Precisely tailoring metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) with high catalytic activity and selectivity for specific chemical reactions remains challenging due to the lack of a qualitative descriptor between their catalytic properties and coordination geometries. Herein, we bridge this gap by integrating density functional theory (DFT) calculations with machine learning (ML) algorithms to deconvolute the electrocatalytic oxygen reduction reaction (ORR) activity of M-N-C SACs across various possible coordination configurations. By correlating the theoretical overpotentials with structural features, an interpretable descriptor simultaneously reflecting the coordination number and the metal-support interaction is identified. This descriptor not only reliably describes the ORR performance trends across diverse metal centers in SACs but also provides a general guideline for engineering coordination geometry to optimize catalytic performance. Guided by these insights, the predicted Cu-SAC featuring low-coordinated Cu-N3 moieties is synthesized, delivering remarkable ORR activity compared with the conventional Cu-N4 sites while maintaining robust structural stability under prolonged electrochemical operation. This study highlights the exceptional potential of interpretable ML combined with theoretical and experimental strategies in elucidating complex structure-property relationships in SACs and accelerating the development of next-generation electrocatalysts for sustainable and efficient energy conversion.

The stable operation of lithium metal batteries (LMBs) requires simultaneous stabilization of anode and cathode interfaces, a challenge that intensifies under extreme operating conditions due to divergent formation mechanisms. Here, we present a hybrid-solvation electrolyte design employing isobutyronitrile (IBN) as the primary solvent to regulate both Li+ solvation and interfacial protection. Functioning as a bifunctional modulator, IBN drives dual-source interfacial chemistry at the anode where anion-enriched solvation and coordinated-solvent decomposition co-generate an inorganic- and nitrogen-rich solid-electrolyte interphase (SEI) while lowering Li+ desolvation barriers. At the cathode surface, excess IBN molecules form an adsorption-derived protective layer that effectively suppresses solvent oxidation and stabilizes the cathode-electrolyte interface (CEI) under high-voltage and high-temperature conditions. Enabled by this design, Li||LiNi0.8Co0.1Mn0.1O2 coin cells exhibit robust operation across wide temperatures (-40°C∼60°C) and high voltages (4.6 V), alongside ultrafast charging capabilities (20 C). Upscaling to practical pouch cells under lean-electrolyte conditions (1.2 g Ah-1) yields a high energy density of 403 Wh kg-1 with a 12-min fast-charging/discharging capability. The hybrid solvation design framework integrates solvent- and anion-driven chemistries in a unified electrolyte, enabling high-energy LMB operation under demanding conditions.

Intelligent thermal management is essential for battery safety in sustainable development. Herein, we incorporate the "intelligence" property into aqueous zinc-ion batteries (AZIBs) by introducing a thermo-responsive graphene oxide/hydroxypropyl cellulose (GO/HPC) composite membrane as a smart thermal protection component. The as-prepared membrane demonstrates exceptional flexibility and mechanical robustness, with a Young's modulus of 3.3 GPa. Taking advantage of the reversible lower critical solution temperature (LCST)-driven phase transition of HPC, the membrane undergoes autonomous shrinkage and ionic shutdown when the ambient temperature reaches 65 degrees C-triggering an immediate self-protective state to suppress thermal runaway in AZIBs. Mechanistically, the conformational transition of HPC (from hydrophilic extended chains to hydrophobic globules) upon heating simultaneously blocks Zn2+ transport and water permeation across the membrane, while the amphiphilic GO surface guides the ordering of liquid crystalline HPC domains to optimize this dual-functional switching behavior. Notably, AZIBs integrated with this intelligent membrane retain 92% and 80% of their initial capacity after a single thermal shutdown-cooling cycle and after 15 repeated shutdown-recovery cycles, respectively, confirming the reversibility of the membrane's thermo-responsive behavior. This work provides a rational material design paradigm for the safety of AZIBs, facilitating their use in practical applications from consumer electronics to large-scale grid energy storage.

