Ribosome-inspired electrocatalysts inducing preferential nucleation and growth of three-dimensional lithium sulfide for high-performance lithium-sulfur batteries

Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.

Nucleation and growth control for iron-and phosphorus-rich phases from a modified steelmaking waste slag

Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable development in the steel industry.We had pre-viously found the possibility of recovering Fe and P resources,i.e.,magnetite(Fe_(3)O_(4)) and calcium phosphate(Ca_(10)P_(6)O_(25)),contained in steel-making slags by adjusting oxygen partial pressure and adding modifier B_(2)O_(3).As a fundamental study for efficiently recovering Fe and P from steelmaking slag,in this study,the crystallization behavior of the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt has been observed in situ,using a confocal scanning laser microscope(CLSM).The kinetics of nucleation and growth of Fe-and P-rich phases have been calculated using a classical crys-tallization kinetic theory.During cooling,a Fe_(3)O_(4) phase with faceted morphology was observed as the 1st precipitated phase in the isothermal interval of 1300-1150℃,while Ca_(10)P_(6)O_(25),with rod-shaped morphology,was found to be the 2nd phase to precipitate in the interval of 1150-1000℃.The crystallization abilities of Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases in the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt were quantified with the in-dex of(T_(U)−T_(I))/T_(I)(where T_(I) represents the peak temperature of the nucleation rate and TU stands for that of growth rate),and the crystalliza-tion ability of Fe_(3)O_(4) was found to be larger than that of Ca_(10)P_(6)O_(25) phase.The range of crystallization temperature for Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases was optimized subsequently.The Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases are the potential sources for ferrous feedstock and phosphate fertilizer,respectively.

Molecular simulation studies on natural gas hydrates nucleation and growth:A review

How natural gas hydrates nucleate and grow is a crucial scientific question.The research on it will help solve practical problems encountered in hydrate accumulation,development,and utilization of hydrate related technology.Due to its limitations on both spatial and temporal dimensions,experiment cannot fully explain this issue on a micro-scale.With the development of computer technology,molecular simulation has been widely used in the study of hydrate formation because it can observe the nucleation and growth process of hydrates at the molecular level.This review will assess the recent progresses in molecular dynamics simulation of hydrate nucleation and growth,as well as the enlightening significance of these developments in hydrate applications.At the same time,combined with the problems encountered in recent hydrate trial mining and applications,some potential directions for molecular simulation in the research of hydrate nucleation and growth are proposed,and the future of molecular simulation research on hydrate nucleation and growth is prospected.

Crystal Growth and Nucleation in Glasses in the Lithium Silicate System

The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi2O·(100 ﹣ x)SiO2 (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li2O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates Ist of lithium disilicate crystals in the 23.4Li2O·76.6SiO2, 26Li2O·74SiO2 and 29.1Li2O·70.9SiO2 glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates Ist for the glass of the stoichiometric lithium disilicate composition 33.51Li2O·66.5SiO2. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li2O-SiO2 system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.

Crystal Nucleation and Growth of Al-based Alloys Produced by Electrolysis

The nucleation and growth of grains in a series of Al-based alloys produced by electrolysis are observed under SEM. The atomic Ti/AI ratios of the nuclei and the distribution of Ti at certain points are analyzed by point EDS. The particles in different atomic Ti/AI ratios might act as the nuclei of α-Al. At the early stage of growth, the spherical Ti-enriched regions might form around these particles within very limited temperature ranges in which the reactions such as the peritectic reactions etc occur. At the latter stage of growth, the dendrites freely develop in the radial orientations, and the concentration of Ti decreases linearly along the dendrite arm and becomes negligible in the region near the periphery of the dendrite. It is believed that the nucleation is closely related with the number and dispersion of primary spherical areas in the melts, and the segregation of Ti leads to the free growth of dendrite, which is necessary for the formation of equiaxial grains.

