Sulfur vacancies and heterogeneous interfaces promote high performance sodium storage of bimetallic chalcogenide hollow nanospheres

Transition metal sulfides have high theoretical capacities and are considered as potential anode materials for sodium-ion batteries.However,due to low inherent conductivity and significant volume expansion,the electrochemical performance is greatly limited.In this study,a nickel/manganese sulfide material(Ni_(0.96)S_(x)/MnS_(y)-NC)with adjustable sulfur vacancies and heterogeneous hollow spheres was prepared using a simple method.The introduction of a concentration-adjustable sulfur vacancy enables the generation of a heterogeneous interface between bimetallic sulfide and sulfur vacancies.This interface collectively creates an internal electric field,improving the mobility of electrons and ions,increasing the number of electrochemically active sites,and further optimizing the performance of Na~+storage.The direction of electron flow is confirmed by Density functional theory(DFT)calculations.The hollow nano-spherical material provides a buffer for expansion,facilitating rapid transfer kinetics.Our innovative discovery involves the interaction between the ether-based electrolyte and copper foil,leading to the formation of Cu_9S_5,which grafts the active material and copper current collector,reinforcing mechanical supporting.This results in a new heterostructure of Cu_9S_5 with Ni_(0.96)S_(x)/MnS_(y),contributing to the stabilization of structural integrity for long-cycle performance.Therefore,Ni_(0.96)S_(x)/MnS_(y)-NC exhibits excellent electrochemical properties following our modification route.Regarding stability performance,Ni0_(.96)S_(x)/MnS_(y)-NC demonstrates an average decay rate of 0.00944%after 10,000 cycles at an extremely high current density of 10000 mA g^(-1),A full cell with a high capacity of 304.2 mA h g^(-1)was also successfully assembled by using Na_(3)V_(2)(PO_(4))_(3)/C as the cathode.This study explores a novel strategy for interface/vacancy co-modification in the fabrication of high-performance sodium-ion batteries electrode.

Designing multi-heterogeneous interfaces of Ni-MoS_(2)@NiS_(2)@Ni_(3)S_(2)hybrid for hydrogen evolution

The transition metal chalcogenides represented by MoS_(2)are the ideal choice for non-precious metal-based hydrogen evolution catalysts.However,whether in acidic or alkaline environments,the catalytic activity of pure MoS_(2)is still difficult to compete with Pt.Recent studies have shown that the electronic structure of materials can be adjusted by constructing lattice-matched heterojunctions,thus optimizing the adsorption free energy of intermediates in the catalytic hydrogen production process of materials,so as to effectively improve the electrocatalytic hydrogen production activity of catalysts.However,it is still a great challenge to prepare heterojunctions with lattice-matched structures as efficient electrocatalytic hydrogen production catalysts.Herein,we developed a one-step hydrothermal method to construct Ni-MoS_(2)@NiS_(2)@Ni_(3)S_(2)(Ni-MoS_(2)on behalf of Ni doping MoS_(2))electrocatalyst with multiple heterogeneous interfaces which possesses rich catalytic reaction sites.The Ni-MoS_(2)@NiS_(2)@Ni_(3)S_(2)electrocatalyst produced an extremely low overpotential of 69.4 mV with 10 mA·cm^(−2)current density for hydrogen evolution reaction(HER)in 1.0 M KOH.This work provides valuable enlightenment for exploring the mechanism of HER enhancement to optimize the surface electronic structure of MoS_(2),and provides an effective idea for constructing rare metal catalysts in HER and other fields.

A finite oxidation strategy for customizing heterogeneous interfaces to enhance magnetic loss ability and microwave absorption of Fe-cored carbon microcapsules

Metallic iron particles are of great potential for microwave absorption materials due to their strong magnetic loss ability.However,the oxidation susceptibility of metallic iron particles in the atmospheric environment is regarded as a major factor causing performance degradation.Although many efforts have been developed to avoid their oxidation,whether partial surface oxidized iron particles can improve the microwave absorbing performance is rarely concerned.In order to explore the effect of partial surface oxidation of iron on its properties,the designed yolk–shelled(Fe/FeO_(x))@C composites with multiple heterointerfaces were synthesized via an in-situ polymerization and a finite reduction–oxidation process of Fe_(2)O_(3)ellipsoids.The performance enhancement mechanisms of Fe/FeO_(x)heterointerfaces were also elaborated.It is demonstrated that the introduction of Fe-based heterogeneous interfaces can not only enhance the dielectric loss,but also increase the imaginary part of the permeability in the higher frequency range to strengthen the magnetic loss ability.Meanwhile,the yolk–shell structure can effectively improve impedance matching and enhance microwave absorption performances via increasing multiple reflection and scattering behaviors of incident microwaves.Compared to Fe@C composite,the effective absorption(reflection loss(RL)<−10 dB)bandwidth of the optimized(Fe/FeO_(x))@C-2 increases from 5.7 to 7.3 GHz(10.7–18.0 GHz)at a same matching thickness of 2 mm,which can completely cover Ku-band.This work offers a good perspective for the enhancement of magnetic loss ability and microwave absorption performance of Fe-based microwave absorption materials with promising practical applications.

