Metal sulfides, especially those containing alloying-capable metal elements, have shown great potential as sodium storage materials. However, the complex reaction process imposes more stringent requirements on the kinetic rate. A simple lattice distortion strategy is first proposed in this work to engineer the p-band center of S in Cu3SbS3 for enhanced Na+ storage. Though the co-doping of Se and accompanying S vacancies, the resultant lattice distortion elongated the bonds between metal and nonmetal elements to weaken their orbital hybridization and lift the p-band center for a high Na+ adsorption. The defects also increase the number of charge carriers for an improved conductivity. All those merits combined to contribute a superior electrochemical reaction kinetic in the Se-Cu3SbS3@rGO anode. It achieved a high capacity of 569.1 mAh g-1 at 0.1 A g-1, excellent rate capability of 273.6 mAh g-1 at 50 A g-1 and superior cycling stability of 387.4 mAh g-1 (90%) after 1000 cycles at 5 A g-1 as well as 92% after 150 cycles at 0.5 A g-1 in the full cells. The insights into the function mechanism of Se-vacancies doping-induced lattice distortion offer valuable insights into the design and development of sulfide-based anode materials and sodium-ion batteries.

Hard carbons are emerging as the most viable anodes for the commercialization of Na-ion batteries. However, their performance limits are far from being disclosed because of ambiguous Na-storage mechanism. Here, we report that nano-space confinement regulates heterogeneous nucleation of quasi-metallic Na clusters in closed pores, uncovering a coupled “intercalation-pore filling” and stage-wise storage mechanism for high capacities. Theoretical studies reveal that the energy barrier for Na-cluster growth decreases as the nanocavity size decreases; however, it remains energetically unfavorable at potentials (V vs. Na/Na+) > 0. Interestingly, in the coupled storage, Na-ion intercalation in nanoconfined orifices triggers stepwise pre-nucleation, reducing energy barriers for spontaneous Na-cluster growth in progressively larger cavities at positive potentials, thus enabling Na-cluster deposition into previously unused closed pores. This understanding guides the rational design of stage-wise closed pores, resulting in superior performance of 500 mAh g−1 at 50 mA g−1 and 344 mAh g−1 at 2000 mA g−1. Mechanistic studies further identify a new stage, where confined nano-spaces at 0.4–0.6 nm facilitate pre-desolvation and enhance Na-ion transport kinetics for high-rate capabilities. This work identifies the origin governing Na-storage behavior in the closed pores of hard carbons, boosting their overall performance beyond prior expectations.

Abstract Hard carbon is a versatile anode for alkali-ion batteries owing to its low cost, structural tunability, and ability to reversibly host multiple alkali-metal ions. However, how structural evolution governs ion-specific storage mechanisms remains unclear, limiting rational optimization across different battery chemistries. Here we synthesize a series of resin-derived hard carbons with continuously evolved microstructures by tuning the carbonization temperature, enabling direct comparison of Li+, Na+, and K+ storage under identical conditions. By correlating interlayer spacing, defect density, closed-pore architecture, and graphitization degree with capacity contributions, kinetics, and diffusion behavior, we establish clear ion-dependent structure–mechanism relationships. Lithium storage is dominated by defect-assisted adsorption in highly disordered carbons with expanded interlayers, delivering 197.75 mAh g−1 after 1000 cycles at 5 A g−1 in full cells. Sodium storage is governed by low-voltage filling of enlarged closed pores enabled by moderate structural ordering, achieving 211.17 mAh g−1 after 500 cycles in full cells and 74.86% capacity retention after 1000 cycles in pouch cells. Potassium storage is mainly controlled by intercalation into graphitic domains with partial pore filling, delivering 97.25 mAh g−1 after 200 cycles. These results reveal an ion-dependent transition in hard-carbon storage mechanisms and provide structure-guided design principles for high-performance alkali-ion battery anodes.

