Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typical...Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typically evaluated by a dimensionless figure of merit (ZT = S2σT/(κe+ κl)), which depends on the delicate interplay among the electrical conductivity (σ), Seebeck coefficient (S), lattice thermal conductivity (κl), and electronic thermal conductivity (κe) [4].展开更多
As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode mate...As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode materials undergo complex ion intercalation and deintercalation processes,accompanied by defect formation and structural evolution.However,the microscopic mechanisms underlying processes such as cation disordering,lattice oxygen loss,and stage structure formation are still not fully understood.To address these challenges,we have developed the Electrode Dynamic Ion Intercalation/Deintercalation Simulator(EDIS),a software platform designed to simulate the dynamic processes of ion intercalation and deintercalation in electrode materials.Leveraging high-precision machine learning potentials,EDIS can efficiently model structural evolution and lithium-ion diffusion behavior under various states of charge and discharge,achieving accuracy approaching that of quantum mechanical methods in relevant chemical spaces.The software supports quantitative analysis of how variations in lithium-ion concentration and distribution affect lithium-ion transport properties,enables evaluation of the impact of structural defects,and allows for tracking of both structural evolution and transport characteristics during continuous cycling.EDIS is versatile and can be extended to sodium-ion batteries and related systems.By enabling in-depth analysis of these microscopic processes,EDIS provides a robust theoretical tool for mechanistic studies and the rational design of high-performance electrode materials for next-generation lithium-ion batteries.展开更多
Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible s...Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.展开更多
Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge t...Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge towards efficient DCBs.Here,we introduce a heteroatom-doped sp^(3) /sp^(2) hybridized carbon fiber membrane(cPAN-Gr)as a universal binder-free active electrode that effectively overcomes this trade-off,enabling efficient Li-ion intercalation chemistry for advanced DCBs.By strategically tuning the sp^(3) and sp^(2) carbon hybridization,the interlayer interaction,geometric and electronic structures of c PANGr are simultaneously optimized,which facilitates rapid Li-ion adsorption,smooth interlayer transport,and efficient electron transport by maximizing the synergy between sp^(2) -and sp^(3) -hybridized carbon.This,coupled with a 3D porous network structure,endows the c PAN-Gr with superior Li-ion storage capability and fast reaction kinetics.Therefore,the c PAN-Gr electrode delivers a high reversible capacity of 345 m A h g^(-1),excellent rate capability(50 C),and an ultralong cycle life over 10,000 cycles,outperforming other reported carbon-based electrodes.Moreover,the constructed DCB exhibits a large specific capacity of 135 m A h g^(-1),long-term cyclability over 500 cycles,and a remarkable energy density of 524.4 Wh kg^(-1).The c PAN-Gr electrode can also be expanded to construct a LiFePO_(4)//cPAN-Gr full battery.Combined theoretical and experimental studies reveal the crucial role of an optimized sp^(3) /sp^(2) ratio(79%)with topological defects and pyridine/pyrrolic N sites on the performance enhancement.This work offers new insights into the design of advanced carbon materials for DCBs and beyond.展开更多
V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve th...V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.展开更多
Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalyti...Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an imp...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.展开更多
Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chlori...Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.展开更多
The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries(AZIBs).Although the conventional ion doping method mitigates the intrinsically slug...The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries(AZIBs).Although the conventional ion doping method mitigates the intrinsically sluggish kinetics,it exacerbates the erosion of Zn^(2+)/H^(+)and free water within the lattice structure,leading to inferior structural stability and capacity fading.Herein,a synchronous dual-modification strategy is introduced to improve the electrochemical performance of the V_(6)O_(13)cathode through an ingenious hydrolysis process involving K_(2)Cr_(2)O_(7).Experimental and calculated results demonstrate that the coating layer formed by chromium oxide supports the structural firmness and strengthens the interfacial chemistry,based on increased electrochemical activity by K^(+)intercalation.Consequently,the optimized sample delivers a capacity of 418 mAh g^(-1)at 0.1 A g^(-1),and excellent cyclic stability of 205 mAh g^(-1)after 6000 cycles at 10 A g^(-1).It is fully charged at a small current of 0.5 A g^(-1)to maintain a reversible capacity of 346 mAh g^(-1)after 72 h in an open circuit state,and there is no obvious capacity decay,highlighting the crucial protective effect of the inactive coating layer.This work presents a straightforward and reliable approach to effectively harmonize the relationship between activity and structural stability for advanced AZIBs cathode.展开更多
Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In...Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.展开更多
Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performa...Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.展开更多
MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties en...MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.展开更多
We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an...We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.展开更多
Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The met...Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.展开更多
Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabl...Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.展开更多
Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transpo...Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transport in topological devices.The presence of these carriers in real materials strongly depends on the Fermi-level position.2M-WSe_(2),with its topological and van der Waals nature,serves as an ideal platform for studying quantum transport in two-dimensional systems,despite the fact that interlayer coupling suppresses the formation of light carriers.In this study,we solvothermally intercalate 1,3-diaminopropane molecules into the interlayer space of 2M-WSe_(2);these molecules effectively adapt to the electronic structure by eliminating interlayer coupling.Simultaneously,slight electron doping via charge transfer results in a small Fermi pocket with an extremely light effective mass,0.04–0.06 me,as revealed by quantum oscillation measurements.This study demonstrates that molecular intercalation is an effective approach for engineering van der Waals topological materials to achieve specific quantum transport properties.展开更多
Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pell...Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pellets.Addressing the gap in the application of organically-intercalated modified bentonite in the pelletizing field,this study introduces an innovative modification process for bentonite that employs the synergistic effect of mechanical force and dimethyl sulfoxide to enhance the intercalation of organic compounds within bentonite,thus significantly enhancing its binding performance.The colloid value and swell capacity of modified bentonite(98.5 m L/3g and 55.0 m L/g)were much higher than the original bentonite(90.5 m L/3g and 17.5 m L/g).With the decrease of bentonite dosage from1.5wt%to 1.0wt%,the drop number of green pellets from a height of 0.5 m and the compressive strengths of roasted pellets using the modified bentonite(6.0 times and 2916 N per pellet)were significantly higher than those of the original bentonite(4.0 times and 2739 N per pellet).This study provides a comprehensive analysis of the intercalation modification mechanism of bentonite,offering crucial technical insights for the development of high-performance modified bentonite as iron ore pellet binders.展开更多
Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herei...Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herein,we engineer tetraethylammonium(TEA)cation intercalation as a dual-function strategy that concurrently enables interlayer distance enlargement and electrostatic shielding effects,resolving Al^(3+) polarization-induced sluggish kinetics and cathode degradation in RABs.TEA intercalation triggers exceptional V2O5 interlayer expansion from 4.37 to 13.10Å,while the modulated charge distribution generates an electrostatic shielding effect that significantly weakens the Coulombic interactions between Al^(3+) and V2O5 frameworks.This dual mechanism collectively enhances ion diffusion kinetics and suppresses lattice stress accumulation.Ex situ X-ray diffraction and transmission electron microscopy analyses confirm that the“molecular pillar effect”of TEA enables minimal and highly reversible structural deformation of the cathode(<2.0%volume change after 200 cycles),demonstrating zero-strain aluminum-storage behavior.The optimized cathode delivers a high reversible capacity of 258 mAh g^(−1) at 0.5 A g^(−1),maintains 99%capacity retention at 5.0 A g^(−1),and exhibits an ultralow capacity decay rate of 0.01%per cycle over 6000 cycles.This work opens new pathways for designing stable high-performance RAB cathodes through synergistic modulation of electronic and lattice structures.展开更多
基金supports from the Department of Education of Liaoning Province (LJ242510147006)
文摘Thermoelectric (TE) materials enable precise, noiseless, and moving-part-free waste heat recovery and solid-state refrigeration through the Seebeck and Peltier effects [1–3]. The efficiency of TE materials is typically evaluated by a dimensionless figure of merit (ZT = S2σT/(κe+ κl)), which depends on the delicate interplay among the electrical conductivity (σ), Seebeck coefficient (S), lattice thermal conductivity (κl), and electronic thermal conductivity (κe) [4].