Efficient Electromagnetic Wave Absorption and Thermal Infrared Stealth in PVTMS@MWCNT Nano‑Aerogel via Abundant Nano‑Sized Cavities and Attenuation Interfaces

Pre-polymerized vinyl trimethoxy silane(PVTMS)@MWCNT nano-aerogel system was constructed via radical polymerization,sol-gel transition and supercritical CO_(2)drying.The fabricated organic-inorganic hybrid PVTMS@MWCNT aerogel structure shows nano-pore size(30-40 nm),high specific surface area(559 m^(2)g^(−1)),high void fraction(91.7%)and enhanced mechanical property:(1)the nano-pore size is beneficial for efficiently blocking thermal conduction and thermal convection via Knudsen effect(beneficial for infrared(IR)stealth);(2)the heterogeneous interface was beneficial for IR reflection(beneficial for IR stealth)and MWCNT polarization loss(beneficial for electromagnetic wave(EMW)attenuation);(3)the high void fraction was beneficial for enhancing thermal insulation(beneficial for IR stealth)and EMW impedance match(beneficial for EMW attenuation).Guided by the above theoretical design strategy,PVTMS@MWCNT nano-aerogel shows superior EMW absorption property(cover all Ku-band)and thermal IR stealth property(ΔT reached 60.7℃).Followed by a facial combination of the above nano-aerogel with graphene film of high electrical conductivity,an extremely high electromagnetic interference shielding material(66.5 dB,2.06 mm thickness)with superior absorption performance of an average absorption-to-reflection(A/R)coefficient ratio of 25.4 and a low reflection bandwidth of 4.1 GHz(A/R ratio more than 10)was experimentally obtained in this work.

Heterostructured bimetallic phosphide nanowire arrays with latticetorsion interfaces for efficient overall water splitting

Designing cost-effective and high-efficiency electrocatalysts is critical to the water splitting performance during hydrogen generation.Herein,we have developed Fe_(2)P-Co_(2)P heterostructure nanowire arrays with excellent lattice torsions and grain boundaries for highly efficient water splitting.According to the microstructural investigations and theoretical calculations,the lattice torsion interface not only contributes to the exposure of more active sites but also effectively tunes the adsorption energy of hydrogen/oxygen intermediates via the accumulation of charge redistribution.As a result,the Fe_(2)P-Co_(2)P heterostructure nanowire array exhibits exceptional bifunctional catalytic activity with overpotentials of 65 and 198 mV at 10 mA cm^(-2) for hydrogen and oxygen evolution reactions,respectively.Moreover,the Fe_(2)P-Co_(2)P/NF-assembled electrolyzer can deliver 10 mA cm^(-2) at an ultralow voltage of1.51 V while resulting in a high solar-to-hydrogen conversion efficiency of 19.8%in the solar-driven water electrolysis cell.

Mechanical properties and friction-wear characteristics of VN/Ag multilayer coatings with heterogeneous and transition interfaces

The heterogeneous multilayer interface of VN/Ag coatings and transition multilayer interface of VN/Ag coatings were prepared on Inconel 781 and Si(100),and the microstructures,mechanical and tribological properties were investigated from 25 to 700℃.The results showed that the surface roughness and average grain size of VN/Ag coatings with transition multilayer interface are obviously larger than those of VN/Ag coatings with heterogeneous multilayer interface.The coatings with transition multilayer interface have higher adhesion force and hardness than the coatings with heterogeneous multilayer interface,and both coatings can effectively restrict the initiation and propagation of microcracks.Both coatings have excellent self-adaptive lubricating properties with a decrease of friction coefficient as the temperature increases,but their wear rates reveal a drastic increase.The phase composition of the worn area of both coatings was investigated,which indicates that a smooth Ag,Magnéli phase(V2O5)and bimetallic oxides(Ag3VO4 and AgVO3)can be responsible to the excellent lubricity of both coatings.To sum up,the coatings with transition multilayer interface have excellent adaptive lubricating properties and can properly control the diffusion rate and release rate of the lubricating phase,indicating that they have great potential in solving the problem of friction and wear of mechanical parts.