Application of the Method of Characteristics to Population Balance Models Considering Growth and Nucleation Phenomena

The population balance modeling is regarded as a universally accepted mathematical framework for dynamic simulation of various particulate processes, such as crystallization, granulation and polymerization. This article is concerned with the application of the method of characteristics (MOC) for solving population balance models describing batch crystallization process. The growth and nucleation are considered as dominant phenomena, while the breakage and aggregation are neglected. The numerical solutions of such PBEs require high order accuracy due to the occurrence of steep moving fronts and narrow peaks in the solutions. The MOC has been found to be a very effective technique for resolving sharp discontinuities. Different case studies are carried out to analyze the accuracy of proposed algorithm. For validation, the results of MOC are compared with the available analytical solutions and the results of finite volume schemes. The results of MOC were found to be in good agreement with analytical solutions and superior than those obtained by finite volume schemes.

Guided lithium nucleation and growth on lithiophilic tin-decorated copper substrate

Lithium metal is the ultimate anode choice for high energy rechargeable lithium batteries owing to its ultra-high theoretical capacity,however,Li dendrites and low Coulombic efficiency(CE)caused by disordered Li plating restrict its practical application.Herein,we develop an ultrathin Sn-decorated Cu substrate(Sn@Cu)fabricated by an electroless plating method to induce ordered Li nucleation and growth behavior.The lithiophilic Sn interfacial layer is found to play a critical role to lower the Li nucleation over-potential and promote fast Li-migration kinetics,and the underlying mechanism is revealed using the first principle calculations.Accordingly,a dense dendrite-free and Li deposition with large granular morphology is obtained,which significantly improved the CE and cycling performance of Li‖Sn@Cu half cells symmetric cells.Symmetric cells using the Li-Sn@Cu electrode display a much-prolonged life span(>1200 h)with low overpotential(~18 mV)at a high current density of 1 mA cm^(-2).Moreover,full cells paired with commercial LiFePO_(4) cathode(1.8 mAh cm^(-2))deliver enhanced cycling stability(0.5 C,300 cycles)and excellent rate performance.This work provides a simple and effective way to bring about high efficiency and long lifespan substrates for practical applications.

TEM OBSERVATION OF NUCLEATION AND GROWTH OF BORIDE DURING BORONIZATION OF STEEL 20 AND INFLUENCE OF PRIOR DEFORMATION

The TEM observation on the single-side thinned specimens was made of the nucleation and growth of boride during boronization for steel 20 and the influence of prior room temperature deformation.The results of X-ray diffraction and electron probe microstructure analysis show that only Fe_2B formed in the surface layer of specimens at the beginning of boronization;the atomic concentration of B in the surface layer increased with the increase of deformation monotonously;and the segregation of B atoms in the dislocation cells hindered the recovery and recrystallization of the deformed structure of the matrix and accelerated the nucleation and growth of boride in the surface layer.

NUCLEATION AND GROWTH OF FERROUS MARTENSITES ALONG BOUNDARIES

Martensites distributed along the austenite grain boundaries and twin boundaries have been examined in Fe-C,Fe-Ni-C and Fe-Cr-Mn-Mo-C alloys.The martensites may nucleate preferentially and grow easily along these boundaries.In the mixed martensites,the preferentially formed one is plate or butterfly martensite

Establishment of nucleation and growth model of silica nanostructured particles and comparison with experimental data

A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model is compared with the experimental value obtained from SAXS data.The model provides a non-ideal improvement in the supersaturation calculation and considers the impact of both mass transfer and surface reaction on the particle growth rate.The nucleation and growth rates are coupled depending on the change in monomer concentration over time,based on which the particle size and distribution are calculated.The growth curve of the silica particles from 3 nm to 20 nm and the change in particle number from 0 to over 10^(20) are calculated,which are consistent with the experimental values,establishing the reliability of the model.The calculations of the growth rate reveal that mass transfer controls the growth of silica particles before 10 min and the surface reaction is the rate-determining step after 10 min.The changes in the model parameters obtained by fitting with the SAXS data under different reaction conditions indicate the sensitivity of the corresponding process to different conditions.Moreover,the relationship between the particle growth rate and monomer concentration change is analyzed using the proposed model.