Catalysts capable of actively switching between distinct reaction pathways represent a paradigm shift in chemical synthesis. Here, we demonstrate a Thermo-Gated Activation phenomenon, which can be achieved by thermally activated escape of hot electrons. We establish that the Pt/TiO2 catalyst interface is kinetically trapped in a deep metastable potential well at low temperatures, blocking a potent plasmon-driven pathway. Above a critical temperature of 170 degrees C, the interface collectively escapes this well by overcoming a macroscopic activation barrier, a direct manifestation of a cooperative phase transition at the catalyst interface driven by thermal fluctuations. This escape event constructs a new, highly entropic dynamic interface that unlocks the pathway for hot-electron injection, redirecting the reaction to a highly efficient decarbonylation route with a remarkable H2 rate of 3137 mol gPt-1 h-1. This work establishes a principle of Thermo-Gated Activation, which triggers a non-equilibrium charge transfer process as a novel blueprint for designing "smart" catalysts.

Na4MnCr(PO4)3 (NMCP) and Na2VTi(PO4)3 (NVTP) are promising binary electrode materials for sodium-ion batteries (SIBs) due to their high theoretical specific capacity and high voltage redox potential associated with V/Mn redox couples. However, the Jahn–Teller distortion induced by Mn3+ in NMCP and inactive V4+/V5+ in NVTP lead to inadequate rate capability and cyclic instability, rendering their utilization impractical. To overcome these intrinsic bottlenecks, we rationally designed and synthesized homogeneous solid-solution medium-entropy Na3.0V0.5Mn0.5Ti0.5Cr0.5(PO4)3 (NVMTCP) NASICON. The synergetic effect of medium-entropy modulation and charge redistribution around the TM–O6 bond at the octahedral site enhances intrinsic lattice stability and electronic conductivity. Consequently, it stabilizes and activates reversible V3+/V4+/V5+ and Mn2+/Mn3+/Mn4+ redox couples. NVMTCP exhibits a high specific capacity of 175.3 mA h g−1 and excellent cyclic stability with 91% capacity retention after 5000 cycles at 2 A g−1. Comprehensive X-ray analysis and theoretical calculations demonstrate shorter and stronger TM–O6 bonding, which facilitates faster electronic kinetics, enabling a smooth phase transition and mitigating the biphasic reaction with a small volume change of 5.3% during sodiation–desodiation. The proposed strategy could be applied to design low-cost, ultra-stable, and high-performance NASICON electrode materials for the commercialization of SIBs.

The exploration on weak-light-driven catalysis is an important approach to reduce the dependence of photocatalysts on strong light and improve the efficiency of solar spectrum utilization. However, the reported photocatalysts typically necessitate high light intensity (e.g., exceeding 100 mW cm(-2)) for catalytic reactions, which cannot be achieved with natural solar light. Herein, a self-sensitization-induced strategy was employed to generate in-situ proton sites, enabling photocatalytic hydrogen evolution reaction (HER) even under low light intensity (10 mW cm(-2)). An indolocarbazole ligand (H2ICDB) was utilized to construct a paddle-wheel dicopper coordination polymer (CuICDB-DMF). By substituting the axially coordinated DMF with methanol or water, CuICDB-MeOH and CuICDB-H2O were obtained. Under weak-light irradiation (10 mW cm(-2)), CuICDB-H2O exhibited the highest photocatalytic HER rate of 838.4 mu mol g(-1) h(-1) when compared to the other two counterparts. Remarkably, the substitution of axially coordinated H2O promotes charge separation and transfer efficiency through optimizing ligand-to-cluster charge transfer (LCCT) process. Moreover, density functional theory (DFT) calculations reveal that coordinated H2O substitution decreases the Gibbs free energy difference of the potential determining step (H2O* -> OH* + H*) in CuICDB-H2O.

P2-type Na0.67MnO2 cathode material has attracted significant attention due to its high specific capacity, and abundant sodium resources for practical sodium-ion batteries (SIBs). However, the complex phase transitions of this material in the charge/discharge processes could lead to rapid voltage/capacity decay, limiting its practical applications. In this study, to suppress this phase transition, stabilize the structure, and regulate Mn ion activity, we use a sol-gel method to dope Fe ions into these materials by partially replacing Mn, resulting in a series of Fedoped P2-type Na0.67MnO2 cathode materials (Na0.67Mn(1-x/6)Fex/6O2 (x = 0, 1, 2, 3, 4). According to our theoretical calculations and experimental optimization experiments, the introduction of Fe ions could stabilize the material structure and reduce the energy barrier for Na+ ion mass transport. As a result, the doped cathode materials (x = 1, 2, 3, 4) exhibit significantly better performance than the pristine Na0.67MnO2 cathode (x = 0). Among the Fe-doped cathode materials (with x = 1, 2, 3, 4), Na0.67Mn0.5Fe0.5O2 (x = 3) delivers the best cycle performance, high-rate capability, and stability, e.g., discharge capacity of 114.7 mAh g- 1 and 79.1 mAh g- 1 at 1.0C and 5.0C respectively, and retains 91.1 % capacity after 200 cycles at 1.0C. This work provides both theoretical insights and practical strategies for designing and fabricating cathode materials for low-cost, robust, and high-performance SIBs.

