Growth and inhibition of zinc anode dendrites in Zn-air batteries:Model and experiment

Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.

Phase-field lattice-Boltzmann study on fully coupled thermal-solute-convection dendrite growth of Al-Cu alloy

Dendrite growth is a complex liquid-solid phase transition process involving multiple physical factors.A phase-field lattice-Boltzmann method was developed to simulate the two-and three-dimension dendrite growth of Al-Cu alloy.The effect of fully coupled thermal-solute-convection interaction on the dendrite growth was investigated by incorporating a parallel-adaptive mesh refinement algorithm into the numerical model.By accurately reproducing the latent heat release,solute diffusion and convective transport behaviors at the liquidsolid interface,the interaction mechanism among thermal-solute-convection transport as well as their coupling effects on the dendrite growth dynamics were discussed.The simulation results show that the release of latent heat slows down the dendrite growth rate,and both natural and forced convection disrupt the symmetrical growth of dendrites.Their combination makes the growth of dendrites more complex,capturing important physical aspects such as recalescence,dendrite tip splitting,dendrite tilting,dendrite remelting,and solute plume in the simulation case.Based on the robustness and powerful ability of the numerical model,the formation mechanisms of these physical aspects were revealed.

Effect of traveling-wave magnetic field on dendrite growth of high-strength steel slab: Industrial trials and numerical simulation

The dendrite growth behavior of high-strength steel during slab continuous casting with a traveling-wave magnetic field was studied in this paper. The morphology of the solidification structure and composition distribution were analyzed. Results showed that the columnar crystals could deflect and break when the traveling-wave magnetic field had low current intensity. With the increase in current intensity, the secondary dendrite arm spacing and solute permeability decreased, and the columnar crystal transformed into an equiaxed crystal. The electromagnetic force caused by the traveling-wave magnetic field changed the temperature gradient and velocity magnitude and promoted the breaking and fusing of dendrites. Dendrite compactness and composition uniformity were arranged in descending order as follows:columnar-toequiaxed transition (high current intensity), columnar crystal zone (low current intensity), columnar-to-equiaxed transition (low current intensity), and equiaxed crystal zone (high current intensity). Verified numerical simulation results combined with the boundary layer theory of solidification front and dendrite breaking–fusing model revealed the dendrite deflection mechanism and growth process. When thermal stress is not considered, and no narrow segment can be found in the dendrite, the velocity magnitude on the solidification front of liquid steel can reach up to 0.041 m/s before the dendrites break.

Possibility of Solid Hydrometeor Growth Zone Identification Using Radar Spectrum Width

In this study,the correlation between simulated and measured radar velocity spectrum width(σ_(v))is investigated.The results show that the dendrites growth zones(DGZs)and needles growth zones(NGZs)mostly contain dendrites(DN)and needles(NE),respectively.Clearσ_(v) zones(1.1<σ_(v)(m s^(-1))<1.3 and 0.3<σ_(v)(m s^(-1))<0.7 for the DGZ and NGZ,respectively)could be identified in the case studies(27 and 28 February 2016)near altitudes corresponding to temperatures of–15°C and–5°C,according to the Japan Meteorological Agency and mesoscale model reanalysis data.Oblate particles with diverse particle shapes were observed in the DGZ withσ_(v)>1.2 m s^(-1),a differential reflectivity(ZDR)higher than 0 dB,and a cross-correlation coefficient(ρhv)less than 0.96.In contrast,prolate particles with relatively uniform shapes were observed in the NGZ withσ_(v)<0.6 m s^(-1),a ZDR less than 0 dB,andρhv higher than 0.97.The simulation results show that the DN exhibited a largerσ_(v) compared to the NE,and this observedσ_(v) was strongly dependent on the wind fluctuations(v’)due to turbulence or wind shear.In contrast,the NE exhibited a significantly smallσ_(v)~0.55 m s^(-1),which converges irrespective of v’.In addition,a strong correlation between the measuredσ_(v) values at five radar elevation angles(θ=6.2°,9.1°,13.1°,19°,and 80°)and those simulated in this study confirmed the significance of the analysis results.