Gel electrolytes represent a promising alternative to liquid counterparts for mitigating free water-induced parasitic reactions at Zn metal anodes. However, the intrinsically sluggish ion transport within homogeneous gel networks severely impedes electrochemical kinetics. Herein, a novel gradient gel-liquid electrolyte (G-PAM) is proposed to reconcile interfacial stability with rapid ion transport. By introducing a Mn2+-rich coating on the cathode-facing side of the separator to locally quench persulfate initiators and inhibit polymerization, precise spatial control over the in-situ gelation of acrylamide monomers is realized, enabling selective gel formation at the anode side while preserving a liquid phase near the cathode. This functional graded electrolyte exhibits high ionic conductivity (2.52 & times; 10-2 S & centerdot;cm-1) comparable to liquid electrolyte, ensuring fast charge transfer kinetics. Moreover, the amide-induced solvation restructuring favors the formation of a thin, stable N-rich solid electrolyte interphase (SEI), which enhances anodic interfacial stability and facilitates uniform Zn deposition. Consequently, ultra-stable Zn plating/stripping over 11,000 h is achieved. Zn||MnO2 full cells exhibit excellent rate performance and long-term cycling stability with minimal capacity decay of only 0.011% per cycle. This in-situ spatial regulation strategy establishes a new paradigm for designing functionally graded electrolytes, paving the way toward practical, high-performance Zn-based batteries.

Hard carbons (HCs) are compelling anodes for sodium-ion batteries, where closed pores are vital for achieving high low-voltage plateau capacity. However, simultaneous engineering closed-pore architectures and the internal carbon microstructure remains challenging. Herein, we propose an in-situ Zn-sacrificial strategy that exploits the dual roles of zinc to rationally tailor the carbonaceous microenvironment. During the pyrolysis, zinc acts as a mild graphitization catalyst, fostering expanded graphitic domains that accelerate Na+ diffusion. Simultaneously, zinc volatilization introduces abundant closed pores anchored with Zn − N4 sites, which strengthen Na+ adsorption and lower the nucleation barrier, thereby improving the utilization of large closed pores and boosting the plateau capacity as well as sodium storage kinetics. Consequently, the resulting Zn-HC-1300 anode delivers a high reversible specific capacity of 385.7 mAh g−1 at 0.05 A g−1 and retains 312.3 mAh g−1 after 400 cycles at 0.1 A g−1. This work establishes an in-situ Zn-sacrificed paradigm integrating catalytic microstructure modulation with precision closed-pore engineering for high-performance sodium-ion batteries.

High-voltage lithium-rich manganese-layered oxides (LRMO) are regarded as one of the most promising cathode materials for the next generation of high-energy-density lithium-ion batteries (LIBs), yet they suffer from severe irreversible lattice oxygen redox and structural degradation during charging-discharging. Herein, we propose a synergetic atomically topological interlocking (ATIL) strategy with W6+ and Sc3+ selectively incorporated into the transition metal (TM) and lithium (Li) layers, respectively. This targeted multi-site doping that simultaneously pin the TM and Li slabs to construct stable interlayer interlocking chains, and in combination with the in-situ formed rocksalt@layered coherent interface, can construct robust ATIL structure and achieve near-zero strain upon cycling. This effectively disrupts the coupled degradation cascade between irreversible cation migration and oxygen release, holistically addressing synergistic problems of bulk stability and interfacial reactivity. As a result, the modified cathodes exhibit significantly improved initial Coulombic efficiency of 90.16%, enhanced cycling stability of 300 cycles @ 90.15% with mitigated voltage decay, superior rate performance and enhanced thermal stability. The full pouch cell configured as LRMO-WS || graphite retains 81.07% of capacity after 1000 cycles at 1 C charge / 2 C discharge, with a voltage drop as low as 0.145 mV/cycle. This work highlights the great prospects of interlocking structure in stabilizing cation/anion redox and provides a viable principle for designing high-performance LRMO.

Atomic-level Fe doping in MoO2/C regulates its electronic structure, strengthens polysulfide adsorption, accelerates catalytic conversion and provides additional active sites. Consequently, the Fe-MoO2/C-S cathode exhibits excellent performance, offering an effective strategy for designing highly catalytically active sulfur hosts for advanced Li-S batteries.