MECHANISM OF THE GROWTH, NUCLEATION, AND HETEROEPITAXY OF METASTABLE DIAMOND FILMS ON ATOMIC SCALE

The mechanism of chemical-vapor-deposited (CVD) diamond film growth has attracted increasing attention recent years, mainly due to the fact that further technological advancement (such as obtaining high-quality films, controlling film growth, and heteroepitaxial growth, etc.) requires a more detailed understanding of the fundamental phenomena responsible for diamond growth.

Nucleation and growth of high purity aluminum grains in directional solidification bulk sample without electromagnetic stirring

A self-made directional solidification device was used to fabricate d 80 mm high purity aluminum ingots. SEM and AFM were used to detect the shape of grain boundaries. The orientation of the grain was studied by X-ray diffractometry. The results show that the nucleation points locate at the intersections of three adjacent grains. The lattice orientation of grains does not alter in the horizontal direction, but gradually approaches the optimum growth direction in the vertical direction during the growth process. All the grains suffer the competition and only the one whose orientation is closest to the preferred direction can occupy the final growth space.

Electrocrystallization nucleation and growth of NiFe alloys on brass substrate

The electrocrystalliztion nucleation and growth process of Ni-Fe alloy was studied using cyclic voltammetry and chronoamperometry. The results show that, in the case of high deposition overpotential, the nucleation/growth process of Ni-Fe binary alloy is 3-D instantaneous, and the growth rate of the previously formed nuclei increases with overpotential. However, at low overpotential, no distinguished nucleation current can be observed.Meanwhile, the discrepancy between the experimental non-dimensional variables(I/Im)2 and those calculated from the theoretical model was elucidated in the light of the molecular orbital theorem.

PPB structure elimination,DRX nucleation mechanisms and grain growth behavior of the3rd-generation PM superalloy for manufacturing aviation components

Previous Particle Boundary(PPB),as the detrimental structure in Powder Metallurgy(PM)components,should be eliminated by subsequent hot process to improve the mechanical properties.The objective is to investigate the Dynamic Recrystallization(DRX)nucleation mechanisms and grain growth behavior of the 3rd-generation PM superalloy with PPB structure.Microstructure observation reveals that PPB decorated with(Ti,Ta,Nb)C carbides belongs to the discontinuous chain-like structure.The elimination of PPB networks can be achieved effectively via hot deformation due to the occurrence of DRX.Four different DRX nucleation mechanisms were proposed and discussed in detail according to the special microstructure characteristics of the PM superalloy.Firstly,local lattice rotations can be detected in the vicinity of(Ti,Ta,Nb)C carbides during hot deformation and thus PPB structure serves as the preferential nucleation sites for DRX grains via Particle-Stimulated Nucleation(PSN).Then,Discontinuous-DRX(DDRX)characterized by grain boundary bulging dominates the microstructure refinement and Continuous-DRX(CDRX)operated by subgrain rotation can be regarded as an important assistant mechanism.At last,the initial Σ3 boundaries would lose their twin characteristics owing to the crystal rotation and then transform into the general High Angle Grain Boundaries(HAGBs).The distorted twins provide additional DRX nucleation sites,viz.,twin-assisted nucleation.Particular attention was focused on the grain growth behavior of the PM superalloy in subsequent annealing process.The recrystallization temperature was determined to be about 1110.C and 1140.C can be considered as the critical temperature for grain growth.The findings would provide theoretical support for microstructure refinement of the 3rd-generation PM superalloy,which is of pivotal significance for improving the mechanical properties of aviation components.

Theoretical investigation of lithium ions’ nucleation performance on metal-doped Cu surfaces

Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.

