A review of solid-state lithium metal batteries through in-situ solidification

High-energy-density lithium metal batteries are the next-generation battery systems of choice,and replacing the flammable liquid electrolyte with a polymer solid-state electrolyte is a prominent conduct towards realizing the goal of high-safety and high-specific-energy devices.Unfortunately,the inherent intractable problems of poor solid-solid contacts between the electrode/electrolyte and the growth of Li dendrites hinder their practical applications.The in-situ solidification has demonstrated a variety of advantages in the application of polymer electrolytes and artificial interphase,including the design of integrated polymer electrolytes and asymmetric polymer electrolytes to enhance the compatibility of solid–solid contact and compatibility between various electrolytes,and the construction of artificial interphase between the Li anode and cathode to suppress the formation of Li dendrites and to enhance the high-voltage stability of polymer electrolytes.This review firstly elaborates the history of in-situ solidification for solid-state batteries,and then focuses on the synthetic methods of solidified electrolytes.Furthermore,the recent progress of in-situ solidification technology from both the design of polymer electrolytes and the construction of artificial interphase is summarized,and the importance of in-situ solidification technology in enhancing safety is emphasized.Finally,prospects,emerging challenges,and practical applications of in-situ solidification are envisioned.

Effect of Co on Solidification Characteristics and Microstructural Transformation of Non-equilibrium Solidified Cu-Ni Alloys

Non-equilibrium solidification structures of Cu55Ni45 and Cu55Ni43Co2 alloys were prepared by the molten glass purification cycle superheating method.The variation of the recalescence phenomenon with the degree of undercooling in the rapid solidification process was investigated using an infrared thermometer.The addition of the Co element affected the evolution of the recalescence phenomenon in Cu-Ni alloys.The images of the solid-liquid interface migration during the rapid solidification of supercooled melts were captured by using a high-speed camera.The solidification rate of Cu-Ni alloys,with the addition of Co elements,was explored.Finally,the grain refinement structure with low supercooling was characterised using electron backscatter diffraction(EBSD).The effect of Co on the microstructural evolution during nonequilibrium solidification of Cu-Ni alloys under conditions of small supercooling is investigated by comparing the microstructures of Cu55Ni45 and Cu55Ni43Co2 alloys.The experimental results show that the addition of a small amount of Co weakens the recalescence behaviour of the Cu55Ni45 alloy and significantly reduces the thermal strain in the rapid solidification phase.In the rapid solidification phase,the thermal strain is greatly reduced,and there is a significant increase in the characteristic undercooling degree.Furthermore,the addition of Co and the reduction of Cu not only result in a lower solidification rate of the alloy,but also contribute to the homogenisation of the grain size.

Solidification/Stabilization of Chromium in Red Mud-based Geopolymer

Up to 1.5wt%of Cr(Ⅲ)salts(CrCl_(3),and Cr_(2)O_(3))and Cr(Ⅵ)salts(Na_(2)CrO_(4),and CaCr_(2)O_(7))were incorporated into red mud-based geopolymers,respectively.The solidification/stabilization,compressive strength,and durability of the Cr-containing geopolymers were investigated.The experimental results indicate that the red mud-based geopolymer could effectively solidify/stabilize different types of Cr salts with solidification/stabilization rates of above 99.61%.Geopolymers are environmentally safe when the dosage of CaCr_(2)O_(7)is≤1.0wt%,or the dosage of CrCl_(3),Cr_(2)O_(3),and Na_(2)CrO_(4)is≤1.5wt%,respectively.The effects of Cr salts on the compressive strength varies with the type and content of Cr salts.The freeze-thaw cycle is more destructive to geopolymer properties than sulfate attack or acid rain erosion.The solidification/stabilization of Cr is mainly attributed to the following reasons:a)The chemical binding of Cr is related to the formation of Cr-containing hydrates(eg,magnesiochromite((Mg,Fe)(Cr,Al)_(2)O_(4)))and doping into N-A-S-H gel and C-A-S-H gel framework;b)The physical effect is related to the encapsulation by the hydration products(e g,N-A-S-H gel and C-A-S-H gel).This study provides a reference for the treatment of hazardous Cr-containing wastes by solid waste-based geopolymers.