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences(Grant No.XDB1040300)the National Natural Science Foundation of China(Grant No.52172258)。
文摘As the core determinant of lithium-ion battery performance,electrode materials play a crucial role in defining the battery's capacity,cycling stability,and durability.During charging and discharging,electrode materials undergo complex ion intercalation and deintercalation processes,accompanied by defect formation and structural evolution.However,the microscopic mechanisms underlying processes such as cation disordering,lattice oxygen loss,and stage structure formation are still not fully understood.To address these challenges,we have developed the Electrode Dynamic Ion Intercalation/Deintercalation Simulator(EDIS),a software platform designed to simulate the dynamic processes of ion intercalation and deintercalation in electrode materials.Leveraging high-precision machine learning potentials,EDIS can efficiently model structural evolution and lithium-ion diffusion behavior under various states of charge and discharge,achieving accuracy approaching that of quantum mechanical methods in relevant chemical spaces.The software supports quantitative analysis of how variations in lithium-ion concentration and distribution affect lithium-ion transport properties,enables evaluation of the impact of structural defects,and allows for tracking of both structural evolution and transport characteristics during continuous cycling.EDIS is versatile and can be extended to sodium-ion batteries and related systems.By enabling in-depth analysis of these microscopic processes,EDIS provides a robust theoretical tool for mechanistic studies and the rational design of high-performance electrode materials for next-generation lithium-ion batteries.
基金financially supported by the supported by Shandong Provincial Natural Science Foundation(ZR2024MB108)Taishan Young Scholar Program(tsqn202312312)Excellent Young Scholars of the Shandong Provincial Natural Science Foundation(Overseas)(2023HWYQ-112)。
文摘Conversion-type electrode materials hold significant promise for potassium-ion batteries(PIBs)due to their high theoretical capacities,yet their practical deployment is hindered by sluggish kinetics and irreversible structural degradation.To overcome these limitations,we propose a rationally engineered nanoreactor architecture that stabilizes defect-rich MoS_(2)via interlayer incorporation of a carbon monolayer,followed by encapsulation within a nitrogen-doped carbon shell,forming a MoSSe@NC heterostructure.This tailored structure synergistically accelerates both K^(+)diffusion kinetics and electron transfer,enabling unprecedented rate performance(107 mAh g^(-1)at 10 Ag^(-1))and ultralong cyclability(86.5%capacity retention after 1200 cycles at 3 A g^(-1)).Mechanistic insights reveal a distinctive“adsorption-conversion”pathway,where sulfur vacancies on exposed S-Mo-S basal planes act as preferential K^(+)adsorption sites,effectively suppressing parasitic phase transitions during intercalation.In situ X-ray diffraction and transmission electron microscopy corroborate the structural reversibility of the conversion reaction,with the carbon matrix dynamically accommodating strain while preserving electrode integrity.This work not only advances the understanding of defect-driven interfacial chemistry in conversion-type materials but also provides a versatile strategy for designing high-performance anodes in next-generation PIBs through heterostructure engineering.