Parameter calculation and result storage for phase-field simulation in α-Mg dendrite growth of Mg-5-wt% Zn alloy

Parameter calculation and result storage, as two necessary steps in phase-field simulation play an important role in ensuring the accuracy of simulation results. A strategy of parameter calculation and result storage is presented for phase-field simulation in α-Mg dendrite growth of Mg-5-wt% Zn alloy under isothermal solidification. Based on the phase diagram and empirical formulas, key parameters of the phase-field model, such as equilibrium partition coefficient k, liquidus slope m, solutal diffusion coefficient in liquid Dl, and solutal diffusion coefficient in solid Ds, can be obtained.Both structured grid method and structured point method can be used to store simulation results, but using the latter method will reduce about 60% storage space and 37.5% storage time compared with the former. Finally, convergent simulation results of α-Mg dendrite growth are obtained and they are in good agreement with the experimental results about optical micrograph, which verify the accuracy of parameters and stability of storage method.

In-situ physical/chemical cross-linked hydrogel electrolyte achieving ultra-stable zinc anode-electrolyte interface towards dendrite-free zinc ion battery

Hydrogen evolution reaction(HER),zinc corrosion,and dendrites growth on zinc metal anode are the major issues limiting the practical applications of zinc-ion batteries.Herein,an in-situ physical/chemical cross-linked hydrogel electrolyte(carrageenan/polyacrylamide/ZnSO_(4),denoted as CPZ)has been developed to stabilize the zinc anode-electrolyte interface,which can eliminate side reactions and prevent dendrites growth.The in-situ CPZ hydrogel electrolyte improves the reversibility of zinc anode due to eliminating side reactions caused by active water molecules.Furthermore,the electrostatic interaction between the SO_(4)^(-)groups in CPZ and Zn^(2+)can encourage the preferential deposition of zinc atoms on(002)crystal plane,which achieve dendrite-free and homogeneous zinc deposition.The in-situ hydrogel electrolyte offers a streamlined approach to battery manufacturing by allowing for direct integration into the battery.Subsequently,the Zn//Zn half battery with CPZ hydrogel electrolyte can enable an ultra-long cycle over 5500 h at a current density of 0.5 mA cm^(-2),and the Zn//Cu half battery reach an average coulombic efficiency of 99.37%.The Zn//V_(2)O_5-GO full battery with CPZ hydrogel electrolyte demonstrates94.5%of capacity retention after 2100 cycles.This study is expected to open new thought for the development of commercial hydrogel electrolytes for low-cost and long-life zinc-ion batteries.

Phase-field simulations of forced flow effect on dendritic growth perpendicular to flow

The effect of supercooled melt forced laminar flow at low Reynolds Number on dendritic growth perpendicular to melt flow direction was investigated with the phase-field method by incorporating melt convection and thermal noise under non-isothermal condition. By taking the dendritic growth of high pure succinonitrile （SCN） supercooled melt as an example, side-branching shape difference of melts with flow and without flow was analyzed. Relationships among supercooled melt inflow velocity, deflexion angle of dendritic arm and dendritic tip growth velocity were studied. Results show that the melt inflow velocity has few effects on the dendritic tip growth velocity. A formula of relationship between the velocity of the melt in front of primary dendritic tip and the dendritic growth time was deduced, and the calculated result was in quantitative agreement with the simulation result.

Modeling of equiaxed and columnar dendritic growth of magnesium alloy

Based on the cellular automaton （CA） method, a numerical model was developed to simulate the dendritic growth of magnesium alloy with HCP crystal structure. The growth kinetics was calculated from the complete solution of the transport equations. By defining a special neighborhood configuration with the square CA cell, and using a set of capturing rules which were proposed by BELTRAN-SANCHEZ and STEFANESCU for the dendritic growth of cubic crystal metals during solidification, modeling of dendritic growth of magnesium alloy with different growth orientations was achieved. Simulation of equiaxed dendritic growth and columnar dendritic growth under directional solidification was carried out, and validation was performed by comparing the simulated results with the experimental results and those in the previously published works.

Phase-field modeling of dendritic growth under forced flow based on adaptive finite element method

A mathematical model combined projection algorithm with phase-field method was applied. The adaptive finite element method was adopted to solve the model based on the non-uniform grid, and the behavior of dendritic growth was simulated from undercooled nickel melt under the forced flow. The simulation results show that the asymmetry behavior of the dendritic growth is caused by the forced flow. When the flow velocity is less than the critical value, the asymmetry of dendrite is little influenced by the forced flow. Once the flow velocity reaches or exceeds the critical value, the controlling factor of dendrite growth gradually changes from thermal diffusion to convection. With the increase of the flow velocity, the deflection angle towards upstream direction of the primary dendrite stem becomes larger. The effect of the dendrite growth on the flow field of the melt is apparent. With the increase of the dendrite size, the vortex is present in the downstream regions, and the vortex region is gradually enlarged. Dendrite tips appear to remelt. In addition, the adaptive finite element method can reduce CPU running time by one order of magnitude compared with uniform grid method, and the speed-up ratio is proportional to the size of computational domain.