Preparation of Laser Cladding Coating Undercooling Cu-based Alloy and Co on Non-equilibrium Solidification Structure

The effect of the gradient content of Co element on the solidification process of Cu-based alloy under deep under cooling conditions was explored.The non-equilibrium solidification structure of the under cooled alloy samples were analyzed.It is found that the rapidly solidified alloy has undergone twice grain refinement during the undercooling process.Characterization and significance of the maximum undercooling refinement structure of Cu60Ni35Co5 at T=253 K were analyzed.High-density defects were observed,such as dislocations,stacking faults networks,and twinning structures.The standard FCC diffraction pattern represents that it is still a single-phase structure.Based on the metallographic diagram,EBSD and TEM data analysis,it is illustrated that the occurrence of grain refinement under high undercooling is due to stress induced recrystallization.In addition,the laser cladding technology is used to coat Co-based alloy(Stellite12) coating on 304 stainless steel substrate;the microstructure of the coating cross-section was analyzed.It was found that the microstructure of the cross-section is presented as columnar crystals,planar crystals,and disordered growth direction,so that the coating has better hardness and wear resistance.By electrochemical corrosion of the substrate and coating,it can be seen that the Co and Cr elements present in the coating are more likely to form a dense passivation film,which improved the corrosion resistance of the coating.

Effect of solidification cooling rate on microstructure and tribology characteristics of Zn-4Si alloy

The main objective of this work was to modify the microstructure and enhance the tribological properties of a new Zn-4Si al-loy through a high solidification cooling rate(SCR).According to the results,by increasing the SCR from 2.0 to 59.5℃/s the average size of primary Si particles and that of the grains reduced from 76.1 and 3780μm to less than about 14.6 and 460μm,respectively.Augment-ing the SCR also enhanced the microstructural homogeneity,decreased the porosity content(by 50%),and increased the matrix hardness(by 36%).These microstructural changes enhanced the tribological behavior.For instance,under the applied pressure of 0.5 MPa,an in-crease in the SCR from 2.0 to 59.5℃/s decreased the wear rate and the average friction coefficient of the alloy by 57%and 23%,respect-ively.The wear mechanism was also changed from the severe delamination,adhesion,and abrasion in the slowly-cooled alloy to the mild tribolayer delamination/abrasion in the high-cooling-rate-solidified sample.

Irregular initial solidification by mold thermal monitoring in the continuous casting of steels:A review

Occasional irregular initial solidification phenomena,including stickers,deep oscillation marks,depressions,and surface cracks of strand shells in continuous casting molds,are important limitations for developing the high-efficiency continuous casting of steels.The application of mold thermal monitoring(MTM) systems,which use thermocouples to detect and respond to temperature variations in molds,has become an effective method to address irregular initial solidification phenomena.Such systems are widely applied in numerous steel companies for sticker breakout prediction.However,monitoring the surface defects of strands remains immature.Hence,indepth research is necessary to utilize the potential advantages and comprehensive monitoring of MTM systems.This paper summarizes what is included in the irregular initial solidification phenomena and systematically reviews the current state of research on these phenomena by the MTM systems.Furthermore,the influences of mold slag behavior on monitoring these phenomena are analyzed.Finally,the remaining problems of the formation mechanisms and investigations of irregular initial solidification phenomena are discussed,and future research directions are proposed.

Numerical simulation on directional solidification and heat treatment processes of turbine blades

Study on turbine blades is crucial due to their critical role in ensuring the efficient and reliable operation of aircraft engines.Nickel-based single crystal superalloys are extensively used in the hot manufacturing of turbine blades due to their exceptional high-temperature mechanical properties.The hot manufacturing of single crystal blades involves directional solidification and heat treatment.Experimental manufacturing of these blades is time-consuming,capital-intensive,and often insufficient to meet industrial demands.Numerical simulation techniques have gained widespread acceptance in blade manufacturing research due to their low energy consumption,high efficiency,and rapid turnaround time.This article introduces the modeling and simulation of hot manufacturing in single crystal blades.The discussion outlines the prevalent mathematical models employed in numerical simulations related to blade hot manufacturing.It encapsulates the advancements in research concerning macro to micro-level numerical simulation techniques for directional solidification and heat treatment processes.Furthermore,potential future trajectories for the numerical simulation of single crystal blade hot manufacturing are also discussed.

