NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsi...NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.展开更多
Here we report on simultaneous lidar observations of sporadic Ni(Nis)layers and sporadic Na(Nas)layers in the atmosphere over Yanqing,Beijing(40.42°N,116.02°E)from April 2019 to October 2022.During 343 night...Here we report on simultaneous lidar observations of sporadic Ni(Nis)layers and sporadic Na(Nas)layers in the atmosphere over Yanqing,Beijing(40.42°N,116.02°E)from April 2019 to October 2022.During 343 nights of observation,68 Nis and 56 Nas were observed.The seasonal variation of Nis and Nas was also obtained,with the highest occurrence of Nis being in July(43%)and that of Nas being in June(61%).We found that the seasonal variation of Nis is similar to that of Nas and that both occur more frequently in summer than in winter.In addition,we found 23 events in which Nis and Nas occur simultaneously.The average peak altitude of Nas is approximately 1 km higher than that of Nis,and the peak density ratio of Nas to Nis is approximately 5,which is half the density ratio of the two main layers.Additionally,the strength factor for Nas is smaller than that for Nis.Through data analysis of sporadic E layers(Es),we found that Nis and Nas has a significant correlation with Es.The neutralization rates of Ni^(+)/Na^(+)were calculated according to the dissociative recombination reaction of Ni^(+)/Na^(+)and the WACCM-Ni(Whole Atmosphere Community Climate Model of Ni).The production rates of Ni and Na were estimated to be approximately 1:4.4,which is consistent with the density ratio of Nis to Nas.The results showed that the neutralization reaction of Ni+,Na+,and electrons in Es is the main reason for the formation of the Nis layer and the Nas layer.展开更多
AlGaN-based deep-ultraviolet(DUV)laser diodes(LDs)face performance challenges due to elec-tron leakage and poor hole injection which is often worsened by polarization effects from conventional elec-tron blocking layer...AlGaN-based deep-ultraviolet(DUV)laser diodes(LDs)face performance challenges due to elec-tron leakage and poor hole injection which is often worsened by polarization effects from conventional elec-tron blocking layers(EBLs).To overcome these limitations,we propose an EBL-free DUV LD design incor-porating a 1-nm undoped Al_(0.8)Ga_(0.2)N thin strip layer after the last quantum barrier.Using PICS3D simula-tions,we evaluate the optical and electrical characteristics.Results show a significant increase in effective electron barrier height(from 158.2 meV to 420.7 meV)and a reduction in hole barrier height(from 149.2 meV to 62.8 meV),which enhance hole injection and reduce electron leakage.The optimized structure(LD3)achieves a 14%increase in output power,improved slope efficiency(1.85 W/A),and lower threshold current.This design also reduces the quantum confined Stark effect and forms dual hole accumulation regions,im-proving recombination efficiency.展开更多
Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,t...Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.展开更多
If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with te...If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with tea and delicate steamed treats instead of coffee.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
A novel trace nickel(Ni)doped tungsten(W)matrix with coated Ni on W grains was prepared by powder metallurgy method.The introduction of Ni can inhibit the reaction between W and barium-calcium aluminates(Ba-Ca alumina...A novel trace nickel(Ni)doped tungsten(W)matrix with coated Ni on W grains was prepared by powder metallurgy method.The introduction of Ni can inhibit the reaction between W and barium-calcium aluminates(Ba-Ca aluminates)during the impregnation process of the matrix.After cathode activation,the surface Ba:O molar ratio is 0.88:1.00,much higher than the Ba dispenser cathode without Ni doping.The XPS results of the cathode surface showed that the metallic Ba appeared on the activated cathode surface,forming dipoles with oxygen,and effectively reducing the cathode surface work function.The pulse electron emission current density at 1100℃_(b)(brightness temperature)was 18.26 A/cm^(2),and the calculated work function was 1.97 eV.It has a low evaporation rate and the accelerated lifetime test predict a lifetime of over 160000 h.First-principles calculations showed that the charge transfer and dipole moment in the NiW-BaO system were both increased compared to the Ba dispenser cathode,thus improving the emission performance of the Ni-W mixed matrix cathode.展开更多
