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.

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.

Electrodeposited PtNi nanoparticles towards oxygen reduction reaction:A study on nucleation and growth mechanism

In this work,highly monodispersed Pt-Ni alloy nanoparticles were directly deposited on carbon substrate through a facile electrodeposition strategy in the solvent system of N,N-dimethylformamide(DMF).A series of carbon supported Pt-Ni alloy electrocatalysts were synthesized under different applied electrode potentials.Among all as-obtained samples,the Pt-Ni/C electrocatalyst deposited at-1.73 V exhibits the optimal specific activity up to 1.850 mA cm^(-2)at 0.9 V vs.RHE,which is 6.85 times higher than that of the commercial Pt/C.Comprehensive physiochemical characterizations and computational evaluations via density functional theory were conducted to unveil the nucleation and growth mechanism of PtNi alloy formation.Compared to the aqueous solution,DMF solvent molecule must not be neglected in avoiding particle agglomeration and synthesis of monodispersed nanoparticles.During the alloy co-deposition process,Ni sites produced through the reduction of Ni(Ⅱ)precursor not only facilitates Pt-Ni alloy crystal nucleation but also in favor of further Pt reduction on the Ni-inserted Pt surface.As for the deposition potential,it adjusts the final particle size.This work provides a hopeful extended Pt-based catalyst layer production strategy for proton exchange membrane fuel cells and a new idea for the nucleation and growth mechanism exploration for electrodeposited Pt alloy.

Nucleation and growth of L1_(2)-Al_(3)RE particles in aluminum alloys:A first-principles study

The internal mechanisms of nucleation and growth of L1_(2)-AI_(3)RE(RE=Sc,Y,La-Lu) second phases in Al alloys were investigated by combining first-principles calculations with quasi-harmonic approximation(QHA).The calculated results show that the diffusion rate D_s and chemical potential AG_V increase with the increase of temperature.With the increase of atomic number,the D_s and the strain energy ΔE_(CS)increase firstly from Sc to La,and then decreases,while the calculated interface energy γ_(α/β) and ΔG_V show opposite tendency.Based on above calculated results,the critical nucleation radius R*and coarsening rate K_(LSW) are obtained from the classical nucleation theory(CNT) and LSW model of the Ostwald ripening of particles,respectively.With the increase of atomic number,the R*increases firstly,and then decreases for all planes at finite temperatures.Whereas the K_(LSW) shows opposite variation to the R^(*).From this point of view,it is reasonably speculated that Y and later RE elements can replace the expensive Sc for heat-resistance Al alloys.The solubility c_(∞) of particles is usually very small at low temperature,and there is obvious solubility only when the temperature reaches 600 K.The surface energies E_(sur) of AI_(3)RE compounds and Al solid solution are respectively larger and smaller than that of pure Al,respectively,except for the surface(001) and(110) of Al_(3)La.For all planes,with the increase of atomic number of RE,E_(sur) decreases firstly from Sc to La,and then increases linearly to Lu.These results are helpful for designing high performance heat-resistance Al alloys.

Size, phase-controlled synthesis,the nucleation and growth mechanisms of NaYF_4:Yb/Er nanocrystals

Near-monodisperse NaYF4：Yb/Er nanoparticles（NPs） with controlled size, phases（α,β） and shapes（sphere, and hexagonal plate） were synthesized by adjusting the NaF to RE（RE = Y, Yb, Er） ratios, the reaction temperature and time in the hot surfactant solutions（oleic acid, 1-octadecene） from the improved one-pot thermal decomposition metal trifluoroacetate, and the precursors were prepared via hydrothermal route. The growth kinetics of β-NaYF4 NPs includes several stages： nucleation, growth of aNaYF4, Ostwald ripening, size shrinkage and growth. The results prove that the temperatures are preferred to the phase transformation compared with the NaF content when other experimental conditions are unchanged. Our work will further facilitate the comprehension of the nucleation and growth mechanisms of the NPs, and provide guidance for their controlled synthesis.