基金financial support from Guangdong Basic and Applied Basic Research Foundation(2020B1515420001and 2023B1515040027)Fundamental Research Funds for the Central Universities,Sun Yat-sen University(23yxqntd002)the Postdoctoral Fellowship Program of CPSF(GZC20242066)。
文摘Dual-carbon batteries(DCBs)have emerged as an appealing candidate for large-scale energy storage,yet the common trade-off between active sites and electronic conduction in carbon materials engenders a main challenge towards efficient DCBs.Here,we introduce a heteroatom-doped sp^(3) /sp^(2) hybridized carbon fiber membrane(cPAN-Gr)as a universal binder-free active electrode that effectively overcomes this trade-off,enabling efficient Li-ion intercalation chemistry for advanced DCBs.By strategically tuning the sp^(3) and sp^(2) carbon hybridization,the interlayer interaction,geometric and electronic structures of c PANGr are simultaneously optimized,which facilitates rapid Li-ion adsorption,smooth interlayer transport,and efficient electron transport by maximizing the synergy between sp^(2) -and sp^(3) -hybridized carbon.This,coupled with a 3D porous network structure,endows the c PAN-Gr with superior Li-ion storage capability and fast reaction kinetics.Therefore,the c PAN-Gr electrode delivers a high reversible capacity of 345 m A h g^(-1),excellent rate capability(50 C),and an ultralong cycle life over 10,000 cycles,outperforming other reported carbon-based electrodes.Moreover,the constructed DCB exhibits a large specific capacity of 135 m A h g^(-1),long-term cyclability over 500 cycles,and a remarkable energy density of 524.4 Wh kg^(-1).The c PAN-Gr electrode can also be expanded to construct a LiFePO_(4)//cPAN-Gr full battery.Combined theoretical and experimental studies reveal the crucial role of an optimized sp^(3) /sp^(2) ratio(79%)with topological defects and pyridine/pyrrolic N sites on the performance enhancement.This work offers new insights into the design of advanced carbon materials for DCBs and beyond.
文摘V_(2)O_(5)·nH_(2)O has been widely studied for aqueous zinc-ion batteries.The intercalation of inorganic ions has been used as a feasible method to improve the capacity of vanadium pentoxide.To further improve the stability,organic small molecule choline chloride intercalation is used to expand the spacing of the vanadium pentoxide layers and increase the cycling stability.Therefore,we consider the introduction of Sr^(2+)to cointercalate with choline chloride.Here,we synthes-ized vanadium pentoxide cointercalated with Sr^(2+)and choline ions(Ch^(+))via a simple hydrothermal method.The electro-chemical performance shows an enhanced cathode capacitance contribution of Sr&Ch-V_(2)O_(5),with a discharge capacity of 526 mAh·g^(-1)at 0.1 A·g^(-1)and a retention rate of 78.9%after 2000 cycles at 5 A·g^(-1).This work offers a novel strategy for the design of organic‒inorganic hybrid materials for use as cathodes in aqueous zinc-ion batteries.
文摘Intercalation catalysis research involves inserting metal ions,molecules,or ionic liquids into the layered structure of catalysts to adjust their electronic structure and surface properties,thereby optimizing catalytic reaction efficiency and selectivity[1–3].This technique has achieved significant progress in areas such as electrocatalysis,catalytic cracking,and energy conversion,especially in reactions like hydrogen generation,oxygen reduction,nitrogen reduction,and carbon dioxide reduction[4–6].Intercalation catalysis can enhance catalyst activity and selectivity,but challenges remain regarding stability,reusability,and industrial application.Future research will focus on developing new intercalation materials,optimizing catalyst design,and exploring their potential applications in complex environments[7].
基金financially supported by the National Natural Science Foundation of China(Nos.22435005,22193042,21921001,52202194,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBSLY-SLH024)。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.