Numerical simulations and theoretical models are developed in this paper for the Detonation-Wave/Boundary-Layer Interactions(DWBLIs)under reflections.Transient flow fields demonstrate the highly non-stationarity of th...Numerical simulations and theoretical models are developed in this paper for the Detonation-Wave/Boundary-Layer Interactions(DWBLIs)under reflections.Transient flow fields demonstrate the highly non-stationarity of the DWBLIs when Mach Reflection(MR)occur,and subsequent analyses show that the subsonic region introduced by the boundary layer exacerbates the instability.Further quantitative analyses show that viscosity has little effect on propulsive performance and the separation wave can be considered as an oblique detonation wave.Influence parameters to DWBLIs such as combustion chamber height,incoming Mach number,equivalence ratio,and inlet channel length are categorized and studied.Besides simulations,theoretical analytical modeling is established for Regular Reflection(RR)and MR of DWBLIs.Multiple formulas for the separation zone length are obtained according to the mass conservation under different transformation type between inviscid and viscid reflections.Comparison with the numerical simulations verifies the validity of the model and it can be further generalized to the curved DWBLIs.The developed model makes the theoretical solution process of DWBLIs possible and provides the key foundation for further analysis and solution.展开更多
Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion ...Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.展开更多
High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stabi...High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.展开更多
Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we...Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.展开更多
The atmospheric surface layer of the tropical coastal ocean is commonly very unstable and experiences weakwind conditions.How the latent(LE)and sensible(H)heat fluxes behave under such conditions are unclear because o...The atmospheric surface layer of the tropical coastal ocean is commonly very unstable and experiences weakwind conditions.How the latent(LE)and sensible(H)heat fluxes behave under such conditions are unclear because of the lack of observation stations in the tropics.Thus,this study aims to analyze LE and H and the microclimate parameters influencing them.The authors deployed an eddy covariance system in a tropical coastal region for seven months.The microclimate parameters investigated were wind speed(U),vapor pressure deficit(Δe),temperature difference(ΔT),wind-vapor pressure deficit(UΔe),wind-temperature difference(UΔT),and atmospheric stability(z/L),where z is height and L is the Monin–Obukhov length.On the daily time scale,the results show that LE was more associated with U thanΔe,while H was more related toΔT than U.Cross-wavelet analysis revealed the strong coherence in the LE-U relationship for periods between one and two days,and for H–ΔT,0.5 to 1 day.Correlation and regression analyses confirmed the time series analyses results,where strong positive correlation coefficients(r)were obtained between LE and U(r=0.494)and H andΔT(r=0.365).Compared to other water bodies,the transfer coefficient of moisture(CE N)was found to be small(=0.40×10^(-3))and independent of stability;conversely,the transfer coefficient of heat(CH N)was closer to literature values(=1.00×10^(-3))and a function of stability.展开更多
The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of thes...The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.展开更多
High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs ...High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.展开更多
Crossflow instability will be present when the vehicle has an angle of attack in hypersonic flow,and it might play a dominant role in hypersonic boundary layer transition.By far the mechanism of crossflow instability-...Crossflow instability will be present when the vehicle has an angle of attack in hypersonic flow,and it might play a dominant role in hypersonic boundary layer transition.By far the mechanism of crossflow instability-induced hypersonic boundary layer transition is still out of understanding,although the large effort has been devoted.Upon this work,the overall roughness effect on instabilities in hypersonic flow was researched experimentally.Surface flush-mounted pressure sensors and infrared camera were employed to investigate the instability waves when different rough surfaces were deployed.The results reveal that the moderate surface roughness level on cone model can suppress the growth of crossflow instabilities at certain azimuthal angles in hypersonic flow.展开更多
The deep coal reservoir in Linxing-Shenfu block of Ordos Basin is an important part of China’s coalbed methane resources.In the process of reservoir reconstruction,the artificial fracture morphology of coal seam with...The deep coal reservoir in Linxing-Shenfu block of Ordos Basin is an important part of China’s coalbed methane resources.In the process of reservoir reconstruction,the artificial fracture morphology of coal seam with gangue interaction is significantly different,which affects the efficient development of coalbed methane resources in this area.In this paper,the surface outcrop of Linxing-Shenfu block is selected,and three kinds of interaction modes between gangue and coal seam are set up,including single-component coal rock sample,coal rock sample with different thicknesses of gangue layer and coal rock sample with different numbers of gangue.Through true triaxial physical simulation and three-dimensional discrete element numerical simulation,the lawof artificial fracture initiation and propagation in multi-gangue interaction coal seam is