Nucleation and growth of Fe-rich phases in Al-5Ti-1B modified Al-Fe alloys investigated using synchrotron X-ray imaging and electron microscopy

Plate-like Fe-rich intermetallic phases directly influence the mechanical properties of recycled Al alloys;thus, many attempts have been made to modify the morphology of these phases. Through synchrotron X-ray imaging and electron microscopy, the underlying nucleation and growth mechanisms of Fe-rich phases during the solidification of Al-5 Ti-1 B-modified Al-2 Fe alloys were revealed in this study. The results showed that the Al-5 Ti-1 B grain refiner as well as the applied pressure both resulted in reduction of the size and number of primary Al_(3)Fe phases and promoted the formation of eutectic Al_(6)Fe phases.The tomography results demonstrated that Al-5 Ti-1 B changed the three-dimensional(3 D) morphology of primary Fe-rich phases from rod-like to branched plate-like, while a reduction in their thickness and size was also observed. This was attributed to the fact that Ti-containing solutes in the melts inhibit the diffusion of Fe atoms and the Al_(3)Fe twins produce re-entrant corner on the twin boundaries along the growth direction. Moreover, the TiB_(2) provides possible nucleation sites for Al_6Fe phases. The nucleation mechanism of Fe-rich phases is discussed in terms of experimental observations and crystallography calculations. The decrease in the lattice mismatch between TiB_(2) and Al_(6)Fe phases was suggested, which promoted the transformation of Al_(3)Fe to Al_(6)Fe phases.

Modeling of Nucleation and Growth of M_(23)C_6 Carbide in Multi-component Fe-based Alloy

Three-dimensional atom probe （3DAP） technique has been used to study the nucleation and growth of M23C6 carbide in a supersaturated multi-component Fe-based alloy aged at 800℃. 3D images indicate that the radius of M23C6 carbide after ageing for 10 min is about 9 nm. Concentration profiles of alloy elements in the carbide are also obtained. Combined with PANDAT and Thermo-Calc software, attempts to model the early stages of precipitation are present. The calculated particle size and composition of M23C6 carbide is in good agreement with 3DAP data.

Early Stages of CeO_(2) Thin-film Nucleation and Growth with Photo Irradiation

In this paper,the early stages of nucleation and photoirradiation growth of CeO_(2) thin films have been studied.Cyclic voltammetry,chronoamperometry and scanning electron microscopy were used to analyze the nucleation process of CeO_(2) thin films deposited on the anode with photo irradiation.Experimental results show that the anodic deposition process with photo illumination is controlled by diffusion.Compared with the dark state,photo illumination mainly contributed to increase the current density of the three-dimensional nucleation process,because photo illumination is helpful to create active sites and accelerate the nucleation progress on the surface that a thin ceria film has been formed.Two-dimensional nucleation process mainly exists within the initial 2 s,and then only three-dimensional instantaneous nucleation process continues,which may be the main reason why the thickness of the CeO_(2) film can continue to grow with photo illumination but not in the dark state.Increasing the deposition overpotential can promote two-dimensional nucleation and growth rate,whilst when the potential exceeds 0.65 V,three-dimensional current density decreases.The limiting factor at that time may be the diffusion rate of cerium ions in the solution towards the electrode substrate.

Effect of pre-recovery on subsequent recrystallization kinetics in moderately deformed and supersaturated Al–Mn alloys

The effect of pre-recovery on the recrystallization kinetics of a supersaturated Al–Mn alloy annealed at 530°C was investigated.The results show that the pre-recovery treatment can lead to faster recrystallization kinetics at the initial stage but cause sluggish recrystallization at the later stage.This different recrystallization behavior is explained by the formation of precipitates-free zones and the consumption of driving force during the pre-recovery treatment.The promoted recrystallization at the early stage can be interpreted by the promotion of recrystallization nucleation through sub-grain growth to a critical size inside precipitates-free zones.A simple model is presented to describe the nucleation of recrystallization with pre-recovery treatment in the supersaturated Al–Mn alloys.