Simulation and experimental validation of three-dimensional dendrite growth

A three-dimensional （3-D） modified cellular automaton （MCA） method was developed for simulating the dendrite morphology of cubic system alloys. Two-dimensional （2-D） equations of growth velocities of the dendrite tip, interface curvature and anisotropy of the surface energy were extended to 3-D system in the model. Therefore, the model was able to describe the morphology evolution of 3-D dendrites. Then, the model was applied to simulate the mechanism of spacing adjustment for 3-D columnar dendrite growth, and the competitive growth of columnar dendrites with different preferred growth orientations under constant temperature gradient and pulling velocity. Directional solidification experiments of NH4Cl-H2O transparent alloy were performed. It was found that the simulated results compared well with the experimental results. Therefore, the model was reliable for simulating the 3-D dendrite growth of cubic system alloys.

Case Studies of the Microphysical and Kinematic Structure of Summer Mesoscale Precipitation Clouds over the Eastern Tibetan Plateau

Three cases of microphysical characteristics and kinematic structures in the negative temperature region of summer mesoscale cloud systems over the eastern Tibetan Plateau(TP)were investigated using X-band dual-polarization radar.The time-height series of radar physical variables and mesoscale horizontal divergence δderived by quasi-vertical profiles(QVPs)indicated that the dendritic growth layer(DGL,-20°C to-10°C)was ubiquitous,with large-value zones of K_(DP)(specific differential phase),Z_(DR)(differential reflectivity),or both,and corresponded to various dynamic fields(ascent or descent).Ascents in the DGL of cloud systems with vigorous vertical development were coincident with large-value zones of Z_(DR),signifying ice crystals with a large axis ratio,but with no obvious large values of K_(DP),which differs from previous findings.It is speculated that ascent in the DGL promoted ice crystals to undergo further growth before sinking.If there was descent in the DGL,a high echo top corresponded to large values of K_(DP),denoting a large number concentration of ice crystals;but with the echo top descending,small values of K_(DP) formed.This is similar to previous results and reveals that a high echo top is conducive to the generation of ice crystals.When ice particles fall to low levels(-10℃ to 0℃),they grow through riming,aggregation,or deposition,and may not be related to the kinematic structure.It is important to note that this study was only based on a limited number of cases and that further research is therefore needed.

Plasma-assisted aerogel interface engineering enables uniform Zn^(2+)flux and fast desolvation kinetics toward zinc metal batteries

The poor reversibility of Zn anodes induced by dendrite growth,surface passivation,and corrosion,severely hinders the practical applicability of Zn metal batteries.To address these issues,a plasmaassisted aerogel(PAG)interface engineering was proposed as efficient ion transport modulator that can simultaneously regulate uniform Zn^(2+)flux and desolvation behavior during battery operation.The PAG with ordered mesopores acted as an ion sieve to homogenize Zn deposition and accelerate Zn^(2+)flux,which is favorable for corrosion resistance and dendrite suppression.Importantly,the plasma-assisted aerogel with abundant hydrophilic groups can facilitate the desolvation kinetics of Zn^(2+)due to the multiple hydrogen-bonding interaction with the activated water molecules,thus accelerating the Zn^(2+)migration kinetics.Consequently,the Zn/Zn cell assembled with PAG-modified separator demonstrates stable plating and stripping behavior(over 1400 h at 1 mA cm^(-2))and high Coulombic efficiency(99.8%at1 mA cm^(-2)after 1100 cycles),and the Zn‖MnO_(2)full cell shows excellent long-term cycling stability and maintains a high capacity of 154.9 mA h g^(-1)after 1000 cycles at 1 A g^(-1).This study provides a feasible approach for the large-scale fabrication of aerogel functionalized separators to realize ultra-stable Zn metal batteries.