基金financial support from the National Natural Science Foundation of China(52372173,52072034)。
文摘Direct electrolysis of seawater offers a transformative technology for sustainable hydrogen production,circumventing the constraint of freshwater scarcity.However,the serious electrode corrosion and competitive chloride oxidation reactions make oxygen evolution reaction(OER)in seawater extremely challenging.Herein,the low-cost and scalable CoFe layered double hydroxides with Cl^(-)intercalation and decorated with Ce(OH)_(3)(named as CoFe-Cl^(-)/Ce(OH)_(3))catalyst is synthesized via rapid electrodeposition under ambient conditions,which is quickly reconstructed into a CeO_(2)decorated and Cl^(-)intercalated CoFeOOH(CoFeOOH-Cl^(-)/CeO_(2))during OER.Theoretical investigation reveals that Cl^(-)intercalation weakens the adsorption ability of Cl^(-)on Co/Fe atoms and hinders unfavorable coupling with chloride,thereby preventing the chlorine corrosion process and enhancing catalytic stability and activity.The CeO_(2)with hard Lewis acidity preferentially binds to OH-with harder Lewis base to ensure the OH-rich microenvironment around catalyst even under high current operating conditions,thus further enhancing stability and improving OER activity.The functionalized CoFe-Cl^(-)/Ce(OH)_(3)delivers 1000 mA cm^(-2)current density at only 329 mV overpotential with excellent stability for 1000 h under alkaline seawater.Electrochemical experiments elucidate the OER catalytic mechanism in which CeO_(2)serves as a co-catalyst for enriching OH-and CoFeOOH-Cl^(-)is the active species.Our work is a substantial step towards achieving massive and sustainable production of hydrogen fuel from immense seawater.
基金financially supported by the Natural Science Foundations of Henan Province(Nos.222300420502 and 232300420093)the Program of Introducing Talents of Discipline to Universities(111 Project,No.D20015)+2 种基金the Key Scientific Research Projects in Higher Education Institutions of Henan Province(No.23ZX019)the Program for Science and Technology Innovation Talents in Universities of Henan Province(No.24HASTIT006)the Key Science and Technology Program of Henan Province(No.222102240044)
文摘The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries(AZIBs).Although the conventional ion doping method mitigates the intrinsically sluggish kinetics,it exacerbates the erosion of Zn^(2+)/H^(+)and free water within the lattice structure,leading to inferior structural stability and capacity fading.Herein,a synchronous dual-modification strategy is introduced to improve the electrochemical performance of the V_(6)O_(13)cathode through an ingenious hydrolysis process involving K_(2)Cr_(2)O_(7).Experimental and calculated results demonstrate that the coating layer formed by chromium oxide supports the structural firmness and strengthens the interfacial chemistry,based on increased electrochemical activity by K^(+)intercalation.Consequently,the optimized sample delivers a capacity of 418 mAh g^(-1)at 0.1 A g^(-1),and excellent cyclic stability of 205 mAh g^(-1)after 6000 cycles at 10 A g^(-1).It is fully charged at a small current of 0.5 A g^(-1)to maintain a reversible capacity of 346 mAh g^(-1)after 72 h in an open circuit state,and there is no obvious capacity decay,highlighting the crucial protective effect of the inactive coating layer.This work presents a straightforward and reliable approach to effectively harmonize the relationship between activity and structural stability for advanced AZIBs cathode.
基金funded by the National Natural Science Foundation of China(Nos.22179098 and 22209153).
文摘Despite its high capacity behavior as the anode for lithium-ion batteries (LIBs), SnO_(2) suffers the poorelectronic conductivity and high volume expansion, which lead to poor cycling stability and rate capability. In this study, we employ defect engineering to design SnO_(2−x)(x = 0, 0.12, 0.2, and 0.3) nanoparticleswith varied oxygen vacancies. Notably, the SnO1.80 electrode with 20 % oxygen vacancies exhibits excellent electrochemical performance. Advanced physical characterizations combined with density functionaltheory (DFT) simulations demonstrate that the improved electrochemical performance can be attributedto the formation of a stable, uniform, and LiF-rich solid-electrolyte interface (SEI) layer through the optimization of oxygen vacancies. This study shows novel insights into the application of defect engineeringwithin oxides for the rational design of the uniform surface layer toward high-energy-density LIBs.