analyzed in depth,and the hydraulic fracture initiation and propagation mode under different interaction modes of gangue layer in Linxing-Shenfu deep coal reservoir was clarified.The research shows that the initiation of artificial fractures in a single coal seam is affected by geologicalengineering factors.The maximum principal stress dominates the direction of fracture propagation,and the stress difference controls the fracture morphology.When the stress difference is 2 MPa,the fracture morphology is complex,which is easy to connect to the weak surface of coal and rock cleat,and the fracturemorphology of the stress difference is mainly a single main fracture.After the thickness of the gangue layer is increased from 2 to 5 cm,it is difficult for the artificial fracture to penetrate the layer vertically after the fracture initiation,and the effective transformation area of the reservoir is limited.The more the number of gangue layers,the greater the hydraulic energy consumption in the process of fracture propagation,and the more difficult the fracture propagation.展开更多
Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted b...Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.展开更多
Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte i...Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte interface.Functional protective coatings on lithium metal surfaces offer a viable solution to these challenges.Herein,an innovative adaptive protective layer for lithium metal anodes based on a thiourea H-bonded supramolecular polymer is developed for the first time.With dense thiourea H-bonding,the lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)incorporated poly(ether-thiourea)protective layer shows strong adhesion to the lithium metal surface and good adaptive properties.The unique viscoelastic and flow characteristics of the poly(ether-thiourea)coating facilitate uniform Li⁺flux,effectively suppressing dendrite formation at the solid electrolyte interface.Furthermore,this innovative polymer integrates in situ generated compounds,such as Li3N and Li_(2)O,significantly enhancing interfacial stability.A comprehensive analysis involving X-ray photoelectron spectroscopy,scanning electron microscopy,X-ray tomography,and COMSOL simulations elucidates the beneficial effects of the adaptive coating.Enhanced performances in Li||Cu,Li||Li,Li||LiFePO_(4),and Li||S cells demonstrate the effectiveness of the poly(ether-thiourea)coating and its undeniable capability to improve lithium deposition and cycling stability.This study highlights a promising new candidate for developing supramolecular materials capable of stabilizing lithium metal anodes.展开更多
The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries...The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.展开更多
The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
基金supported by the Natural Science Foundation of China Grant No.52272289 and 5240223,and JSPS(Japan Society for the Promotion of Science)of Grant No.22K19088,23H00313,24H02202,and 24H02205。
文摘NiFe-layered double hydroxides(NiFe-LDHs)are among the most promising earth-abundant electrocatalysts for the oxygen evolution reaction(OER)in alkaline media.However,their practical application is hindered by intrinsic activity limitations and poor stability,primarily due to the asymmetric adsorption of oxygen intermediates.To overcome this,the binding strength must be synergistically tuned to a moderate level to optimize catalytic performance.Here,we engineered NiFeCoCr LDH through Co doping to enhance electrical conductivity and controlled Cr leaching to introduce cationic vacancies for modulating intermediate binding strength in NiFe LDH.X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses reveal that NiFe-LDH with Co doping and Cr vacancies modulates the Ni oxidation state and local coordination environment,leading to a balanced electronic structure and enhanced structural complexity around the Ni sites.Additionally,these vacancies can trap OH^(-)/H_(2)O species,which can serve as a reservoir for OH^(-) transfer,facilitating the rapid formation of OER intermediates and enhancing catalytic performance at high current densities.As a result,V_(Cr)-NiFeCo LDH achieves 1.6 A cm^(-2)current density at 1.7 V vs.RHE while maintaining stable operation for over 1000 h at 500 mA cm^(-2).Density functional theory(DFT)calculations validate the synergistic effects of Co doping and Cr-induced vacancies on intermediate binding energies and improved OER kinetics.Overall,this work presents a rational design strategy to simultaneously enhance the activity and durability of NiFe-based OER catalysts for their application in high-performance alkaline water electrolysis.
基金supported by the Specialized Research Fund for State Key Laboratories,Chinese Meridian Project,the Specialized Research Fund for the State Key Laboratory of Solar Activity and Space Weather,postgraduate Education Reform and Quality Improvement Project of Henan Province(Grant No.YJS2024JD32)Natural Science Foundation Project of Henan Province(Grant No.242300420253)National Natural Science Foundation of China for Young Scientists(Grant No.42504156)funding.