A diffusion model for solute atoms diffusing and aggregating in nuclear structural materials

In nuclear structural materials, the nuclear irradiations induce the precipitations of soluble elements or produce the insoluble elements such as He atoms that may form clusters, heavily shortening the service life-times of the materials. In the present work, a diffusion model is developed to predict where and how fast the solute atoms （either soluble or insoluble） aggregate, and this model is applied to the study of the formation and growth of He bubbles in metal tritides （PdT0.6, ErT2, NbT0.0225, VT0.5, TaT0.097, TiT1.5, ZrT1.6） within one thousand days. The results are in good agreement with the available experimental observations and suggest that searching for metals with a barrier of more than 1.1 eV for a single He atom diffusion and making more defects in metal tritides can significantly reduce the growth of He bubbles and extend the service time of the metals.

Synergistic effects of chloride anions and carboxylated cellulose nanocrystals on the assembly of thick three-dimensional high-performance polypyrrole-based electrodes

Porous three-dimensional (3D) structures generally improve the performance of electrodes by increasing their active surface area and the diffusion speed of electrolyte ions during charging/discharging.Threedimensional polypyrrole (PPy) based films were created by electrodepositing PPy in the presence of varying amounts of chloride anions (Cl^(-)) and polyanionic ribbonlike nanoparticles (carboxylated cellulose nanocrystals (CNC-COO-)) as scaffold material.The assembly mechanism of the 3D PPy electrodes combines the effect of different nucleation and growth mechanisms during electropolymerization and deposition of the formed PPy with CNC-COO-and with Cl^(-).The highest area capacitance of these electrode materials was 1.39 F cm^(-2)(150.2 F g^(-1)) at a current density of 1 m A cm^(-2)(0.1 A g^(-1)).More importantly,at a high current density of 20 m A cm^(-2)(2.2 A g^(-1)),the thick (ca.130μm),3D,and high mass loading(9.2 mg cm^(-2)) Cl^(-):CNC-COO-/PPy films exhibited an excellent areal capacitance of 0.85 F cm^(-2)(70.8 F g^(-1)),increasing about 16%over CNC-COO-/PPy films prepared without Cl^(-)present during electrodeposition.In addition,an aqueous Cl^(-):CNC-COO-/PPy (with Cl^(-):CNC-COO-=2.0) symmetric supercapacitor had an outstanding energy density of 41.15μWh cm^(-2)(4.46 Wh kg^(-1)) and excellent cycling stability,while even improving on its original areal capacitance (to 111.2%of its original capacitance) after cycling3000 cycles at 8 m A cm^(-2),indicating their potential in energy storage devices.

Electrochemical Quartz Crystal Microbalance(EQCM) Characterization of Electrodeposition and Catalytic Activity of Pd-based Electrocatalysts for Ethanol Oxidation

Pd was electrochemically deposited on gold-coated quartz crystals at nanogram-level. The coulombic efficiency and initial nucleation and growth mechanism of potentiostatic Pd deposition were investigated via in situ electrochemical quartz crystal microbalance（EQCM）. The coulombic efficieneies are 84%, 93% and 95% for Pd deposition at 0.3, 0.2 and 0.1 V（vs. SCE）, respectively. The results of chronoamperometric measurements show that the Pd deposition proceeded by an instantaneous nucleation（at 0.3 V） or progressive nucleation（at 0.2 and 0.1 V） in a three-dimensional（3D） growth mode. The catalytic activity of Pd-based electrocatalyst for ethanol oxidation was characterized in an alkaline solution. It was found that the highest mass activity for ethanol oxidation on Pd-based electrocatalyst is 1.8× 10^4 A/（g Pd） deposited at 0.3 V for 5 s.