ABSTRACT Amorphous copper‐based catalysts with a large number of undercoordination sites exhibit promising catalytic performance for the electrocatalytic CO 2 reduction reaction (eCO 2 RR). However, their structure stability of amorphous Cu x O is significant for achieving high‐efficiency catalytic performance and excellent stability. Herein, amorphous Cu x O nanoparticles embedded uniformly in mesoporous silica spheres (Cu x O@mSiO 2 ) were fabricated via a modified Stöber method combined with in situ electrochemical pre‐reduction. Experimentally, the Cu─O─Si interface suppresses the over‐reduction of CuO to metallic Cu and modulates the electronic structure of Cu species. It can be demonstrated that the resulting amorphous Cu x O switches the adsorption of * CHO and * OCCO intermediates from conventional Cu‐anchoring configurations to lattice oxygen‐anchoring counterparts, significantly weakening the thermodynamic restriction for post‐CO coupling toward C 2+ pathway. Ideally, the Cu x O@mSiO 2 ‐0.4 catalyst achieves a C 2+ Faradaic efficiency of 40.1% with a partial current density of −10.8 mA∙cm −2 at −1.7 V vs. RHE, which is two times greater than that of crystalline CuO‐derived Cu. Furthermore, Cu x O@mSiO 2 maintains stable catalytic activity and selectivity over 9 h of continuous eCO 2 RR reaction.

Lithium oxalate (Li2C2O4) is regarded as a promising prelithiation agent due to its high specific capacity and cost-effectiveness. However, its intrinsically poor electronic conductivity and sluggish reaction kinetics result in a high lithium liberation potential (typically above 4.5 V), which challenges the stability of electrolytes and electrode materials, and deteriorates overall battery performance. In this work, the intermetallic NiBi3 catalyst with metallic conductivity and strong interfacial interaction is introduced to promote the low-potential decomposition of Li2C2O4. Benefiting from the synergistic electronic effect between Ni and Bi, the incorporation of Bi effectively modulates the electronic structure of Ni sites viad-p orbital hybridization, thereby enhancing the adsorption and activation of Li2C2O4, weakening the Li2C2O4 framework and facilitating its decomposition. When coupled with ultrahigh-Ni NCM96 cathodes, the NiBi3-Li2C2O4 prelithiation system provides higher charge capacity (273.3 mAh g-1) and improved reaction kinetics compared to the pristine counterpart. Furthermore, full-cell configurations based on SiOx anodes exhibit enhanced lithium compensation capability, maintaining a capacity retention of 52.9% after 150 cycles at 0.5C. These results demonstrate that intermetallic NiBi3 is an efficient catalyst for activating Li2C2O4 and provides a viable strategy for developing high-performance cathode prelithiation systems.

Amorphous copper-based catalysts with a large number of undercoordination sites exhibit promising catalytic performance for the electrocatalytic CO2 reduction reaction (eCO2RR). However, their structure stability of amorphous CuxO is significant for achieving high-efficiency catalytic performance and excellent stability. Herein, amorphous CuxO nanoparticles embedded uniformly in mesoporous silica spheres (CuxO@mSiO2) were fabricated via a modified Stöber method combined with in situ electrochemical pre-reduction. Experimentally, the Cu─O─Si interface suppresses the over-reduction of CuO to metallic Cu and modulates the electronic structure of Cu species. It can be demonstrated that the resulting amorphous CuxO switches the adsorption of *CHO and *OCCO intermediates from conventional Cu-anchoring configurations to lattice oxygen-anchoring counterparts, significantly weakening the thermodynamic restriction for post-CO coupling toward C2+ pathway. Ideally, the CuxO@mSiO2-0.4 catalyst achieves a C2+ Faradaic efficiency of 40.1% with a partial current density of -10.8 mA∙cm-2 at -1.7 V vs. RHE, which is two times greater than that of crystalline CuO-derived Cu. Furthermore, CuxO@mSiO2 maintains stable catalytic activity and selectivity over 9 h of continuous eCO2RR reaction.