文摘Here we report on simultaneous lidar observations of sporadic Ni(Nis)layers and sporadic Na(Nas)layers in the atmosphere over Yanqing,Beijing(40.42°N,116.02°E)from April 2019 to October 2022.During 343 nights of observation,68 Nis and 56 Nas were observed.The seasonal variation of Nis and Nas was also obtained,with the highest occurrence of Nis being in July(43%)and that of Nas being in June(61%).We found that the seasonal variation of Nis is similar to that of Nas and that both occur more frequently in summer than in winter.In addition,we found 23 events in which Nis and Nas occur simultaneously.The average peak altitude of Nas is approximately 1 km higher than that of Nis,and the peak density ratio of Nas to Nis is approximately 5,which is half the density ratio of the two main layers.Additionally,the strength factor for Nas is smaller than that for Nis.Through data analysis of sporadic E layers(Es),we found that Nis and Nas has a significant correlation with Es.The neutralization rates of Ni^(+)/Na^(+)were calculated according to the dissociative recombination reaction of Ni^(+)/Na^(+)and the WACCM-Ni(Whole Atmosphere Community Climate Model of Ni).The production rates of Ni and Na were estimated to be approximately 1:4.4,which is consistent with the density ratio of Nis to Nas.The results showed that the neutralization reaction of Ni+,Na+,and electrons in Es is the main reason for the formation of the Nis layer and the Nas layer.
文摘AlGaN-based deep-ultraviolet(DUV)laser diodes(LDs)face performance challenges due to elec-tron leakage and poor hole injection which is often worsened by polarization effects from conventional elec-tron blocking layers(EBLs).To overcome these limitations,we propose an EBL-free DUV LD design incor-porating a 1-nm undoped Al_(0.8)Ga_(0.2)N thin strip layer after the last quantum barrier.Using PICS3D simula-tions,we evaluate the optical and electrical characteristics.Results show a significant increase in effective electron barrier height(from 158.2 meV to 420.7 meV)and a reduction in hole barrier height(from 149.2 meV to 62.8 meV),which enhance hole injection and reduce electron leakage.The optimized structure(LD3)achieves a 14%increase in output power,improved slope efficiency(1.85 W/A),and lower threshold current.This design also reduces the quantum confined Stark effect and forms dual hole accumulation regions,im-proving recombination efficiency.
基金supported by grants from the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(MSIT)(RS-2024-00407116)+1 种基金by the Ministry of Education(NRF-2018R1A6A1A03024231)support from the NRF grant funded by the MSIT(RS-2024-00406724)。
文摘Interfacial engineering is crucial for developing high-performance Ni-rich layered cathodes for lithiumion batteries.Here,we introduce an interfacial precipitation(IP)strategy,guided by first-principles calculations,to create a functionally graded cathode during precursor synthesis.Based on thermodynamic principles of bulk insolubility and phase separation kinetics,we achieved the selective precipitation of Co onto the surface of a Ni-rich hydroxide precursor.Upon high-temperature lithiation,this engineered precursor spontaneously forms a unique,bifunctional Co-rich spinel-like layer on the final LiNi_(0.88)Co_(0.06)Mn_(0.06)O_(2)(NCM)cathode.This architecture suppresses detrimental Li/Ni cation mixing and protects the active material.Consequently,the IP-driven NCM cathode demonstrates vastly superior rate capability,delivering 140.8 m A h g^(-1)at 5C,compared to 112.9 mA h g^(-1)for its conventionally prepared counterpart.This enhancement is attributed to significantly lower charge-transfer resistance and faster kinetics.Remarkably,in a full-cell configuration,the IP-driven NCM cathode maintains 81.5%capacity after 1000 cycles at an aggressive 5C rate.This work presents a thermodynamically driven,scalable strategy for designing advanced cathodes with exceptional high-power performance and stability.
文摘If you're tired of megacities that feel like nothing but glass,steel,and constant rush,Guangzhou moves at its own pace.Here,a 19th-century ancestral hall stands next to a 600-meter tower,and the day begins with tea and delicate steamed treats instead of coffee.
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 Natural Science Foundation of China(Nos.U2341209 and 52130407).
文摘A novel trace nickel(Ni)doped tungsten(W)matrix with coated Ni on W grains was prepared by powder metallurgy method.The introduction of Ni can inhibit the reaction between W and barium-calcium aluminates(Ba-Ca aluminates)during the impregnation process of the matrix.After cathode activation,the surface Ba:O molar ratio is 0.88:1.00,much higher than the Ba dispenser cathode without Ni doping.The XPS results of the cathode surface showed that the metallic Ba appeared on the activated cathode surface,forming dipoles with oxygen,and effectively reducing the cathode surface work function.The pulse electron emission current density at 1100℃_(b)(brightness temperature)was 18.26 A/cm^(2),and the calculated work function was 1.97 eV.It has a low evaporation rate and the accelerated lifetime test predict a lifetime of over 160000 h.First-principles calculations showed that the charge transfer and dipole moment in the NiW-BaO system were both increased compared to the Ba dispenser cathode,thus improving the emission performance of the Ni-W mixed matrix cathode.