Dry electrode technology (DET) presents a transformative alternative to conventional slurry‐based fabrication for lithium‐ion batteries (LIBs), offering a solvent‐free route that resolves critical environmental and manufacturing challenges. By eliminating toxic organic solvents and energy‐intensive drying steps, DET substantially simplifies the fabrication process while reducing energy consumption and production costs. Critically, this technology enables the fabrication of thick, compact, and uniform electrodes, which is essential for boosting energy density and exceptionally compatible with the manufacturing of solid‐state batteries. This review critically examines the fundamental solvent‐free bonding mechanisms that serve as the foundation for microstructural control in DET. Two of the most promising and industrially relevant methodologies are focused: Dry powder spray coating technology that involves thermoplastic binders (e.g., polyvinylidene fluoride (PVDF)), and shear‐induced polymer fibrillation coating technology that uses fibrillable polymers (e.g., polytetrafluoroethylene (PTFE)). The distinct bonding mechanisms, processing principles, and resulting microstructural characteristics of these techniques are discussed in depth, illustrating strategies for engineering optimized electrode architectures. Finally, recent advances are showcased in applying DET to high‐mass‐loading electrodes, fast‐charging cells, and solid‐state battery configurations, and identify critical directions for future research and scale‐up efforts to accelerate the industrial adoption of this sustainable manufacturing paradigm.

We demonstrate in-situ image encryption based on alpha-In2Se3/Bi2O2Se heterostructure ferroelectric phototransistors (FePTs) that integrate photosensing, memory, and encryption functionalities at the edge-sensor level. Our FePT heterojunction executes multiple encryptions via ferroelectric and photoelectric polarizations, benefiting from the unique ferroelectric-semiconducting features of both alpha-In2Se3 and Bi2O2Se. More particularly, the self-oxidation of Bi2O2Se to beta-Bi2SeO5 forms the lattice-matched dielectric interlayer that facilitates the ferroelectric coupling of alpha-In2Se3/Bi2O2Se heterostructure, leading to the remarkable ferroelectric polarization window of 5.6 V, programmable conductance states of 128, and endurance cycles of 104 for ferroelectric semiconductors. And the anisotropic photoresponse yields an ultrahigh polarization ratio of 3400%. By exploiting these features, we manufacture an in-sensor encryption system with an exceptional key space of N-128 (i.e., N is pixel), reaching an ultralow ciphertext correlation coefficient of 1% and decryption accuracy of 98% in a 100x100-pixel FePT array via single-round key exchange. Our work bridges the gap between secure encryption and efficient computation of edge sensing.

Conventional binders, commonly involving mechanical interlocking force and molecular interaction bonding, could not thoroughly address substantial volumetric expansion and subsequent rapid capacity degradation of silicon anodes during cycling, limiting large-scale commercial application of high-energy-density of Si-based anodes. Herein, we propose a new binding mechanism, i.e., conformational change induced by silk fibroin (SF) to address these issues. Triggered by polyacrylic acid (PAA), SF undergoes a conformational change from an amorphous phase to beta-sheet-rich structure and constructs a hierarchically ordered framework PAA-SF, which provides excellent mechanical strength through the formation of densely packed structures. Additionally, the unique beta-sheet-rich structure of the PAA-SF binder could facilitate lithium-ion diffusion via coordination bonds with lithium ions. Consequently, the PAA-SF binder effectively mitigates stress from the volume expansion, enhances the rate capability, and constructs a stable SEI layer, thereby extending the cycling stability of silicon anodes. The cells with this binder can sustain a high reversible capacity of 600 mAh g- 1 after 1100 cycles at 4.2 A g-1. The concept of a conformational change-based binding mechanism opens a promising avenue for the commercialization of silicon and other silicon-carbon anodes.

