pores often compromises rate performance. In this study, an in-situ gas etching strategy is developed, leveraging the chemical interaction between volatile species generated during starch pyrolysis and phenolic resin precursors to construct HC featuring abundant closed pores with highly roughened inner walls. The optimized HC exhibits exceptional electrochemical performance, delivering a high reversible specific capacity of 368.85 mAh g-1 and an ICE of 89.8%. Importantly, it demonstrates outstanding rate capability, retaining a specific capacity of 262.11 mAh g-1 at an ultra-high current density of 5 A g-1. This vapor-phase-mediated structural engineering approach offers a promising route for the rational design of high-performance hard carbon anodes, advancing their practical deployment in high-power SIBs.