基金support of the National Natural Science Foundation of China(Nos.U20A2069,U21B6003,12302389 and 12472337)the Advanced Aero-Power Innovation Workstation,China(No.HKCX2024-01-017)。
文摘Numerical simulations and theoretical models are developed in this paper for the Detonation-Wave/Boundary-Layer Interactions(DWBLIs)under reflections.Transient flow fields demonstrate the highly non-stationarity of the DWBLIs when Mach Reflection(MR)occur,and subsequent analyses show that the subsonic region introduced by the boundary layer exacerbates the instability.Further quantitative analyses show that viscosity has little effect on propulsive performance and the separation wave can be considered as an oblique detonation wave.Influence parameters to DWBLIs such as combustion chamber height,incoming Mach number,equivalence ratio,and inlet channel length are categorized and studied.Besides simulations,theoretical analytical modeling is established for Regular Reflection(RR)and MR of DWBLIs.Multiple formulas for the separation zone length are obtained according to the mass conservation under different transformation type between inviscid and viscid reflections.Comparison with the numerical simulations verifies the validity of the model and it can be further generalized to the curved DWBLIs.The developed model makes the theoretical solution process of DWBLIs possible and provides the key foundation for further analysis and solution.
基金support from the National Natural Science Foundation of China(NSFC 21905092,22475072 and 22075085)the Fundamental Research Funds for the Central Universities+1 种基金supported by the Shanghai Frontiers Science Center of Molecule Intelligent SynthesesEast China Normal University Multifunctional Platform for Innovation(004)。
文摘Artificial photosynthesis of hydrogen peroxide(H_(2)O_(2))from earth-abundant water and oxygen is a sustainable approach,however current photocatalysts suffer from low production rate and solar-to-chemical conversion efficiency(<1.5%).Herein,we report that nickelchromium layered double hydroxide with intercalated nitrate(NiCrOOH-NO_(3))and a thickness of~4.4 nm is an efficient photocatalyst,enabling a H_(2)O_(2)production yield of 28.7 mmol g^(-1)h^(-1)under visible light irradiation with3.92%solar-to-chemical conversion efficiency.Experimental and computational studies have revealed an inherent facet-dependent reduction-oxidation reaction behavior and spatial separation of photogenerated electrons and holes.An unexpected role of intercalated nitrate is demonstrated,which promotes excited electron—hole spatial separation and facilitates the electron transfer to oxygen intermediate via delocalization.This work provides understandings in the impact of nanostructure and anion in the design of advanced photocatalysts,paving the way toward practical synthesis of H_(2)O_(2)using fully solar-driven renewable energy.
基金the financial support by Advanced Materials-National Science and Technology Major Project(2024ZD0607400)the National Natural Science Foundation of China(No.52402305)+4 种基金the high-level innovation and entrepreneurship talent project of Qinchuangyuan(No.QCYRCXM-2023-084)the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20230570 and 2024M752552Key projects of Shaanxi Province,China(2023GXLH-001)Natural Science Basic Research Program of Shaanxi(Program No.2024JCYBQN-0494,No.2022TD-27)the State Key Laboratory for Electrical Insulation and Power Equipment(No.EIPE23125)。
文摘High-entropy layered hydroxides(HELHs),an emerging frontier in entropy-stabilized materials derived from layered double hydroxides(LDHs),have captivated attention with their unparalleled tunability,thermodynamic stability,and electrochemical performance.The integration of the high-entropy concept into LDHs empowers HELHs to surmount the constraints of conventional materials through compositional diversity,structurally disordered configurations,and synergistic multi-element interactions.This review systematically embarks on their synthesis methodologies,functional mechanisms,and applications in energy conversion/storage and biomedicine.Advanced synthesis strategies,such as plasma-assisted hydrothermal methods,facilitate precise control over HELH architectures while supporting scalable production.HELHs demonstrate superior electrochemical performance in critical reactions,including oxygen evolution reaction,water oxidation,hydrogen evolution,and glucose electrooxidation.Future directions encompass integrating in situ characterization with simulations,leveraging machine learning for composition screening,and expanding HELHs application through interdisciplinary collaborations.This work establishes a comprehensive roadmap for advancing HELHs as next-generation multifunctional platforms for sustainable energy and biomedical technologies.