基金supported by the National Key R&D Program of China(2022YFA1203400)the National Natural Science Foundation of China(W2441009)。
文摘Magnesium-ion batteries hold promise as future energy storage solutions,yet current Mg cathodes are challenged by low voltage and specific capacity.Herein,we present an AI-driven workflow for discovering high-performance Mg cathode materials.Utilizing the common characteristics of various ionic intercalation-type electrodes,we design and train a Crystal Graph Convolutional Neural Network model that can accurately predict electrode voltages for various ions with mean absolute errors(MAE)between0.25 and 0.33 V.By deploying the trained model to stable Mg compounds from Materials Project and GNoME AI dataset,we identify 160 high voltage structures out of 15,308 candidates with voltages above3.0 V and volumetric capacity over 800 mA h/cm^(3).We further train a precise NequIP model to facilitate accurate and rapid simulations of Mg ionic conductivity.From the 160 high voltage structures,the machine learning molecular dynamics simulations have selected 23 cathode materials with both high energy density and high ionic conductivity.This Al-driven workflow dramatically boosts the efficiency and precision of material discovery for multivalent ion batteries,paving the way for advanced Mg battery development.
基金supported by the National Key Research and Development Program of China(Grant Nos.2022YFA1402404 and 2023YFA1406304)the National Natural Science Foundation of China(Grant Nos.92161201,T2221003,12104221,12104220,12274208,12025404,12004174,91961101,T2394473,62274085,12374043,and U2032208)+1 种基金the Natural Science Foundation of Jiangsu Province(Grant Nos.BK20230079,BK20243013,and BK20233001)the Fundamental Research Funds for the Central Universities(Grant Nos.020414380192 and 2024300432).
文摘MnBi_(2)Te_(4),which is emerging as an intrinsic antiferromagnetic(AFM)topological insulator,provides a unique platform to investigate the interplay between magnetism and topology.Modulating its magnetic properties enables the observation of exotic quantum phenomena such as the quantum anomalous Hall effect,axion insulator states,and Majorana fermions.While the intercalation of Bi_(2)Te_(3)can tune its magnetism,synthesizing pure-phase MnBi_(2)Te_(4)with uniform Bi_(2)Te_(3)intercalation remains challenging,and the fixed interlayer spacing of Bi_(2)Te_(3)limits magnetic coupling tunability.Here,we utilize electrochemical organic molecule intercalation to expand the van der Waals gap of MnBi_(2)Te_(4)and modulate its magnetic properties.Through x-ray diffraction(XRD)characterizations,we confirm that the interlayer spacing of MnBi_(2)Te_(4)is expanded from 13.6°A to 30.5°A and 61.0°A by intercalating quaternary ammonium cations(THA^(+)and CTA^(+)),respectively.The THA-MnBi_(2)Te_(4)exhibits dual complex magnetic behavior,combining AFM ordering with a Neel temperature(T_(N))of 12 K and a small ferromagnetic hysteresis loop at 2 K.The CTA-MnBi_(2)Te_(4)shows robust ferromagnetism,with a Curie point(T_(C))of 15 K,similar to that of the MnBi_(2)Te_(4)monolayer.These results demonstrate that remarkable changes in the magnetic properties of MnBi_(2)Te_(4)can be achieved via electrochemical intercalation,providing new insights into manipulating magnetism in layered magnetic materials.
基金supported by the National Natural Science Foundation of China(Grant Nos.22090042 and 22175018).
文摘We systematically investigated the structural and superconducting properties of polycrystalline 2H-Li_(x)TaSe_(2)(0.1≤x≤1.0)synthesized via a high-temperature solid-state reaction.Lithium(Li)intercalation induces an expansion along the c-axis and intralayer distortions within the Ta-Se coordination network.The superconducting transition temperature(T_(c))is increased to 2.95 K at x=0.1 driven by the synergistic enhancement of the electronic density of states at the Fermi level,N(EF),and strengthened electron-phonon coupling.With further Li doping,although N(EF)continues to increase,lattice stiffening and pronounced distortions in the Ta-Se coordination polyhedra weaken the electron-phonon interaction,ultimately suppressing superconductivity.These findings highlight the critical role of intralayer structural modulation in governing structure-tunable superconductivity in layered materials.