The rational design of proton-based energy storage systems requires a fundamental understanding of proton behavior under nanoscale confinement. Herein, we elucidate the desolvation dynamics and charge-transfer mechanisms of confined protons within interlayer-engineered Ti3C2Tx MXenes through a combined theoretical and experimental approach. Density functional theory (DFT) calculations reveal that proton transport strongly depends on the interlayer spacing: when the gallery distance exceeds 0.6 nm, hydrated protons (H5O2 +) undergo efficient desolvation and interfacial charge transfer, whereas narrower spacing traps protons in a suspended, fully solvated state, thereby impeding charge transport. Guided by these insights, Mo-doped MXenes (Mo-MXene) with tunable interlayer spacing were synthesized, exhibiting enlarged galleries and enhanced surface charge density. The optimized Mo-MXene-based hybrid supercapacitors deliver a high volumetric energy density of 94.2 Wh L-1 at a power density of 398.9 W L-1, and more importantly, maintain an impressive energy density of 74.0 Wh L-1 even at an ultrahigh power density of 156.7 kW L-1. This study establishes interlayer spacing as a decisive structural parameter governing proton desolvation and electron-transfer coupling, providing a universal design strategy for high-rate, high-capacitance proton-based electrochemical energy storage systems.

Efficient proton transport in 2D confined electrodes critically depends on the flexibility of interfacial hydrogen-bond networks. However, the interfacial issue becomes more pronounced in the 2D confined space. The strong hydrogen bonds between confined water molecules and surface ─O terminations of MXenes immobilize protons and hinder charge storage kinetics. Here, we introduce an edge-coordination strategy to achieve precise electronic delocalization modulation in Ti3C2Tx MXene by anchoring carboxyl-functionalized carbon quantum dots (CQDs) at positively charged edges. The CQDs induce substantial electron delocalization on surface ─O sites, which simultaneously weakens rigid hydrogen bonds and facilitates interfacial charge transfer. This regulation establishes a dynamic hydrogen-bond network that supports continuous Grotthuss-type proton migration within the confined channels. Consequently, the optimized CQDs@MXene electrode delivers a volumetric capacitance of 2507.2 F cm-3, retains 65.8% at 1000 mV s-1, and maintains nearly 100% stability over 10 000 cycles. In situ vibrational spectroscopy and density functional theory reveal that the electron delocalization drives the weak hydrogen-bond interface and charge transfer coupling governs proton transport kinetics. This work establishes electronic delocalization as an effective paradigm for manipulating hydrogen-bond dynamics and interfacial charge transport for ultrafast ion transport in confined electrochemical systems.

The attractive MoSe2 anodes face the problems of low conductivity and Se loss. Introducing electron donor has proven effective in enhancing metallic 1T content for improved performance. However, it remains difficult to mitigate the degradation of 1T phase and the loss of active materials, which continues to hinder the cycling stability. Guided by research experience and DFT results, low-valence Cu+ atoms were selected as both electron donors and vacancy creators in this work to synergistically address these two challenges. The donated electrons from Cu+ to Mo atoms facilitate the phase transition from semi-conducting 2H to metallic 1T in MoSe2 for accelerated reaction kinetics with a high capacity of 257.0 mAh g(-1) at 50 A g(-1). Meanwhile, the low-valence atoms assisted the formation of accompanying vacancies. The exposed the Cu+ donor enhanced the PF6(-) adsorption and also catalyze the formation of NaF-rich SEI layer. This effectively mitigated the loss of activity materials and the volume expansion issues, resulting in a high capacity of 364.6 mAh g(-1) (similar to 124.6% of its original capacity) after 18,000 cycles at 10 A g(-1). The insight gained from the doping of low-valence metal atoms offer a promising pathway for the SEI-modulating strategy and also the future development of other type electrode materials.