基金the financial support from Research Institute for Smart Energy at the Hong Kong Polytechnic University(Grant No.CDB2)the support of the Hong Kong PhD Fellowship Scheme(Grant No.PF21-65328)。
文摘Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage,but their commercialization is hindered by zinc anode challenges,notably parasitic reactions and dendrite growth.Herein,we present a biodegradable biomass-derived protective layer,primarily composed of curcumin,as a zincophilic interface for AZMBs.The curcumin-based layer,fabricated via a homogeneous solution process,exhibits strong adhesion,uniform coverage,and robust mechanical integrity.Rich polar functional groups in curcumin facilitate homogeneous Zn~(2+)flux and suppress side reactions.The curcumin-based layer shows a favorable affinity for zinc trifluoromethanesulfonate(Zn(OTf)_(2))electrolyte,which is the representative of organic zinc salts,enabling optimal thickness for both protection and ion transport.The protected Zn anodes demonstrate an extended lifespan of 2500 h in symmetrical cells and a high Coulombic efficiency of 99.15%.Furthermore,Zn(OTf)_(2)-based system typically exhibits poor stability at high current densities.Fortunately,the lifespan of symmetrical cells was extended by 40-fold at the high current density.When paired with an Na V_(3)O_(8)·1.5H_(2)O(NVO)cathode,the system achieves 86.5%capacity retention after 3000 cycles at a large specific current density of 10 A g^(-1).These results underscore the efficacy of the curcumin-based protective layer in enhancing the reversibility and stability of metal electrodes,specifically relieving the instability of Zn(OTf)_(2)-based systems at high current densities,advancing its commercial viability.
基金supported by a PETRONAS-Academia Collabora-tion Dialogue 2022 Grant[Grant number PACD 2022]from PETRONAS Research Sdn.Bhd。
文摘The atmospheric surface layer of the tropical coastal ocean is commonly very unstable and experiences weakwind conditions.How the latent(LE)and sensible(H)heat fluxes behave under such conditions are unclear because of the lack of observation stations in the tropics.Thus,this study aims to analyze LE and H and the microclimate parameters influencing them.The authors deployed an eddy covariance system in a tropical coastal region for seven months.The microclimate parameters investigated were wind speed(U),vapor pressure deficit(Δe),temperature difference(ΔT),wind-vapor pressure deficit(UΔe),wind-temperature difference(UΔT),and atmospheric stability(z/L),where z is height and L is the Monin–Obukhov length.On the daily time scale,the results show that LE was more associated with U thanΔe,while H was more related toΔT than U.Cross-wavelet analysis revealed the strong coherence in the LE-U relationship for periods between one and two days,and for H–ΔT,0.5 to 1 day.Correlation and regression analyses confirmed the time series analyses results,where strong positive correlation coefficients(r)were obtained between LE and U(r=0.494)and H andΔT(r=0.365).Compared to other water bodies,the transfer coefficient of moisture(CE N)was found to be small(=0.40×10^(-3))and independent of stability;conversely,the transfer coefficient of heat(CH N)was closer to literature values(=1.00×10^(-3))and a function of stability.
基金financially supported by the National Natural Science Foundation of China(52274295)the Natural Science Foundation of Hebei Province(E2025501032,E2025501028)+3 种基金the Fundamental Research Funds for the Central Universities(N2523045,N2423051,N2423005,N2423019)the Science and Technology Project of Hebei Education Department(QN2024238)the Central Guided Local Science and Technology Development Fund Project of Hebei Province(254Z1102G)the Basic Research Program Project of Shijiazhuang City for Universities Stationed in Hebei Province(241790937A)。
文摘The P2-type Fe/Mn-based layered oxides,with cost advantages and high theoretical capacity,are considered one of the promising cathode materials for sodium-ion batteries(SIBs).However,the commercial development of these materials is impeded by two main factors:the MnO_(6) structure distortion induced by the Jahn-Teller(J-T)effect of Mn^(3+),and the unfavorable phase transitions that occur during the insertion and extraction of Na^(+).Here,we present a strategy to improve structural stability by incorporating cost-effective,robust Al-O bonds.This approach induces localized adjustments in the electronic structu re and a pinning effect,which limits the deformation of the transition metal(TM)layers,strengthens the electrostatic bonding within the TM layers,and expands the Na layer spacing.Consequently,the Na_(0.67)Fe_(0.4)Mn_(0.54)Al_(0.06)O_(2) cathode demonstrates a capacity of 168.8 mAh g^(-1) at 0.1 C,maintaining89.2%of its original capacity after 200 cycles at 1 C.Through in situ electrochemical impedance spectroscopy(EIS)with dynamic resistance transformation(DRT)analysis,ex situ X-ray absorption spectroscopy(XAS),and in situ X-ray diffraction(XRD),the study demonstrates a reduction in the J-T effect,enhanced kinetic performance,and the inhibition of detrimental phase transitions.This study offers new avenues to the development and design of future low-cost Fe/Mn-based cathodes.