Volume-averaged modeling of multiphase solidification with equiaxed crystal sedimentation in a steel ingot

Macrosegregation is a critical factor that limits the mechanical properties of materials.The impact of equiaxed crystal sedimentation on macrosegregation has been extensively studied,as it plays a significant role in determining the distribution of alloying elements and impurities within a material.To improve macrosegregation in steel connecting shafts,a multiphase solidification model that couples melt flow,heat transfer,microstructure evolution,and solute transport was established based on the volume-averaged Eulerian-Eulerian approach.In this model,the effects of liquid phase,equiaxed crystals,columnar dendrites,and columnar-to-equiaxed transition(CET)during solidification and evolution of microstructure can be considered simultaneously.The sedimentation of equiaxed crystals contributes to negative macrosegregation,where regions between columnar dendrites and equiaxed crystals undergo significant A-type positive macrosegregation due to the CET.Additionally,noticeable positive macrosegregation occurs in the area of final solidification in the ingot.The improvement in macrosegregation is beneficial for enhancing the mechanical properties of connecting shafts.To mitigate the thermal convection of molten steel resulting from excessive superheating,reducing the superheating during casting without employing external fields or altering the design of the ingot mold is indeed an effective approach to control macrosegregation.

Exploration of the coupled lattice Boltzmann model based on a multiphase field model:A study of the solid-liquid-gas interaction mechanism in the solidification process

A multiphase field model coupled with a lattice Boltzmann(PF-LBM)model is proposed to simulate the distribution mechanism of bubbles and solutes at the solid-liquid interface,the interaction between dendrites and bubbles,and the effects of different temperatures,anisotropic strengths and tilting angles on the solidified organization of the SCN-0.24wt.%butanedinitrile alloy during the solidification process.The model adopts a multiphase field model to simulate the growth of dendrites,calculates the growth motions of dendrites based on the interfacial solute equilibrium;and adopts a lattice Boltzmann model(LBM)based on the Shan-Chen multiphase flow to simulate the growth and motions of bubbles in the liquid phase,which includes the interaction between solid-liquid-gas phases.The simulation results show that during the directional growth of columnar dendrites,bubbles first precipitate out slowly at the very bottom of the dendrites,and then rise up due to the different solid-liquid densities and pressure differences.The bubbles will interact with the dendrite in the process of flow migration,such as extrusion,overflow,fusion and disappearance.In the case of wide gaps in the dendrite channels,bubbles will fuse to form larger irregular bubbles,and in the case of dense channels,bubbles will deform due to the extrusion of dendrites.In the simulated region,as the dendrites converge and diverge,the bubbles precipitate out of the dendrites by compression and diffusion,which also causes physical phenomena such as fusion and spillage of the bubbles.These results reveal the physical mechanisms of bubble nucleation,growth and kinematic evolution during solidification and interaction with dendrite growth.

Lunar In Situ Large-Scale Construction:Quantitative Evaluation of Regolith Solidification Techniques

Lunar habitat construction is crucial for successful lunar exploration missions.Due to the limitations of transportation conditions,extensive global research has been conducted on lunar in situ material processing techniques in recent years.The aim of this paper is to provide a comprehensive review,precise classification,and quantitative evaluation of these approaches,focusing specifically on four main approaches:reaction solidification(RS),sintering/melting(SM),bonding solidification(BS),and confinement formation(CF).Eight key indicators have been identified for the construction of low-cost and highperformance systems to assess the feasibility of these methods:in situ material ratio,curing temperature,curing time,implementation conditions,compressive strength,tensile strength,curing dimensions,and environmental adaptability.The scoring thresholds are determined by comparing the construction requirements with the actual capabilities.Among the evaluated methods,regolith bagging has emerged as a promising option due to its high in situ material ratio,low time requirement,lack of hightemperature requirements,and minimal shortcomings,with only the compressive strength falling below the neutral score.The compressive strength still maintains a value of 2–3 MPa.The proposed construction scheme utilizing regolith bags offers numerous advantages,including rapid and large-scale construction,ensured tensile strength,and reduced reliance on equipment and energy.In this study,guidelines for evaluating regolith solidification techniques are provided,and directions for improvement are offered.The proposed lunar habitat design based on regolith bags is a practical reference for future research.