Layered transition metal dichalcogenides (LTMDs), such as MoS2, are promising anode materials for high-energy-density lithium-ion batteries (LIBs) due to their high specific capacities. However, their practical applications are hindered by poor cycling stability resulting from the instable structure during charge/discharge and inherently low electronic conductivity. To tackle these issues, herein, this study presents the design and synthesis of spongy silicon-doped MoS2 induced by the long-chain molecules in mesopores. The material consists of few-layered nanofragments with high porosity, resulting in abundant edge sites and sulfur vacancies. These structural features can promote Li+ transport and accommodate electrode volume changes during charge/discharge. Electrochemical and theoretical analyses reveal that silicon doping enhances the electronic conductivity of MoS2, while the nanostructure design enables reversible Li+ diffusion along the edges, distinct from Li+ storage in the interlayers of conventional MoS2 anodes. Notably, the material delivers a high reversible capacity of 767.9 mAh g-1 at 0.1 A g-1 and exhibits remarkable rate capability. Moreover, it demonstrates superior cycling stability with over 83% capacity retention even after 1000 cycles at 1.0 A g-1, outperforming most existing MoS2-based anode materials. This work paves a new way for designing high-performance LTMD-based anodes for LIBs and beyond.

All-solid-state lithium-ion batteries (ASSLIBs) based on sulfide solid-state electrolytes (S-SSEs) are considered as one of the most promising choices to address the safety hazards of traditional lithium-ion batteries. However, the high-voltage cathodes, such as LiCoO2 (LCO) with high-valence Co (+3), tend to spontaneously oxidize S-SSEs, causing polarization increase and rapid degradation. Herein, a self-sacrificing reductive interphase consisting of CoO/Li2CO3/C, is in situ constructed on LCO surface via a simple carbon-induced thermal reduction of LCO. With such a design, the Co valence of LCO surface is reduced to +2, reducing the oxidative nature of LCO to avoid reactions with S-SSEs. As a result, ASSLIBs using Li10GeP2S12 (LGPS) S-SSEs achieve a high initial capacity of 144.9 mAh g-1 at 0.2 C and retard 93.1% of initial capacity after 100 cycles. Additionally, excellent rate cyclability of 109.2 mAh g-1 at 1.0 C with 81.5% retentive capacity for 200 cycles is attained as well. Comprehensive evidence strongly demonstrates the effectiveness of this self-sacrificing reductive interphase in inhibiting the interfacial reactions and ensuring long-term cyclability. The proposed concept of a self-sacrificing reductive interface in this study paves the way for stabilizing the cathode/SSEs interface and offers a novel approach for the design of high-performance sulfide-based ASSLIBs. The notion of interface reconstruction through self-sacrificial reduction is proposed. Citric acid is employed as reducing agent for the thermal reduction of LCO, facilitating the generation of an in situ coating on the surface of LCO. This coating is devised to impede the interface reaction, establish stability within the LCO/LGPS interface, and enhance the long-term cycling potential of all-solid-state batteries.image

Due to the seamless interfaces between solid polymer electrolytes (SPEs) and electrode materials, SPEs-based all-solid-state sodium-ion batteries (ASSSIBs) are considered promising energy storage systems. However, the sluggish Na + transport and uncontrollable Na dendrite propagation still hinder the practical application of SPEs-based ASSSIBs. Herein, Ca-doped CeO 2 (Ca−CeO 2 ) nanotube framework is synthesized and integrated with poly (ethylene oxide) methyl ether acrylate-perfluoropolyether copolymer (PEOA-PFPE), resulting in multifunctional solid nanocomposite electrolytes (namely SNEs, i.e., PEOA-PFPE/Ca−CeO 2 ). Our investigations demonstrate that the fluorous effect incurred by the fluorine-containing PEOA-PFPE and the oxygen vacancy effect induced by the Ca−CeO 2 framework could synergistically promote the dissociation of sodium salt, ultimately enhancing the Na + mobility in SNEs. Besides, the resultant SNEs construct rapid Na + transport channels and homogenize the Na deposition in SNEs/Na interface, which effectively prevents the Na dendrite growth. Furthermore, the assembled carbon-coated sodium vanadium phosphate (NVP@C)||PEOA-PFPE/Ca−CeO 2 ||Na coin cell delivers impressive rate capability of 97.9 mAh g −1 at 2 C and outstanding cycling stability with capacity retention of 84.3 % after 300 cycles at 1 C. This work illustrates that constructing multifunctional SNEs via incorporating functional inorganic frameworks into fluorine-containing SPEs could be a promising strategy for the commercialization of robust and high-performance ASSSIBs.