基金supported by the National Natural Science Foundation of China(Grant Nos.52202282,52402054,22471283,and 52202327)Natural Science Foundation of Tianjin City(Grant Nos.22JCYBJC00040,24JCQNJC00970)。
文摘High-capacity O3-type layered NiFeMn-based oxides are promising cathodes for sodium-ion batteries,though their practical deployment is constrained by the inherent limitations of Fe redox chemistry.Traditional designs generally enforcing stoichiometric symmetry(Ni=Mn)yield low Fe redox activity.Herein,we propose a valence engineering strategy that breaks conventional Ni/Mn stoichiometry to reconfigure Fe's local chemical environment and unlock unprecedented redox depth.Density functional theory(DFT)calculations reveal that the designed NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode exhibits a reduced Bader charge on Fe(1.598 vs.1.638 in NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2))and elevated Fe 3d orbital energy,signifying enhanced Fe redox activity.This configuration enables an exceptional Fe^(2.60+)/Fe^(3.88+)redox(1.28 e~-per Fe),delivering a reversible capacity of184.3 mAh g^(-1)within 2-4.2 V at 0.2 C,markedly exceeding the benchmark NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(161.3 mAh g^(-1))with low reaction depth of Fe^(3.01+)/Fe^(3.61+).The intensified cationic redox reaction enables an ultrahigh energy density of 596 Whkg-1.The NaNi_(0.35)Fe_(0.225)Mn_(0.425)O_(2)cathode demonstrates robust performance over a broad temperature range from-15℃to 60℃.In situ and ex situ characterizations unveil a reversible O3■P3■OP2 phase transition with minimal volume change(1.88%)that circumvents detrimental deleterious O'3 intermediates and intragranular cracking.This work establishes valence engineering as a paradigm to consolidate cationic redox reaction in high-energy layered sodium oxide cathodes.
基金supported by the National Natural Science Foundation of China(No.11972357)。
文摘Crossflow instability will be present when the vehicle has an angle of attack in hypersonic flow,and it might play a dominant role in hypersonic boundary layer transition.By far the mechanism of crossflow instability-induced hypersonic boundary layer transition is still out of understanding,although the large effort has been devoted.Upon this work,the overall roughness effect on instabilities in hypersonic flow was researched experimentally.Surface flush-mounted pressure sensors and infrared camera were employed to investigate the instability waves when different rough surfaces were deployed.The results reveal that the moderate surface roughness level on cone model can suppress the growth of crossflow instabilities at certain azimuthal angles in hypersonic flow.
基金supported by National Key Laboratory of Petroleum Resources and Engineering,China University of Petroleum,Beijing(No.PRE/open-2307).
文摘The deep coal reservoir in Linxing-Shenfu block of Ordos Basin is an important part of China’s coalbed methane resources.In the process of reservoir reconstruction,the artificial fracture morphology of coal seam with gangue interaction is significantly different,which affects the efficient development of coalbed methane resources in this area.In this paper,the surface outcrop of Linxing-Shenfu block is selected,and three kinds of interaction modes between gangue and coal seam are set up,including single-component coal rock sample,coal rock sample with different thicknesses of gangue layer and coal rock sample with different numbers of gangue.Through true triaxial physical simulation and three-dimensional discrete element numerical simulation,the lawof artificial fracture initiation and propagation in multi-gangue interaction coal seam is analyzed in depth,and the hydraulic fracture initiation and propagation mode under different interaction modes of gangue layer in Linxing-Shenfu deep coal reservoir was clarified.The research shows that the initiation of artificial fractures in a single coal seam is affected by geologicalengineering factors.The maximum principal stress dominates the direction of fracture propagation,and the stress difference controls the fracture morphology.When the stress difference is 2 MPa,the fracture morphology is complex,which is easy to connect to the weak surface of coal and rock cleat,and the fracturemorphology of the stress difference is mainly a single main fracture.After the thickness of the gangue layer is increased from 2 to 5 cm,it is difficult for the artificial fracture to penetrate the layer vertically after the fracture initiation,and the effective transformation area of the reservoir is limited.The more the number of gangue layers,the greater the hydraulic energy consumption in the process of fracture propagation,and the more difficult the fracture propagation.