Recent research progress on the phase-field model of microstructural evolution during metal solidification

Solidification structure is a key aspect for understanding the mechanical performance of metal alloys,wherein composition and casting parameters considerably influence solidification and determine the unique microstructure of the alloys.By following the principle of free energy minimization,the phase-field method eliminates the need for tracking the solid/liquid phase interface and has greatly accelerated the research and development efforts geared toward optimizing metal solidification microstructures.The recent progress in the application of phasefield simulation to investigate the effect of alloy composition and casting process parameters on the solidification structure of metals is summarized in this review.The effects of several typical elements and process parameters,including carbon,boron,silicon,cooling rate,pulling speed,scanning speed,anisotropy,and gravity,on the solidification structure are discussed.The present work also addresses the future prospects of phase-field simulation and aims to facilitate the widespread applications of phase-field approaches in the simulation of microstructures during solidification.

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.

High-Performance Quasi-Solid-State Pouch Cells Enabled by in situ Solidification of a Novel Polymer Electrolyte

Conventional lithium-ion batteries(LIBs)with liquid electrolytes are challenged by their big safety concerns,particularly used in electric vehicles.All-solid-state batteries using solid-state electrolytes have been proposed to significantly improve safety yet are impeded by poor interfacial solid–solid contact and fast interface degradation.As a compromising strategy,in situ solidification has been proposed in recent years to fabricate quasi-solid-state batteries,which have great advantages in constructing intimate interfaces and cost-effective mass manufacturing.In this work,quasi-solid-state pouch cells with high loading electrodes(≥3 m Ah cm^(-2))were fabricated via in situ solidification of poly(ethylene glycol)diacrylate-based polymer electrolytes(PEGDA-PEs).Both single-layer and multilayer quasi-solid-state pouch cells(2.0 Ah)have demonstrated stable electrochemical performance over500 cycles.The superb electrochemical stability is closely related to the formation of robust and compatible interphase,which successfully inhibits interfacial side reactions and prevents interfacial structural degradation.This work demonstrates that in situ solidification is a facile and cost-effective approach to fabricate quasi-solid-state pouch cells with both excellent electrochemical performance and safety.

Effects of mechanical vibration on filling and solidification behavior, microstructure and performance of Al/Mg bimetal by lost foam compound casting

Al/Mg bimetal was prepared by lost foam solid-liquid compound casting,and the effects of mechanical vibration on the filling and solidification behavior,microstructure and performance of the bimetal were investigated.Results show that the mechanical vibration has a remarkable influence on the filling and solidification processes.It is found that after mechanical vibration,the filling rate increases and the filling rate at different times is more uniform than that without vibration.In addition,the mechanical vibration also increases the wettability between liquid AZ91D and A356 inlays.The mechanical vibration reduces the horizontal and vertical temperature gradient of the casting and makes the temperature distribution of the whole casting more uniform.Compared to the Al/Mg bimetal without vibration,the shear strength is improved by 39.76%after the mechanical vibration is applied,due to the decrease of the inclusions and Al_(12)Mg_(17) dendrites,and the refinement and uniform distribution of the Mg_(2)Si particles in the interface of the Al/Mg bimetal.

In-situ observation of porosity formation during directional solidification of Al-Si casting alloys

In-situ observation of porosity formation during directional solidification of two Al-Si alloys (7%Si and 13%Si) was made by using of micro-focus X-ray imaging.In both alloys,small spherical pores initially form in the melt far away from the eutectic solid-liquid (S/L) interface and then grow and coagulate during solidification.Some pores can float and escape from the solidifying melt front at a relatively high velocity.At the end of solidification,the remaining pores maintain spherical morphology in the near eutectic alloy but become irregular in the hypoeutectic alloy.This is attributed to different solidification modes and aluminum dendrite interactions between the two alloys.The mechanism of the porosity formation is briefly discussed in this paper.