基金supported by the International Science & Technology Cooperation Program of China(2010DFB63680)the National Natural Science Foundation of China(21376220)Zhejiang Provincial Natural Science Foundation of China(LY16B060009,LY12B03008)~~
文摘Highly dispersed tungsten carbide（WC） nanoparticles（NPs） sandwiched between few-layer reduced graphene oxide（RGO） have been successfully synthesized by using thiourea as an anchoring and inducing reagent.The metatungstate ion,[H2W（12）O（40）]^6-,is assembled on thiourea-modified graphene oxide（GO） by an impregnation method.The WC NPs,with a mean diameter of 1.5 nm,are obtained through a process whereby ammonium metatungstate first turns to WS2,which then forms an intercalation compound with RGO before growing,in situ,to WC NPs.The Pt/WC-RGO electrocatalysts are fabricated by a microwave-assisted method.The intimate contacts between Pt,WC,and RGO are confirmed by X-ray diffraction,scanning electron microscope,transmission electron microscope,and Raman spectroscopy.For methanol oxidation,the Pt/WC-RGO electrocatalyst exhibited an electrochemical surface area value of 246.1 m^2/g Pt and a peak current density of1364.7 mA/mg Pt,which are,respectively,3.66 and 4.77 times greater than those of commercial Pt/C electrocatalyst（67.2 m^2/g Pt,286.0 mA/mg Pt）.The excellent CO-poisoning resistance and long-term stability of the electrocatalyst are also evidenced by CO stripping,chronoamperometry,and accelerated durability testing.Because Pt/WC-RGO has higher catalytic activity compared with that of commercial Pt/C,as a result of its intercalated structure and synergistic effect,less Pt will be required for the same performance,which in turn will reduce the cost of the fuel cell.The present method is facile,efficient,and scalable for mass production of the nanomaterials.
基金supported by the National KeyR&D Program of China(Grant No.2024YFB3817400)the National Natural Science Foundation of China(Grants No.12274276 and No.U24A6002)+1 种基金the Natural Science Foundation of Shanxi Province(China)(Grant No.202403021223008)Supported by Scientific and Technology Innovation Programs of Higher Education Institutions in Shanxi(Grant No.2024Q017 and No.2025L043).
文摘Layered transition-metal compounds(LTMCs)feature stacked architectures,strong magnetic anisotropy,and tunable magnetic order,making them promising material platforms for low-power spintronic technologies and for enabling topological functionalities in the post-Moore era.Here we review recent progress on two-dimensional(2D)magnetism in LTMCs,emphasizing material taxonomy,intrinsic magnetic properties,and external-field controls.This review first presents a classification of LTMCs by crystal structure and chemistry—binary halides,chalcogenides,and ternary families(e.g.,MPX_(3),M_(m)X_(n)Te_(k),MnBi_(2)Te_(4))—followed by a summary of their coupling mechanisms,ordering temperatures,and dimensional effects.It then analyzes the modulation of exchange interactions,magnetic anisotropy,and topological states by electric-field gating,strain engineering,and ion intercalation,with representative experimental demonstrations.Notable advances include room-temperature ferromagnetic metals and semiconductors,observation of the quantum anomalous Hall effect(QAHE)in MnBi2Te4,and synergistic control of magnetic-topological states under multiple external stimuli.Persistent challenges involve the limited availability of intrinsic 2D magnetic semiconductors with high Curie temperatures(Tc),incomplete understanding of the microscopic couplings at interfaces and under quantum confinement,and device-level stability.We conclude by outlining opportunities that lie in the integration of multiscale characterization,first-principles theory,and cross-scale fabrication to precisely co-engineer magnetism,topology,and electronic structure,thereby advancing LTMCs toward spintronic and topological-quantum applications.