基金supported by the National Key R&D Program of China(2023YFB2406000)the National Natural Science Foundation of China(22479057,52172201,51732005)。
文摘Sodium layered oxides stand out as one of the most promising cathodes for sodium-ion batteries due to their high energy density,elemental abundance,and scalability.However,their practical applications are restricted by interplanar gliding,cation migration,and the formation of intragranular microcracks,which collectively lead to rapid structural degradation and capacity loss.Herein,we rationally design an ultrastable O3-type Na_(0.94)Ca_(0.03)Ni_(1/3)Fe_(1/3)Mn_(1/3)O_(2) cathode,in which Ca^(2+)cations act as pillars within the NaO_(2)slabs,suppressing the irreversible phase transitions and Na/TM cation migration commonly observed in layered oxides.Multiscale in situ and ex situ techniques,combined with post-mortem analysis,reveal that the Ca-pillared pinning effect not only effectively suppresses the interplanar gliding and stress accumulation within the crystal phase but also restrains Na/TM cation migration and surface reconstruction in near-surface regions.Benefiting from the combined effects of structural stabilization,the Ca-pillared cathode exhibits a superior cycling stability,retaining 81.6%of its capacity after 1000 cycles at 2 C within the voltage range of 2.0-4.0 V,along with significantly enhanced wide-temperature(from-40 to 80℃)performance.This work highlights another critical role of Ca pillars in suppressing cation migration and surface structural degradation beyond preventing adverse interplanar gliding,offering valuable insights for designing long-life and wide-temperature layered oxide cathodes.
基金Yongsheng Zhang(CSC no.202106050027),Xiaolong He(CSC no.202106340039),Yinyu Xiang(CSC no.201806950083)acknowledge the financial support from the Chinese Scholarship Council(CSC)the Advanced Materials Research program of the Zernike Institute under the Bonus Incentive Scheme of the Dutch Ministry for Education,Culture and Science(OCW)the Battery NL-Next Generation Battery based on Understanding Materials Interfaces project(with project number NWA 1389.20.089)of the NWA research program“Research on Routes by Consortia(ORC)”funded by the Dutch Research Council(NWO)。
文摘Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte interface.Functional protective coatings on lithium metal surfaces offer a viable solution to these challenges.Herein,an innovative adaptive protective layer for lithium metal anodes based on a thiourea H-bonded supramolecular polymer is developed for the first time.With dense thiourea H-bonding,the lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)incorporated poly(ether-thiourea)protective layer shows strong adhesion to the lithium metal surface and good adaptive properties.The unique viscoelastic and flow characteristics of the poly(ether-thiourea)coating facilitate uniform Li⁺flux,effectively suppressing dendrite formation at the solid electrolyte interface.Furthermore,this innovative polymer integrates in situ generated compounds,such as Li3N and Li_(2)O,significantly enhancing interfacial stability.A comprehensive analysis involving X-ray photoelectron spectroscopy,scanning electron microscopy,X-ray tomography,and COMSOL simulations elucidates the beneficial effects of the adaptive coating.Enhanced performances in Li||Cu,Li||Li,Li||LiFePO_(4),and Li||S cells demonstrate the effectiveness of the poly(ether-thiourea)coating and its undeniable capability to improve lithium deposition and cycling stability.This study highlights a promising new candidate for developing supramolecular materials capable of stabilizing lithium metal anodes.
基金supported by the financial support from the Guangdong Basic and Applied Basic Research Foundation(No.2023B1515120095)the National Natural Science Foundation of China(Nos.52471229 and 52171210)the Jilin Province Science and Technology Department Program(No.20240101004JJ).
文摘The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction(HER)at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries.In this work,we propose sorbitan oleate(Span 80)as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO_(4),demonstrating multifunctional performance.The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface,forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions.Simultaneously,carbon chains can enhance the desolvation effect of[Zn(H_(2)O)_(6)]^(2+),leading to improve rate performance.Additionally,the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode,promoting uniform Zn^(2+)deposition and suppressing dendrite growth.The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability,sustaining reversible plating/stripping for 570 h at 50 mA/cm^(2) and the Zn||V_(2)O_(5) full cell retains exceptional stability over 2000 cycles at 1 A/g.Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants.This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