Supercapacitors(SCs) stand out among various energy storage devices owing to their high power density and long-term cycling stability. As new two-dimensional material, MXenes have become a research hotspot in recent years owing to their unique structure and rich surface functional groups. Compared with other materials, MXenes are more promising for SCs owing to their tunable precursors, structural stability, and excellent electrical conductivity. However, the rate performance and electrochemical reaction activity of MXene materials are poor, and stacking severely limits their application. Therefore, various modification strategies are employed to improve the electrochemical performance of MXene materials. As the modification strategy of MXene electrode materials often involves increasing the number of ion transport channels to expose more active sites, the packing density is also affected to different degrees. Therefore, achieving a balance between high volumetric capacitance and rapid ion transport has become a key issue for the application of MXene-based SCs in wearable devices and microdevices. In this paper, the latest progress in the preparation methods and modification strategies of MXenes in recent years is reviewed with the aim of achieving both high volumetric capacitance and high ion transport for expanding the application of MXene-based SCs in microdevices and wearable devices.

The development of high-performance electrode materials is typically constrained by capacity fading from irreversible structural evolution and restricted ion transport kinetics. To address these challenges, this study employs a synchronous stress-electrochemical reconstruction strategy to construct 3D copper selenide nanowires with ultrafast sodium ion transport capabilities. Experimental and theoretical analyses elucidate the synchronous evolution mechanism of CuSe2 transforming into Cu2Se nanowires under dual effects of pressure and electrochemical cycling. The synchronized growth of ultrahigh-aspect-ratio nanowires along the high-energy (111) crystal plane (0.329 nm spacing) provides abundant active sites for rapid sodium-ion insertion/extraction. Benefiting from the 3D networked architecture composed of ultrafine nanowires in monolithic electrodes, the composite effectively mitigates volume variations and selenide species loss. Consequently, the reconstruction electrode demonstrates exceptional rate capability (573.1 mAh g-1 at 0.2 A g-1 and 451.8 mAh g-1 at 50 A g-1) and outstanding cycling stability (581.9 mAh g-1 after 300 cycles at 0.2 A g-1). This in situ stress-electrochemical reconstruction strategy overcomes the physical limitations of conventional synthesis-assembly paradigms, achieving atomic-level coupling between active materials and current collectors, while offering a novel paradigm for developing adaptive electrode systems.

The development of Zn metal anodes is challenged by non-uniformity of ion flux causing inhomogeneous deposition and strong solvation of Zn(H2O)6 2+ resulting in adverse side reactions. Applying intermediate protecting layers with high affinity to Zn2+ is a popular and effective solution, but it also limits the ion migration. A functional MXene-based interlayer is designed in this work to modify the glass fiber separator achieving balanced adsorption energy and ion migration. By coating porous silica on the MXene surface, the instinct advanatges of MXene are mostly reserved while the adsorption energy to Zn2+ is optimized. Such an interlayer enables high flux and uniformity of desolvated Zn2+, contributing to rapid deposition kinetic for excellent rate performance and inhibited side reactions for long-term cycling stability. As a result, the functionalized Zn metal anode delivers steady plating/stripping cycles for more than 5000 h at 0.1 mA cm-2 and 700 h at 5.0 mA cm-2. The Zn||MnO2 full cells with this separator also exhibit superior rate capabilities (173 mAh g-1 at 2.0 A g-1) and excellent cycle performance (254.7 mAh g-1 after 1000 cycles at 0.5 A g-1). This work provides a feasible strategy for preparing functional interlayers toward superior Zn or other metal anodes.

Hard carbon is the most commercially viable anode material for sodium-ion batteries (SIBs), yet its application in ester-based electrolytes is hindered by sluggish interfacial ion diffusion and limited sodium nucleation kinetics. After comprehensive evaluation, an interfacial chemistry regulation strategy was proposed based on orbital hybridization between bismuth and electrolyte ions, which was realized through the introduction of ammonium bismuth citrate. The surface bismuth particles regulate the formation of a NaF-rich SEI through improved anion affinity. In collaboration with the in situ generated highly ion-conductive Na3N, a thin, compact and homogeneous SEI was constructed to enable fast and stable interfacial Na+ migration kinetics. Moreover, the Bi atoms can diffuse into the hard carbon structures, expanding the carbon interlayers to facilitate ion diffusion and intercalation as well as enhancing the sodiophilicity in closed pores to lower the nucleation barrier. Benefiting from these merits, the resulting T2-BiN exhibits superior sodium-storage kinetics with outstanding rate capability (185.6 mA h g-1 at 0.5 A g-1) and long-term cycling stability (84.4% after 400 cycles at 0.5 A g-1) in the ester-based electrolyte. Even the practical full cell showed no capacity decay over 400 cycles at 2C. This work provides a simple and effective interfacial modification strategy, offering new insights into the advancement of hard carbon anodes for high-performance SIBs.