Experimental and Computational Study of the Effect of Temperature on the Electro-Polymerization Process of Thiophene

Temperature effect on the nucleation and growth mechanisms (NGM) of poly(thiophene) (PTh) was investigated through experimental and computational tools. The computational simulation method was based on a kinetic Monte Carlo algorithm. It reproduced key processes such as diffusion, oligomerization, and the precipitation of oligomers onto the electrode surface. Electrochemical synthesis conditions at temperatures between 263 and 303 K were optimized. The deconvolution of the i-t transients reflected two contributions: a progressive nucleation with three-dimensional growth controlled by diffusion and the other by charge transfer, PN3Ddif and PN3Dct, respectively. As temperature decreased, a diminution of the charge associated to each contribution was observed and the nucleation induction time increased. Experimental and computational evidence indicated that temperature does not change the nucleation and growth mechanism (NGM). This effect was ascribed to kinetic factors rather than to film conductivity. This work contrasts simulation and experimental evidence and demonstrates how computational simulations can help to understand the electrochemical process of conducting polymers formation.

Effect of mixing temperature on microstructure of an Al-Si alloy prepared by controlled diffusion solidification

The effects of mixing temperature,i.e.,the temperatures of two precursor melts(pure Al and Al-12Si),on the temperature and solute fields of resultant mixture,the nucleation and growth,and the size and morphology of primary grains during controlled diffusion solidification(CDS) of Al-8Si alloy were investigated by using simulation and calculation.The results indicate that a lower mixing temperature is helpful for achieving more supercooled microscale Al-rich pockets in the mixture,and increasing the width and supercooling degree of supercooling zone in the Al-rich pockets,and thus,the nucleation rate.The nuclei grow up in nondendritic mode,resulting in spheroidal,at least,nondendritic grains.In a successful CDS,the superheat degrees of the two precursor melts should be limited within several degrees,and it is not necessary to extra stipulate the superheat degree of target alloy melt(Al-8Si) when the requirement about Gibbs energies of the three melts is matched.Subsequent observation on casting microstructures shows that the employed simulation and calculation processes are reasonable and the achieved results are reliable.

Impact of uneven distribution of grain characteristics on yield strength and martensitic transformation of as-hot-rolled medium-entropy alloys

As-hot-rolled medium-entropy alloys(MEAs)with unevenly distributed grain sizes of face-centered cubic grains exhibit better yield strength without uniform elongation loss compared to cold-rolled and an-nealed ones.Successive operation of dynamic recrystallization(DRX)during several hot rolling passes leads to a wide range of grain sizes from submicrons to tens of micrometers due to the grain growth after nucleation:early recrystallized grains are coarser than recently recrystallized ones.Not only the grain size but internal dislocation density of the recently recrystallized grain is low.During the tensile deformation of the hot-rolled MEAs at-196 ℃,dislocation pile-ups in the relatively soft and fine DRX grains enhance yield stress and hetero-deformation-induced strain hardening.Thanks to the enhanced yield stress of the as-hot-rolled MEAs,stress-induced martensitic transformation easily occurs.Notably,partially DRXed MEAs hot-rolled at 800 ℃ have lower yield stress than fully DRXed ones,hot-rolled at 900 and 1000 ℃.This is attributed to the softening effect of the stress-induced body-centered cubic martensitic transformation in unrecrystallized coarse grains prior to the yielding,which lowers the yield stress of the partially DRXed ones.After yielding,the martensitic transformation facilitates strain hard-ening and early necking is precluded.This study presents a fresh outlook on the uneven distribution of grain sizes by hot rolling beneficial to mechanical responses of uniform elongation of~45%despite the as-rolled states with an advantage of simplified thermo-mechanical processes.