Solidification microstructure of Ti-43Al alloy by twin-roll strip casting

As a near-net-shape technology,the twin-roll strip casting(TRC)process can be considered to apply to the fabrication of TiAl alloy sheets.However,the control of the grain distribution is very important in strip casting because the mechanical properties of strips are directly determined by the solidification microstructure.A three-dimensional(3D)cellular automation finite-element(CAFE)model based on ProCAST software was established to simulate the solidification microstructure of Ti-43Al alloy.Then,the influence of casting temperature and the maximum nucleation density(nmax)on the solidification microstructure was investigated in detail.The simulation results provide a good explanation and prediction for the solidification microstructure in the molten pool before leaving the kissing point.Experimental and simulated microstructure show the common texture<001>orientation in the columnar grains zone.Finally,the microstructure evolution of the Ti-43Al alloy was analyzed and the solidification phase transformation path during the TSC process was determined,i.e.,L→L+β→β→β+α→α+γ+β/B2 phase under a faster cooling rate and L→L+β→β→β+α→γ+lamellar(α_(2)+γ)+β/B2 phase under a slower cooling rate.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Effect of Cooling Rates on Solidification Microstructures and Tensile Property of a Novel Wrought Superalloy

The effects of cooling rates on solidification behaviors,segregation characteristics and tensile property of GH4151 alloy were investigated using microstructure characterization and tensile test.Firstly,a relationship between the secondary dendrite arm spacing and cooling rate was determined and it was confirmed to be valid.Secondly,it can be found from microstructure observations that the morphology of(Nb,Ti)C carbides transits from blocky and script type to fine script type and spotty type,and the refinedγ'phase was observed due to decrease of segregation with increasing cooling rates.Thirdly,the solidification microstructures of the industrial-scale samples were analyzed.The morphology ofηphase changes from indistinguishable shape,fine needle-like shape to large block-like shape with increasing ingot diameter.As a result,the mechanical properties of alloy decrease due to increase of brittle precipitations.The experimental results show that the precipitation behavior of GH4151 is affected by segregation degree of elements,and the segregation degree is determined by solute distribution process and solid back-diffusion process.

Interplay of laser power and pore characteristics in selective laser melting of ZK60 magnesium alloys:A study based on in-situ monitoring and image analysis

This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.

Dislocation mechanism of Ni_(47)Co_(53) alloy during rapid solidification

Dislocations and other atomic-level defects play a crucial role in determining the macroscopic properties of crystalline materials,but it is extremely difficult to observe the evolution of dislocations due to the limitations of the most advanced experimental techniques.Therefore,in this work,the rapid solidification processes of Ni_(47)Co_(53) alloy at five cooling rates are studied by molecular dynamics simulation,and the evolutions of their microstructures and dislocations are investigated as well.The results show that face-centered cubic(FCC) structures are formed at the low cooling rate,and the crystalline and amorphous mixture appear at the critical cooling rate,and the amorphous are generated at the high cooling rate.The crystallization temperature and crystallinity decrease with cooling rate increasing.Dislocations are few at the cooling rates of 1×10^(11) K/s,5×10^(12) K/s,and 1×10^(13) K/s,and they are most abundant at the cooling rates of 5×10^(11) K/s and1 × 10^(12) K/s,in which their dislocation line lengths are both almost identical.There appear a large number of dislocation reactions at both cooling rates,in which the interconversion between perfect and partial dislocations is primary.The dislocation reactions are more intense at the cooling rate of 5×10^(11) K/s,and the slip of some dislocations leads to the interconversion between FCC structure and hexagonal close packed(HCP) structure,which causes the twin boundaries(TBs) to disappear.The FCC and HCP are in the same atomic layer,and dislocations are formed at the junction due to the existence of TBs at the cooling rate of 1 ×10^(12) K/s.The present research is important in understanding the dislocation mechanism and its influence on crystal structure at atomic scales.