Hollow sphere of heterojunction(NiCu)S/NC as advanced anode for sodium-ion battery

Metal sulfide is considered as a potential anode for sodium-ion batteries(SIBs),due to the high theoretical capacity,strong thermodynamic stability and low-cost.However,their cycle capacity and rate performance are limited by the excessive expansion rate and low intrinsic conductivity.Herein,heterogeneous hollow sphere NiS-Cu_(9)S_(5)/NC(labeled as(NiCu)S/NC)based on Oswald ripening mechanism was prepared through a simple and feasible methodology.From a structural perspective,the hollow structure provides an expansion buffer and raises the electrochemical active area.In terms of electron/ion during the cycles,Na^(+)storage mechanism is optimized by NiS/Cu_(9)S_(5)heterogeneous interface,which increases the storage sites and shortens the migration path of Na^(+).The formation of built-in electric field strengthens the electron/ion mobility.Based on the first principle calculations,it is further proved the formation of heterogeneous interfaces and the direction of electron flow.As the anode for SIBs,the synthesized(NiCu)S/NC delivers high reverse capacity(559.2 mA h g^(-1)at 0.5 A g^(-1)),outstanding rate performance(185.3 mA h g^(-1)at 15 A g^(-1)),long-durable stability(342.6 mA h g^(-1)at 4 A g^(-1)after 1500cycles,150.0 m A h g^(-1)at 10 A g^(-1)after 20,000 cycles with 0.0025%average attenuation rate).The matching cathode electrode Na_(3)V_(2)(PO_(4))_(3)/C is assembled with(NiCu)S/NC for the full-battery that achieves high energy density(253.7 W h kg^(-1))and reverse capacity(288.7 mA h g^(-1)).The present work provides a distinctive strategy for constructing electrodes with excellent capacity and stability for SIBs.

Enhanced ionic conductivity in LAGP/LATP composite electrolyte

Nasicon materials （sodium superionic conductors） such as Li1.5A10.5Ge1.5（PO4）3 （LAGP） and Li1.4Al0.4Til.6（PO4）3 （LATP） have been considered as important solid electrolytes due to their high ionic conductivity and chemical stability. Compared to LAGP, LATP has higher bulk conductivity around 10^-3 S/cm at room temperature; however, the apparent grain boundary conductivity is almost two orders of magnitude lower than the bulk, while LAGP has similar bulk and grain boundary conductivity around the order of 10-4 S/cm. To make full use of the advantages of the two electrolytes, pure phase Li1.5A10.5Ge1.5（PO4）3 and Li1.4A10.4Ti1.6（PO4）3 were synthesized through solid state reaction, a series of composite electrolytes consisting of LAGP and LATP with different weight ratios were designed. XRD and variable temperature AC impedance spectra were carried out to clarify the crystal structure and the ion transport properties of the composite electrolytes. The results indicate that the composite electrolyte with the LATP/LAGP weight ratio of 80：20 achieved the highest bulk conductivity which shall be due to the formation of solid solution phase Li1.42Alo.42Geo.3Ti1 .28（PO4）3, while the highest grain boundary conductivity appeared at the LATP/LAGP weight ratio of 20：80 which may be due to the excellent interfacial phase between Li1＋xAlxGeyTi2-x-y（PO4）3/LATE All the composite electrolytes demonstrated higher total conductivity than the pure LAGP and LATE which highlights the importance of heterogeneous interface on regulating the ion transport properties.

Construction of dual heterogeneous interface between zigzag-like Mo–MXene nanofibers and small CoNi@NC nanoparticles for electromagnetic wave absorption

Two-dimensional(2D)transition metal carbides(MXene)possess attractive conductivity and abundant surface functional groups,providing immense potential in the field of electromagnetic wave(EMW)absorption.However,high conductivity and spontaneous aggregation of MXene suffer from limited EMW response.Inspired by dielectric–magnetic synergy effect,the strategy of decorating MXene with magnetic elements is expected to solve this challenge.In this work,zigzag-like Mo_(2)TiC_(2)–MXene nanofibers(Mo-based MXene(Mo–MXene)NFs)with cross-linked networks are fabricated by hydrofluoric acid(HF)etching and potassium hydroxide(KOH)shearing processes.Subsequently,Co-metal–organic framework(MOF)and derived CoNi layered double hydroxide(LDH)ultrathin nanosheets are grown inside Mo–MXene NFs,and the N-doped carbon matrix anchored by CoNi alloy nanoparticles formed by pyrolysis is firmly embedded in the Mo–MXene NFs network.Benefiting from synergistic effect of highly dispersed small CoNi alloy nanoparticles,a three-dimensional(3D)conductive network assembled by zigzag-like Mo–MXene NFs,numerous N-doped hollow carbon vesicles,and abundant dual heterogeneous interface,the designed Mo–MXene/CoNi–NC heterostructure provides robust EMW absorption ability with a reflection loss(RL)value of−68.45 dB at the thickness(d)of 4.38 mm.The robust EMW absorption performance can be attributed to excellent dielectric loss,magnetic loss,impedance matching(Z),and multiple scattering and reflection triggered by the unique 3D network structure.This work puts up great potential in developing advanced MXene-based EMW absorption devices.

