Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

An improved ion-exchange/diffusion method for ～(15)N isotope tracing analysis of nitrate in surface waters from watersheds

An improved method,suitable for collecting nitrate from surface waters in the watershed for 15 N isotope tracing analysis,was developed on the basis of the anion exchange coupled with diffusion through systematic simulation and comparison experiments.The results showed that the nitrate could be separated and enriched from the waters efficiently by using the improved method.Being simple and practical in operation principle and procedures,cost-economic,and highly efficient in nitrate separation/enrichment,the method met the requirements of δ 15 N mass spectrum analysis and would lay a foundation for the application of 15 N isotope tracing approach to the research on non-point source pollution in watershed.

Numerical Simulation on Intergranular Microcracks in Interconnect Lines Due to Surface Diffusion Induced by Stress-,Electro-and Thermo-migration

Based on the weak formulation for combined surface diffusion and evaporation-condensation,a governing equation of the finite element is derived for simulating the evolution of intergranular microcracks in copper interconnects induced simultaneously by stressmigration,electromigration and thermomigration.Unlike previously published works,the effect of thermomigration is considered.The results show that thermomigration can contribute to the microcrack splitting and accelerate the drifting process along the direction of the electric field.The evolution of the intergranular microcracks depends on the mechanical stress field,the temperature gradient field,the electric field,the initial aspect ratio and the linewidth.And there exists a critical electric fieldχ_c,a critical stress field■,a critical aspect ratioβ_c and a critical linewidth■.When■or■,the intergranular microcrack will split into two or three small intergranular microcracks.Otherwise,the microcrack will evolve into a stable shape as it migrates along the interconnect line.The critical stress field,the critical electric field and the critical aspect ratio decrease with a decrease in the linewidth,and the critical linewidth increases with an increase in the electric field and the aspect ratio.The increase of the stress field,the electric field or the aspect ratio and the decrease of the linewidth are not only beneficial for the intergranular microcrack to split but also accelerate the microcrack splitting process.

Diffusion of lanthanum in nanocrystallized surface layer during plasma rare earth nitriding of 3J33B steel

Plasma rare earth nitriding of nanocrystallized surface layer of 3J33B steel at 350 and 410℃ for different time was studied. The microstructure observation and X-ray diffraction（XRD） analysis show that the nitriding layer consists of compound layer （γ′-Fe4N） and diffusion layer （α-Fe）. Lanthanum content profiles in nanocrystallized surface layer were measured using glow discharge spectometry（GDS）. The results show that lanthanum can diffuse into the surface layer of the steel to a large depth. Based on the experimental results mentioned above, the diffusion coefficients and activation energy of lanthanum in γ′ phase are calculated to be 1.03×10 -15 cm2/s （350℃）, 1.75×10 -15 cm2/s （410℃） and 31.313kJ/mol, respectively.

Adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co(200): A first-principles density-functional study

First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.

Boundary scheme for lattice Boltzmann modeling of micro-scale gas flow in organic-rich pores considering surface diffusion

We propose a boundary scheme for addressing multi-mechanism flow in a porous medium in slip and early transition flow regimes, which is frequently encountered in shale gas reservoirs. Micro-gaseous flow in organic-rich shale involves a complex flow mechanism. A self-developed boundary scheme that combines the non-equilibrium extrapolation scheme and the combined diffusive reflection and bounce-back scheme(half-way DBB) to embed the Langmuir slip boundary into the single-relaxation-time lattice Boltzmann method(SRT-LBM) enables us to describe this process, namely, the coupling effect of micro-gaseous flow and surface diffusion in organic-rich nanoscale pores. The present LBM model comes with the careful consideration of the local Knudsen number, local pressure gradient, viscosity correction model, and regularization procedure to account for the rarefied gas flows in irregular pores. Its validity and accuracy are verified by several benchmarking cases, and the calculated results by this boundary scheme accord well with our analytical solutions.This boundary scheme shows a higher accuracy than the existing studies. Additionally, a subiteration strategy is presented to tackle the coupled micro-gaseous flow and surface diffusion, which necessitates the iteration process matching of these two mechanisms. The multi-mechanism flow in the self-developed irregular pores is also numerically investigated and analyzed over a wide range of parameters. The results indicate that the present model can effectively capture the coupling effect of micro-gaseous flow and surface diffusion in a tree-like porous medium.

The diffusion and concentration effects of formamide on a TiO₂surface in the presence of a water solvent

The formamide-titanium oxide interaction mechanism is a research target of great importance for understanding the elementary events of the origin of life: the synthesis of nucleoside bases and formation of biological molecules needed for life. Titanium oxide (TiO2) can act as a strongly adsorbing surface or a catalytic material. In the present study, a comparative molecular dynamics analysis performed to clarify the adsorbing and diffusion properties of liquid formamide on a TiO2 surface in the presence of water molecules. The structural features of the formamide concentration effect (the accumulation of molecules) on a TiO2 surface in the presence and absence of water solvent are cleared up. Modification of the formamide diffusion abilities mediated by a water solvent is observed to correlate with the formamide-water concentration distribution on the surface.