Interfacial challenges, including unstable electrode/electrolyte interfaces and sluggish ion transport, remain critical barriers to the deployment of solid polymer electrolytes (SPEs) in high-energy-density lithium metal batteries. However, the formation of a desired LiF/Li3N-rich solid-electrolyte interphase (SEI) remains challenging due to the presence of anion-depletion layer and the high reduction barrier of sulfonyl-imide moieties in conventional FSI-/TFSI- anions. Herein, benzamide was employed to functionalize the kaolinite in PEO-based SPEs. The high dipole moment of benzamide anchors TFSI- anions via its -NH2 groups, resulting in an enhanced Li+ transference number of 0.69 and a room-temperature ionic conductivity of 1.4 x 10-4 S cm- 1. This interaction also enriches anions at the anode/SPE interface, promoting the generation of LiF. Simultaneously, the electrophilic -NH2 groups facilitate the in-situ generation of Li3N. The resultant conformal, highly Li+-conductive LiF/Li3N-rich SEI layer accelerates Li deposition kinetics and effectively suppresses dendrite growth, enabling highly stable lithium plating/stripping for over 2400 h. Full cells employing LFP and NCM811 cathodes maintain outstanding cycling stability over 500 and 200 cycles, respectively. Moreover, pouch cells show excellent mechanical robustness and safety under deformation and abuse conditions, underscoring the exceptional promise of this functionalized SPE for safe and durable all-solid-state lithium metal batteries.

Intercalation pseudocapacitance is the key point to achieving the balance between the volumetric capacitance and the rate performance of energy storage. However, the low pseudocapacitive reactivity of the active center still limits the energy density of the pseudocapacitance devices. Herein, we propose a strategy that regulates the p-d hybridization of confined MXene via the co-doping of B and O atoms (BO-MXene) for outstanding electrochemical performance. Both experiments and density functional theory (DFT) reveal that the inner doped O atoms in low 2p orbital energy strengthen the hybridization of Ti and electron-deficient B in MXene for high retention of B atoms, weaken the Ti-O covalency in MXene. As a result, the weakened p-d hybridization of Ti and O for the outer surface and strengthened p-d hybridization of Ti and B for the inner, promote the adsorption of protons and electron transfer, respectively. Further, the BO-MXene-based hybrid supercapacitors achieve a significant volumetric energy density of 56.86 Wh L-1 at 25.6 kW L-1. This electronic structure via tuning the p-d hybridization in MXene proposes a new path for designing proton-confined intercalation pseudocapacitance.

It is of great significance to stabilize catalytic active sites and study the coupling mechanism between catalyst construction and performance. In this work, [NCN](2-) anions are introduced into [Bi2O2](2+) interlayer to prepare two-dimensional (2D) Bi2O2NCN nanosheets via in-situ topotactic transformation. Experimental results show that strong electronegativity and ingenious structural transformation of [NCN](2-) can effectively avoid the destruction and self-reduction of highly active bismuth-oxygen (Bi-O) structures as well as regulate the micro-environment around active sites, which is beneficial for adsorption and activation of CO2 to formate. The Bi2O2NCN exhibits outstanding activity and stability during the electrocatalytic CO2 reduction (ECR) process for 20 h with a stable current density of similar to 100 mA center dot cm(-2) and formate faradaic efficiency (FEformate) similar to 90 %. This work investigates the effect of ion coordination on suppressing Bi-based electrocatalyst from self-reduction and modulating the local microenvironment, which provides an ingenious approach for optimizing catalyst structure and enhancing ECR performance.