Boosting charge transfer via interface charge reconstruction between amorphous NiFe-LDH and crystalline NiCo_(2)O_(4)for efficient alkaline water/seawater oxidation

Electrocatalysts with optimal efficiency and durability for the oxygen evolution reaction(OER)are becoming increasingly important as the demand for alkaline water/seawater electrolysis technology grows.Herein,a novel rose-shaped NiFe-layered double hydroxide(LDH)/NiCo_(2)O_(4)composed of amorphous wrinkled NiFe-LDH and highly crystalline NiCo_(2)O_(4)was synthesized with rich heterointerfaces.Many unsaturated metal sites are generated due to significant charge reconstruction at the heterointerface between the crystalline and amorphous phases.These metal sites could trigger and provide more active sites.The density functional theory(DFT)reveals that a new charge transfer channel(Co-Fe)was formed at the heterointerface between NiFe-LDH as electron acceptor and NiCo_(2)O_(4)as electron donor.The new charge transfer channel boosts interfacial charge transfer and enhances catalytic efficiency.The NiFe-LDH/NiCo_(2)O_(4)/nickel foam(NF)drives current densities of 10 and 100 mA·cm−2 with overpotentials of 193 and 236 mV,respectively.The composite electrode demonstrates a fast turnover frequency(0.0143 s−1)at 1.45 V vs.RHE(RHE=reversible hydrogen electrode),which is 5.5 times greater than pure NiCo_(2)O_(4),suggesting its superior intrinsic activity.Additionally,NiFe-LDH/NiCo_(2)O_(4)/NF electrode exhibited negligible degradation after 150 h of uninterrupted running in alkaline seawater oxidation.This study introduces a method for preparing high-efficiency electrocatalysts utilized in alkaline water/seawater electrolysis.

Structure regulating of metal clusters in carbonized metallic organic frameworks for high-efficient microwave absorption via tuning interaction strength between metals and ligands

Carbonized metallic organic frameworks(CMOF)have been attracting attention in microwave absorption(MA)research area because of their diverse structures,tunable compositions,and rich porosity.Herein,structure regulation on metal clusters in CMOF is achieved by tuning the interaction strength between metals and ligands to enhance microwave absorption performance.Due to relatively weak interaction among copper cations and ligands,copper nanoclusters(CuNC)can be uniformly formed and embedded within the cobalt/zinc(Co/Zn)CMOF.Firstly,copper cations are added to the Co/Zn bimetallic zeolitic imidazolate frameworks(ZIFs).Secondly,the CMOF composite particles with CuNCs(CuNCs/CoZn-CMOF)were developed by a pyrolysis process.The CuNCs/CoZn-CMOF with an appropriate amount of CuNCs can harmonize both dielectric and magnetic losses.As a result,the minimum reflection loss(RLmin)reaches–45.1 dB at a matching thickness of 2.30 mm and the effective absorption bandwidth(EAB)is 8.80 GHz at a thickness of 3.10 mm.The broadband response to electromagnetic waves is attributed to interfacial polarization at CuNCs surface and heterogeneous interfaces,impedance matching and multiple scattering of electromagnetic waves.This study provides a feasible method to develop CMOF microwave absorption materials with high EAB values.