The development of high-density and closely spaced frustrated Lewis pairs (FLPs) is crucial for enhancing catalyst activity and accelerating reaction rates. However, constructing efficient FLPs by breaking classical Lewis bonds poses a significant challenge. Here, this work has made a pivotal discovery regarding the Jahn-Teller effect during the formation of grain boundaries in carbon-encapsulated Ni/NiOx (Ni/NiOx@C). This effect facilitates the formation of high-density O (VO) and Ni (VNi) vacancy sites with different charge polarities, specifically FLP-VO-C basic sites and FLP-VNi-C acidic sites. The synergistic interaction between FLP-VO-C and FLP-VNi-C sites not only reduces energy barriers for water adsorption and splitting, but also induces a strong photothermal effect. This mutually reinforcing effect contributes to the exceptional performance of Ni/NiOx@C as a cocatalyst in photothermal-assisted photocatalytic hydrogen production. Notably, the Ni/NiOx@C/g-C3N4 (NOCC) composite photocatalyst exhibits remarkable hydrogen production activity with a rate of 10.7 mmol g-1 h-1, surpassing that of the Pt cocatalyst by 1.76 times. Moreover, the NOCC achieves an impressive apparent quantum yield of 40.78% at a wavelength of 380 nm. This work paves the way for designing novel defect-state multiphase cocatalysts with high-density and adjacent FLP sites, which hold promise for enhancing various catalytic reactions.

Lithium–sulfur batteries (LSBs) currently suffer from severe polysulfide shuttling, slow redox kinetics at the sulfur cathode, and irreversible dendrite growth at the lithium anode. To address these issues, a dual interfacial engineering strategy on both the cathode and anode is proposed. For the cathode, iminated polyaniline (iPANI) is used to achieve energetic engineering to induce mid‐energy level to the adsorption of polysulfides, and catalyze the redox conversion of sulfur species, and realize morphological engineering via self‐assembly of iPANI onto a scaffold integrated by reduced graphene oxide (rGO) and carbon nanotubes (CNTs), namely iPANI@rGO‐CNTs. For the anode, the highly conductive and lithiophilic nature and porous nanostructure of the iPANI@rGO‐CNTs composite facilitates the uniform deposition of lithium‐ions, significantly preventing the growth of lithium dendrites. Density functional theory calculations suggest that the iminated functional group at the excited state in iPANI can significantly suppress the shuttling effect, catalyze the conversion of sulfur species, and enhance the conversion of the sulfur species on the sulfur cathode. With the synergic effects of the iPANI@rGO‐CNTs nanoreactors, the as‐prepared LSBs deliver an excellent rate capability and outstanding cycling life. This large‐scale production and application of the iPANI@rGO‐CNTs nanocomposite may lead to the eventual commercialization of LSBs.

Cocatalyst engineering with non‐noble metal nanomaterials can play a vital role in low‐cost, sustainable, and large‐scale photocatalytic hydrogen production. This research adopts slow carburization and simultaneous hydrocarbon reduction to synthesize carbon‐encapsulated Mo/Mo2C heterostructure nanoparticles, namely Mo/Mo2C@C cocatalyst. Experimental and theoretical investigations indicate that the Mo/Mo2C@C cocatalysts have a nearly ideal hydrogen‐adsorption free energy (ΔGH*), which results in the accelerated HER kinetics. As such, the cocatalysts are immobilized onto organic polymer semiconductor g‐C3N4 and inorganic semiconductor CdS, resulting in Mo/Mo2C@C/g‐C3N4 and Mo/Mo2C@C/CdS catalysts, respectively. In photocatalytic hydrogen evolution application under visible light, the Mo/Mo2C@C with g‐C3N4 and CdS can form the Schottky junctions via appropriate band alignment, greatly suppressing the recombination of photoinduced electron‐hole pairs. The surface carbon layer as the conducting scaffolds and Mo metal facilitates electron transfer and electron‐hole separation, favoring structural stability and offering more reaction sites and interfaces as electron mediators. As a result, these catalysts exhibit high H2 production rates of 2.7 mmol h−1 g−1 in basic solution and 98.2 mmol h−1 g−1 in acidic solution, respectively, which is significantly higher than that of the bench‐mark Pt‐containing catalyst. The proposed cocatalyst engineering approach is promising in developing efficient non‐noble metal cocatalysts for rapid hydrogen production.