Synthesis of Y_2O_3:Eu^(3+) phosphors by surface diffusion and their photoluminescence properties

Y2O3:Eu3+ phosphors were synthesized by the surface diffusion method (SDM). X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS) were used to characterize the structure, morphology and component of Y2O3:Eu3+ phosphors. The photoluminescent (PL) properties were also investigated. The results reveal that the PL intensity of Y2O3:Eu3+ phosphors prepared by the surface diffusion method (SDM) is much higher than that prepared by homogeneous co-precipitation. The luminescence efficiency of the sample (Y0.997, Eu0.003)2O3 prepared by the SDM is almost 1.9 times that by homogeneous co-precipitation. The concentration of Eu3+ in the phosphor Y2O3:Eu3+ prepared by the surface diffusion can be reduced greatly owing to the activator, Eu3+ ions, distributing mainly in the outer layer of the phosphors where the photon generation process occurs.

EVOLUTION OF ROUGHNESS ON THE SURFACE OF A STRAINED ELASTIC MATERIAL DUE TO STRESS-DRIVEN SURFACE DIFFUSION

The free energy of a stressed crystal is assumed to consist of elastic strain energy and surface energy, and the chemical potential for surface diffusion at constant temperature is obtained under this assumption. A gradient in chemical potential results in diffusive mass transport along the surface. The result is applied in considering the phenomena of instability of a flat surface in a stressed material under fluctuations in surface shape, and the transient evolution of surface roughness due to an initial perturbation in the nearly flat free surface of the material, both under plane strain conditions.

Effect of Electric Field-Assisted Diffusion on Surface Layer Structure and Mechanical Properties of Soda-Lime Glasses

Soda-lime glasses were treated by electric field-assisted diffusion（EFAD） process. The mechanical properties and structural evolution on both glass anode and cathode surfaces were investigated, respectively. It was found that the EFAD resulted in the formation of a Na depletion layer on anode surface, which caused the relaxation of the glass anode surface network and the formation of a number of defects. Correspondingly, the hardness and flexural strength declined in anode surface compared to that of the original glass. On the other hand, the EFAD also created a compressive layer on cathode surface, causing the improvement of the hardness and flexural strength on cathode surface. The defected structure could be reconstructed by additional annealing process.

First-principles study of diffusion behaviour of point defects in the O-terminated (0001) surface in wurtzite ZnO

A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated （0001） surface in wnrtzite ZnO was performed. The 0 vacancy and interstitial are found to diffuse much more easily in surface than in bulk. The Zn vacancy has a similar migration barrier for both bulk and surface, but has much smaller barrier for the diffuse-in process. The Zn interstitial is difficult to diffuse in the surface directly, but it can diffuse into the bulk relatively easily. Specific values of corresponding migration barriers are obtained.

Surface diffusion of Si, Ge and C adatoms on Si (001) substrate studied by the molecular dynamics simulation

Depositions of Si, Ge and C atoms onto a preliminary Si （001） substrate at different temperatures are investigated by using the molecular dynamics method. The mechanism of atomic self-assembling occurring locally on the flat terraces between steps is suggested. Diffusion and arrangement patterns of adatoms at different temperatures are observed. At 900 K, the deposited atoms are more likely to form dimers in the perpendicular [110] direction due to the more favourable movement along the perpendicular [110] direction. C adatoms are more likely to break or reconstruct the dimers on the substrate surface and have larger diffusion distances than Ge and Si adatoms. Exchange between C adatoms and substrate atoms are obvious and the epitaxial thickness is small. Total potential energies of adatoms and substrate atoms involved in the simulation cell are computed. When a newly arrived adatom reaches the stable position, the potential energy of the system will decrease and the curves turns into a ladder-like shape. It is found that C adatoms can lead to more reduction of the system energy and the potential energy of the system will increase as temperature increases.

Preparation of Hydrophobic Surface on Titanium by Micro-Rolling and Laser Diffusion Carbonitriding

The application of rolling for fabricating grate on titanium stripe has been explored in this paper. Then the mechanically robust Ti（C,N） diffusion layer was synthetized directly on the grates by laser carbonitriding in the mixture gas of nitrogen and methane. The results shows that the carbonitriding process is accelerated by temperature enhancement with decreasing scanning speed, The Ti（C,N） diffusion layer is kept at 2 ~nn in thickness, when the scanning speed is smaller than 4 mm/s. The contact angle increases from 20~ to 143.6~ by designing an appropriate grate size and surface roughness. Meanwhile, the relationship between hydrophobicity, hardness performance and scanning speed is also discussed. The hardness of diffusion layer increases with decreasing laser scanning speed, and is up to 11.2 GPa. The surface structure and hydrophobic state are maintained after three cycles of sandpaper abrasion, which has improved the robustness of surface grate.