Insights into the nucleation,grain growth and phase transformation behaviours of sputtered metastableβ-W films

Metastable phase in tungsten film is of great interests in recent years due to its giant spin Hall effects,however,little information has been known on its nucleation,growth and phase transformation.In this paper,a 900 nm-thick tungsten film with double-layer structure(α-W underlayer andβ-W above it)was produced on SiO_(2)/Si substrate by high vacuum magnetron sputtering at room temperature.The structural properties ofβ-W were systemically investigated by X-ray diffraction,transmission electron microscopy,thermodynamic calculation,first-principle and phase-field simulations.It is found that theβ-W nucleation is energetically favoured on the SiO_(2)surface compared to theα-W one.As the film thickening proceeds,β-W[211]turns to be preferred direction of growth owing to the elastic strain energy minimization,which is verified by phase-field simulations.Moreover,theβ→αphase transformation takes place near the film-substrate interface while the rest of the film keeps theβ-W phase,leading to a doublelayer structure.This localized phase transition is induced by lower Gibbs free energy ofα-W phase at larger grain sizes,which can be confirmed by thermodynamic calculation.Further in-situ heating TEM analysis of the as-deposited film reveals that theβ→αphase transformation is fulfilled byα/βinterface propagation rather than local atomic rearrangements.Our findings offer valuable insights into the intrinsic properties of metastable phase in tungsten.

Grain refinement of commercial pure Al treated by Pulsed Magneto-Oscillation on the top surface of melt

Commercial pure Al can be refined by Pulsed Magneto-Oscillation(PMO) treatment applied via a plate induction coil above the top surface of the melt. The proportion of the equiaxed zone area increases with decreasing Height to Diameter(H/D) ratios from 3.5 to1.8 and further to 1.0. Meanwhile, it increases and then decreases with increasing peak current for the three kinds of ingots with H/D ratios of 3.5, 1.8 and 1.0, respectively. However, when the H/D ratio decreases to 0.44, the area proportion of equiaxed zone can reach the maximum value with a lower peak current. FEA software simulation indicates that smaller H/D ratio results in larger current density, electromagnetic force and convection on the top surface of the melt, favoring nucleation and subsequent grain formation. Through evaluating Joule heating effect by PMO, it was found that the proper amount of Joule heating benefits grain refinement. Excessive Joule heating can reduce the size of the equiaxed zone and change the growth morphology of the grains.

Effects of novel self-inoculation method on microstructure of AM60 alloy

A novel cast processing method,self-inoculation method (SIM),was proposed.The process involves the addition of self-inoculant to melt,then pouring the melt to a mould through a multi-stream mixing cooling channel.In this paper,the process parameters were investigated.Results indicate that the melt treatment temperature,the amount of self-inoculant added,and the slope angle of the cooling channel are the key factors for SIM process.The optimized parameters are that the melt treatment temperature is between 680 and 700°C;the addition of self-inoculant is between 5wt.% and 7wt.%;and the slope angle of the cooling channel is between 30° and 45°.Further analysis reveals that SIM changes the solidification microstructure of slurry by controlling the nucleation and growth of the primary phase in the melt.

CAVITATED BIFURCATION FOR INCOMPRESSIBLE HYPERELASTIC MATERIAL

The spherical cavitated bifurcation for a hyperelastic solid sphere made of the incompressible Valanis-Landel material under boundary dead-loading is examined. The analytic solution for the bifurcation problem is obtained. The catastrophe and concentration of stresses are discussed. The stability of solutions is discussed through the energy comparison. And the growth of a pre-existing micro-void is also observed.

Formation of fine fully-lamellar microstructure of TiAl-based alloy in rapid heating cyclic heat treatment process

The optical observation results of neocrystallization nucleation and growth of fine fully lamellar (FFL) α 2/ γ microstructure of a TiAl based alloy in rapid heating cyclic heat treatment process were reported. The characteristics of α+γ→α transformation under rapid heating conditions were analysed. A model for explaining the nucleation and growth mechanism of FFL α 2/ γ microstructure was proposed.