Organic electrode materials (OEMs), valued for their sustainability and structural tunability, have been attracting increasing attention for wide application in sodium-ion batteries (SIBs) and other rechargeable batteries. However, most OEMs are plagued with insufficient specific capacity or poor cycling stability. Therefore, it′s imperative to enhance their specific capacity and cycling stability through molecular design. Herein, we designed and synthesized a heteroaromatic molecule 2,3,8,9,14,15-hexanol hexaazatrinaphthalene (HATN-6OH) by the synergetic coupling of catechol (the precursor of ortho -quinone)/ ortho -quinone functional groups and HATN conjugated core structures. The abundance of catechol/ ortho -quinone and imine redox-active moieties delivers a high specific capacity of nine-electron transfer for SIBs. Most notably, the π–π interactions and intermolecular hydrogen bond forces among HATN-6OH molecules secure the stable long-term cycling performance of SIBs. Consequently, the as-prepared HATN-6OH electrode exhibited a high specific capacity (554 mAh g −1 at 0.1 A g −1 ), excellent rate capability (202 mAh g −1 at 10 A g −1 ), and stable long-term cycling performance (73 % after 3000 cycles at 10 A g −1 ) in SIBs. Additionally, the nine-electron transfer mechanism is confirmed by systematic density functional theory (DFT) calculation, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and Raman analysis. The achievement of the synergetic coupling of the redox-active sites on OEMs could be an important key to the enhancement of SIBs and other metal-ion batteries.

The research and development of potassium ion battery (KIB) is still currently at infancy stage due to the lack of materials that facilitate rapid K+ transport and subsequently deliver high energy capacity and power density. Our Density Functional Theory (DFT) calculations suggest that the high potassium adsorption energy (3.01 eV) on 1D-C3N4, a lower potassium diffusion barrier and the superior electronic conductivity of graphene will be beneficial for the intercalation of K+. In this work, a 1D/2D C3N4/reduced graphene oxide (rGO) composite was designed and synthesized as an anode material to address these needs via a hydrothermal/freeze drying method. As a host for K+ ions, the as prepared composite delivered a remarkable specific capacity of 464.9 mAh/g after 200 cycles at 1 A/g and 228.6 mAh/g after 1000 cycles a 10 A/g, which is one of the best reported so far. The exceptional performance of this composite can be attributed to the large surface area for additional active sites, shorter K+ diffusion distance, structural stability and the synergistic interaction between 1D C(3)N4 and 2D rGO. This work broadens the design and application of composites and fosters the advancement in potassium ion battery research.

Defect engineering involves the manipulation of the type, concentration, mobility or spatial distribution of defects within crystalline structures and can play a pivotal role in transition metal oxides in terms of optimizing electronic structure, conductivity, surface properties and mass ion transport behaviors. And of the various transition metal oxides, titanium-based oxides have been keenly investigated due to their extensive application in electrochemical storage devices in which the atomic-scale modification of titanium-based oxides involving defect engineering has become increasingly sophisticated in recent years through the manipulation of the type, concentration, spatial distribution and mobility of defects. As a result, this review will present recent advancements in defect-engineered titanium-based oxides, including defect formation mechanisms, fabrication strategies, characterization techniques, density functional theory calculations and applications in energy conversion and storage devices. In addition, this review will highlight trends and challenges to guide the future research into more efficient electrochemical storage devices.Graphic AbstractThis work reviews the recent advances in defect-engineered Ti-based oxides, including the mechanism of defect formation, fabrication strategies, the characterization techniques, density functional theory calculations and the applications in energy conversion and storage.

Sodium-based layered oxides are among the leading cathode candidates for sodium-ion batteries, toward potential grid energy storage, having large specific capacity, good ionic conductivity, and feasible synthesis. Despite their excellent prospects, the performance of layered intercalation materials is affected by both a phase transition induced by the gliding of the transition metal slabs and air-exposure degradation within the Na layers. Here, this problem is significantly mitigated by selecting two ions with very different MO bond energies to construct a highly ordered Ni6 -ring superstructure within the transition metal layers in a model compound (NaNi2/3 Sb1/3 O2 ). By virtue of substitution of 1/3 nickel with antimony in NaNiO2 , the existence of these ordered Ni6 -rings with super-exchange interaction to form a symmetric atomic configuration and degenerate electronic orbital in layered oxides can not only largely enhance their air stability and thermal stability, but also increase the redox potential and simplify the phase-transition process during battery cycling. The findings reveal that the ordered Ni6 -ring superstructure is beneficial for constructing highly stable layered cathodes and calls for new paradigms for better design of layered materials.