基金supported by the National Key Research and Development Program of China (Grant No.2023YFA1406301)the National Natural Science Foundation of China (Grant Nos.52250308 and 52525205)。
文摘Band inversion induced by spin–orbit coupling in topological semimetals typically generates light charge carriers with high Fermi velocities,which are highly desirable for low-dissipation and coherent quantum transport in topological devices.The presence of these carriers in real materials strongly depends on the Fermi-level position.2M-WSe_(2),with its topological and van der Waals nature,serves as an ideal platform for studying quantum transport in two-dimensional systems,despite the fact that interlayer coupling suppresses the formation of light carriers.In this study,we solvothermally intercalate 1,3-diaminopropane molecules into the interlayer space of 2M-WSe_(2);these molecules effectively adapt to the electronic structure by eliminating interlayer coupling.Simultaneously,slight electron doping via charge transfer results in a small Fermi pocket with an extremely light effective mass,0.04–0.06 me,as revealed by quantum oscillation measurements.This study demonstrates that molecular intercalation is an effective approach for engineering van der Waals topological materials to achieve specific quantum transport properties.
基金financial support by the National Key Research and Development Program of China(No.2023YFC2907801)the Hunan Provincial Natural Science Foundation of China(No.2023JJ40760)the Scientific and Technological Project of Yunnan Precious Metals Laboratory,China(No.YPML-2023050276)。
文摘Bentonite is a necessary binder in producing pellets.Its excessive use reduces the iron grade of pellets and increases production costs.Minimizing bentonite dosage is essential for producing high-quality iron ore pellets.Addressing the gap in the application of organically-intercalated modified bentonite in the pelletizing field,this study introduces an innovative modification process for bentonite that employs the synergistic effect of mechanical force and dimethyl sulfoxide to enhance the intercalation of organic compounds within bentonite,thus significantly enhancing its binding performance.The colloid value and swell capacity of modified bentonite(98.5 m L/3g and 55.0 m L/g)were much higher than the original bentonite(90.5 m L/3g and 17.5 m L/g).With the decrease of bentonite dosage from1.5wt%to 1.0wt%,the drop number of green pellets from a height of 0.5 m and the compressive strengths of roasted pellets using the modified bentonite(6.0 times and 2916 N per pellet)were significantly higher than those of the original bentonite(4.0 times and 2739 N per pellet).This study provides a comprehensive analysis of the intercalation modification mechanism of bentonite,offering crucial technical insights for the development of high-performance modified bentonite as iron ore pellet binders.
基金supported by the Key R&D Program of Zaozhuang city,China(2024GH12)the Zaozhuang Gathering of Talents Program。
文摘Developing advanced cathode modification strategies to address the inherent high charge density of Al^(3+) is essential for achieving high-energy-density and long-cycle-life rechargeable aluminum batteries(RABs).Herein,we engineer tetraethylammonium(TEA)cation intercalation as a dual-function strategy that concurrently enables interlayer distance enlargement and electrostatic shielding effects,resolving Al^(3+) polarization-induced sluggish kinetics and cathode degradation in RABs.TEA intercalation triggers exceptional V2O5 interlayer expansion from 4.37 to 13.10Å,while the modulated charge distribution generates an electrostatic shielding effect that significantly weakens the Coulombic interactions between Al^(3+) and V2O5 frameworks.This dual mechanism collectively enhances ion diffusion kinetics and suppresses lattice stress accumulation.Ex situ X-ray diffraction and transmission electron microscopy analyses confirm that the“molecular pillar effect”of TEA enables minimal and highly reversible structural deformation of the cathode(<2.0%volume change after 200 cycles),demonstrating zero-strain aluminum-storage behavior.The optimized cathode delivers a high reversible capacity of 258 mAh g^(−1) at 0.5 A g^(−1),maintains 99%capacity retention at 5.0 A g^(−1),and exhibits an ultralow capacity decay rate of 0.01%per cycle over 6000 cycles.This work opens new pathways for designing stable high-performance RAB cathodes through synergistic modulation of electronic and lattice structures.