A MODEL FOR BAINITIC TRANSFORMATION KINETICS WITH PARABOLIC NUCLEATION RATE

Based on the assumptions of parabolic variation of nucleation rate versus time and transformation kinetics depending mainly on nucleation rate, a different model for bainitic transformation kinetics in hypoeutectoid steels was established. And this model was proved to be effective in the description of bainitic transformation by comparison with the result of conventional Avrami equation.

Nucleation of Fe-Rich Intermetallic Phases on α-Al_(2)O_(3) Oxide Films in Al-Si Alloys

Nucleation of Fe-rich intermetallic phases on α-Al2O3 oxide films was analyzed in five experimental Al-Fe-Mn-Si alloys. In an attempt to verify the role of α-Al2O3 films in nucleating Fe-rich intermetallics, experiments have been conducted under conditions where formed in situ oxide films were present. Some Fe-rich intermetallics are observed to be related with the oxide films in the microstructure, the present results are in accordance with some research that suggest that the Fe-rich intermetallic phases nucleate upon the oxide films. The intermetallic phases and α-Al2O3 films were unambiguously identified with the help of complementary techniques such as thermal analysis, SEM/EDS and X-ray diffraction.

NUCLEATION AND GPOWTH OF FERROUS MARTENSITES

In situ observations of the nucleation and growth of ferrous martensites,including ε-, lenticular,butterfly,thin-plate and composite-plate ones at low temperature stage on optical or transmission electron microscope were carried out.The results confirmed the faulting model for the formation of ε-martensite proposed by Olso and Cohen.The grain boundaries and tri- ple points are the favourable nucleation sites for the thin plates,and their surface relief grown initially like a small needle.The lenticular martensite was observed as two stages of formation.According to the dislocation resolving reaction. (a/6)[111]_b→(a/3)[]_b+(a/2)[111]_b,the emission dislocation(=(a/2)[111]_b)acting as the dislocation source for the transition of lattice invariant shear from twinning to slip was proposed.

Decline of nucleation in the heating process with a high heating rate

The effect of the heating rate on the nucleation of metallic glass in a rapid heating process starting from the glass transition temperature is investigated. The critical nucleus radius increases with the increase of the temperature of the undercooling liquid. If the increment rate of the critical nucleus radius, owing to the heating process, is higher than the growth rate of the nuclei, the nuclei generated at the low temperature will become the embryos at the high temperature. This means that the high heating rate can make no nucleation happen in the heating process. In consideration of the interfacial energy, the growth rate of the nuclei increases with the increase of their size and the growth rate of the critical nucleus is zero. Thus, the lower heating rate can also make the nuclei decline partially. Finally, this theory is used to analyze the nucleation process during laser remelting metallic glass.

Volume and Surface Nucleation of Crystals in Glass Based on Blast-Furnace Slag

Using differential thermal analysis, X-ray phase analysis, electron microscopy, and optical microscopy, the nucleation of crystals in glass obtained by blending metallurgical slag with silicon dioxide has been studied. The type of crystallization (homogeneous or heterogeneous, volume or surface) is revealed for each of nine compositions of synthesized glass. It is shown that the first crystalline phase in a volume crystallizing glass is perovskite (CaO·TiO2);in this phase a nucleation of the main phase occurs: melilite (solid solution of gehlenite 2CaO·Al2O3·SiO2 in akermanite 2CaO·MgO·2SiO2). The fundamental characteristics of homogeneous (for a catalizing phase, perovskite) and heterogeneous (for a catalyzed phase, melilite) of crystallization are determined: the steady state nucleation rate Ist, time of unsteady state nucleation τ, crystal growth rate U, and activation energy of frictional flow. The temperature dependences of Ist, τ, and U are obtained. The kinetics of the crystallization of glass is studied and the rates of the surface crystal growth are determined in the glass of nine compositions. The influence of grinding the particles of the original glass on the sequence of deposition of the crystalline phases was studied. Practical recommendations are presented for the use of blast-furnace slag as a raw material for the synthesis of glass and their further utilization.