Diffusion-controlled Adsorption Kinetics at Air/Solution Surface Studied by Maximum Bubble Pressure Method

In studying the diffusion-controlled adsorption kinetics of aqueous surfactant solutions at the air/solution surface by means of the maximal bubble pressure method, Fick's diffusion equation for a sphere should be used. In this paper the equation was solved by means of Laplace transformation under different initial and boundary conditions. The dynamic surface adsorption F(t) for a surfactant solution, which was used to describe the diffusion-controlled adsorption kinetics at the solution surface, was derived. Different from the planar surf aceadsorption, the dynamic surface adsorption Г(t) for the short time consists of two terms: one is the same as Ward-Tordai equation and the other reflects the geometric effect caused by the spherical bubble surface. This effect should not be neglected for the very small radius of the capillary. The equilibrium surface tension γeq and the dynamic surface tension γ(t) of aqueous C10E6 [CH3(CH2)9(OCH2CH2)6OH] solution at temperature 25℃ were measured by means of Wilhelmy plate method and maximal bubble pressure method respectively. As t→0, the theoretical analysis is in good agreement with experimental results and the dependence of γ(t) on (√t+r0/√πD)^2 is linear.

SURFACE SELF-DIFFUSION ANISOTROPY OF TUNGSTEN ATOMS ON W(112) PLANE

Surface self-diffusion anisotropy of tungsten on W(112)plane has been measured along(Ⅱ)and across(丄)channels existed on this plane by using the field emission fluctuation method in two forms of the probeholes.In the round probehole the thermal activation energy E=13.0kcal,and the prefactor of the surface self-diffusion coefficient Dq=^.5X 70_7cm2s-1;in the long narrow rectangular slit,E(Ⅱ)=13.2kcal,D0(Ⅱ)=7.1×10-7crr^and E(丄)=6.2kcal,Do(丄)=1.8×10^(-9)cm^(2)s^(-1) at T=500-700K.The experimental data suggest that a W atom diffusing across channels should not climb over the channel wall,which would certainly require a much higher activation energy,but instead,displace an atom in the wall.This process reqwes a much smaller activation energy;however,since it involves concerted motion of at least two atoms,it will also have a much smaller prefactor.

SURFACE SELF-DIFFUSION AND THERMAL ROUGHENING OF TUNGSTEN SURFACES STUDIED BY FIELD EMISSION FLUCTUATION METHOD

Surface self-diffusion measurements of tungsten atoms and other defects were carried out by means of field emission fluctuation method at various positions along the zones(011)-(112)and(011)-(001).The experimental results shod that the self-diffusion on stepped surface can be used to investigate thermal roughening procedures.

Improving sound diffusion in a reverberation tank using a randomly fluctuating surface

Underwater reverberation environments that satisfy the conditions of uniformity and isotropy of the diffuse field can be used to measure the acoustic characteristics of underwater targets.This study combines two practical indicators—the standard deviation of the absolute sound pressure field(to indicate uniformity)and the analysis of the wavenumber spectrum in the spherical harmonics domain(to indicate isotropy)—for an accurate evaluation of the diffusion of the sound field in a reverberation tank.A method is proposed that can improve the narrow-band diffusion of the sound field by employing a randomly fluctuating surface.An acoustic experiment was performed in a reverberation water tank(1.2 m×1 m×0.8 m),where a randomly fluctuating surface was generated by making waves.The experimental results show that as the wave motion contributes effectively to the random reflection of sound rays in all directions,the uniformity and isotropy are improved significantly when the surface is fluctuating randomly.This work helps to ensure accurate measurements of the characteristics of underwater targets in reverberation tanks.

Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters（hexamer and above）, the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster,vacancy formation, filling, and shifting can be observed from the results.

Driving the Diffusion of Cesium Atoms of Graphite Monolayers on Metal Surfaces into Rhenium (1010)

It has been shown experimentally for the first time that diffusion of cesium n rhenium takes place at irradiation of atoms flux heated up to Т ≤ 1800 K -C. Analysis of thermal desorption spectra showed that cesium forms two high-temperature phases during adsorption of cesium on graphite monolayer in rhenium heated up to 1800 K. The first, intercalated phase starts filling immediately and grows up to maximum concentration. The second, diffusion phase appears with slight delay and grows incessantly during adsorption. It is for the first time that the Fick Equation has been applied for such kind of diffusion. Correspondences and average displacement L = f(Т,t) have been obtained at diffusion of surface cesium in rhenium in the interval of temperatures 1600 K Т ν = 5 × 1013 cm-2·s-1, U = +2000 V, T = 1700 K, effectiveness of cesium diffusion δCs in the system of Re(1010)-C was identified with application of suggested methods, which showed δCs = 0.45. Activation energies of Сs atoms diffusion in rhenium from rhenium were found and values Е1p = 5.65 ± 0.05 eV and Еp1 = 5.85 ± 0.05 eV were obtained respectively. Effect of electrical field on intercalation and cesium diffusion in Re-C was observed.