Ultrathin self-assembly MXene/Co-based bimetallic oxide heterostructures as superior and modulated microwave absorber

Lightweight and high-efficiency absorbing materials equipped with tunable electromagnetic properties are the foremost important factors for driving applications of 5 G smart era and military stealth.Stim-ulated by the remarkable merits of heterogeneous interface engineering,a series of unique flower-like Co-based multiphases nanostructures were successfully synthesized through identical hydrothermal method,and subsequently anchored on the Ti_(3)C_(2)T_(x)nanosheets.The suitable metal ion modulation is feasible to regulate the components,heterogeneous interfaces and defects for tailoring the electromag-netic parameters and microwave absorption(MA)property.Notably,the permittivity decreases of CMOT(CoO/MCo_(2)O_(4)/Ti_(3)C_(2)T_(x),M=Fe,Cu,Zn)composites proceed gradually in the order of Fe^(2+),Cu^(2+),Zn^(2+),while the MA performance with tunable absorption peak could be modulated subtly.The asobtained CFOT-12(10 wt%),CCOT-15(10 wt%)and CZOT-15(15 wt%)exhibit excellent MA capacity with a minimum reflection loss(RL_(min))of-41.06,-52.67,-52.52 dB and corresponding effective absorption bandwidth(EAB)of 3.68,4.48,3.92 GHz at 2.10,1.90,1.80 mm,respectively.This work expands a novel approach to construct multicomponent heterostructure for tuning the EM parameters and absorbing property,as well as realize the high efficient and light weight.

Multiscale structure and interface engineering of Fe/Fe_(3)C in situ encapsulated in nitrogen-doped carbon for stable and efficient multi-band electromagnetic wave absorption

Most reported electromagnetic wave absorption(EWA)materials show significant effective absorption in a certain frequency range,but their performances deteriorate dramatically as the frequency changes.As the range of working frequencies for electronic devices is gradually widening,it is of great interest to explore frequency-insensitive EWA materials that can achieve efficient absorption in every waveband by simply changing the absorption thickness.To this end,a multi-scale absorber(Fe/Fe_(3) C@NC)is rationally synthesized by chemical foaming and in-situ growth strategy.By controlling the growth of carbon nan-otubes,the Fe/Fe_(3) C@NC-2 exhibits a well-constructed 3D multi-scale architecture.Thanks to dipole po-larization,interface polarization and magnetic-dielectric energy conversion,the Fe/Fe_(3) C@NC-2 overcomes the frequency dispersion behavior and keeps a stable dielectric attenuation capability across the entire frequency range.Consequently,it delivers a superb full-band absorption of-50.1,-59.83,-55.87 and-51.91 dB in the S,C,X and Ku bands,respectively.The maximum radar cross-sectional reduction reaches 35.44 dB m^(-2) when the incidentθis 20°,testifying its impressive performance.Surprisingly,this EWA material also shows a remarkable resistance to oxidation and corrosion derived from the tightly coated carbon layers.This work provides new insight into the design of multi-band and stable EWA materials for practical application.

Hierarchical Ni_(3)S_(4)@MoS_(2)nanocomposites as efficient electrocatalysts for hydrogen evolution reaction

Hydrogen evolution reaction(HER)through water splitting is a promising way to solve the energy shortage.Noble-metal-free HER electrocatalysts with high efficiency is very important for practical applications.Herein,we prepare the Ni_(3)S_(4)@MoS_(2)electrocatalyst on carbon cloth(CC)through a two-step hydrothermal process.The Ni_(3)S_(4)nanorods are uniformly integrated with the MoS_(2)nanosheets,forming a hierarchical structure and heterogeneous interfaces.The fast electron transfer on the interface enhances the kinetics of catalytic reaction.The hierarchical structure provides more exposed active sites.The Ni_(3)S_(4)@MoS_(2)/CC exhibits good catalytic activity and long-term stability for HER.This work provided a practicable strategy to develop efficient electrocatalysts for HER in alkaline media.

Interfacial dislocations dominated lateral growth of long-period stacking ordered phase in Mg alloys

Understanding the interface between strengthening precipitates and matrix in alloys, especially at the atomic level, is a critical issue for tailoring the precipitate strengthening to achieve desired mechanical properties. Using high-resolution scanning transmission electron microscopy, we here clarify the semicoherent interfaces between the matrix and long-period stacking ordered(LPSO) phases, including 18 R and 14 H, in Mg–Zn–Y alloys. The LPSO/Mg interface features the unique configuration of the Shockley partial dislocations, which produces a near zero macroscopic strain because the net Burgers vectors equal zero. The 18 R/Mg interface characterizes a dissociated structure that can be described as a narrow slab of 54 R. There are two dislocation arrays accompanied to the 18 R/54 R and 54 R/Mg interface, resulting a slight deviation(about 2.3°). The 14 R/Mg interface exhibits the dislocation pairs associated with solute atoms. We further evaluate the stability and morphology of the corresponding interfaces based on elastic interaction, via calculating the mutual strong interactions between dislocation arrays, as well as that between the dislocations and solute atoms. The synchronized migration of interfacial dislocations and solute atoms, like move-drag behavior, dominates the lateral growth of LPSO phases in Mg alloys.