Engineering hydrophobic protective layers on zinc anodes for enhanced performance in aqueous zinc-ion batteries

Aqueous zinc-ion batteries possess substantial potential for energy storage applications;however,they are hampered by challenges such as dendrite formation and uncontrolled side reactions occurring at the zinc anode.In our investigation,we sought to mitigate these issues through the utilization of in situ zinc complex formation reactions to engineer hydrophobic protective layers on the zinc anode surface.These robust interfacial layers serve as effective barriers,isolating the zinc anode from the electrolyte and active water molecules and thereby preventing hydrogen evolution and the generation of undesirable byproducts.Additionally,the presence of numerous zincophilic sites within these protective layers facilitates uniform zinc deposition while concurrently inhibiting dendrite growth.Through comprehensive evaluation of functional anodes featuring diverse functional groups and alkyl chain lengths,we meticulously scrutinized the underlying mechanisms influencing performance variations.This analysis involved precise modulation of interfacial hydrophobicity,rapid Zn^(2+)ion transport,and ordered deposition of Zn^(2+)ions.Notably,the optimized anode,fabricated with octadecylphosphate(OPA),demonstrated exceptional performance characteristics.The Zn//Zn symmetric cell exhibited remarkable longevity,exceeding 4000 h under a current density of 2 mA cm^(-2)and a capacity density of 2 mA h cm^(-2),Furthermore,when integrated with a VOH cathode,the complete cell exhibited superior capacity retention compared to anodes modified with alternative organic molecules.

Free dendritic growth model incorporating interfacial nonisosolutal nature due to normal velocity variation

Considering both the effects of the interfacial normal velocity dependence of solute segregation and the local nonequilibrium solute diffusion,an extended free dendritic growth model was analyzed.Compared with the predictions from the dendritic model with isosolutal interface assumption,the transition from solutal dendrite to thermal dendrite moves to higher undercoolings,i.e.,the region of undercoolings with solute controlled growth is extended.At high undercoolings,the transition from the mainly thermal-controlled growth to the purely thermal-controlled growth is not sharp as predicted by the isosolute model,but occurs in a range of undercooling,due to both the effects of the interfacial normal velocity dependence of solute segregation and the local nonequilibrium solute diffusion.Model test indicates that the present model can give a satisfactory agreement with the available experimental data for the Ni-0.7% B（mole fraction） alloy.

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.

Numerical simulation of dendrite growth in Ni-based superalloy casting during directional solidification process

An understanding of dendrite growth is required in order to improve the properties of castings. For this reason, cellular automaton-finite difference(CA-FD) method was used to investigate the dendrite growth during directional solidification(DS)process. The solute diffusion model combined with macro temperature field model was established for predicting the dendrite growth behavior. Model validation was performed by the DS experiment, and the cooling curves and grain structures obtained by the experiment presented a reasonable agreement with the simulation results. The competitive growth of dendrites was also simulated by the proposed model, and the competitive behavior of dendrites with different misalignment angles was also discussed in detail.Subsequently, 3D dendrites growth was also investigated by experiment and simulation, and both were in good accordance. The influence on dendrites growth of initial nucleus was investigated by three simulation cases, and the results showed that the initial nuclei just had an effect on the initial growth stage of columnar dendrites, but had little influence on the final dendritic morphology and the primary dendrite arm spacing.

Phase field modeling of multiple dendrite growth of Al-Si binary alloy under isothermal solidification

Phase field method offers the prospect of being able to perform realistic numerical experiments on dendrite growth in metallic systems. In this study, the growth process of multiple dendrites in AI-2-mole-%-Si binary alloy under isothermal solidification was simulated using phase field model. The simulation results showed the impingement of arbitrarily oriented crystals and the competitive growth among the grains during solidification. With the increase of growing time, the grains begin to coalesce and impinge the adjacent grains. When the dendrites start to impinge, the dendrite growth is obviously inhibited.

A lattice Boltzmann–cellular automaton study on dendrite growth with melt convection in solidification of ternary alloys

A lattice Boltzmann （LB）-cellular automaton （CA） model is employed to study the dendrite growth of A1-4.0 wt%Cu- 1.0 wt%Mg alloy. The effects of melt convection, solute diffusion, interface curvature, and preferred growth orientation are incorporated into the coupled model by coupling the LB-CA model and the CALPHAD-based phase equilibrium solver, PanEngine. The dendrite growth with single and multiple initial seeds was numerically studied under the conditions of pure diffusion and melt convection. Effects of initial seed number and melt convection strength were characterized by new- defined solidification and concentration entropies, The numerical result shows that the growth behavior of dendJ-ites, the final microstructure, and the micro-segregation are significantly influenced by melt convection during solidification of the ternary alloys. The proposed solidification and concentration entropies are useful characteristics bridging the solidification behavior and the microstructure evolution of alloys.

Phase field modeling of dendrite growth

Single dendrite and multi-dendrite growth for Al-2 mol pct Si alloy during isothermal solidification are simulated by phase field method. In the case of single equiaxed dendrite growth, the secondary and the necking phenomenon can be observed. For multi-dendrite growth, there exists the competitive growth among the dendrites during solidification. As solidification proceeds, growing and coarsening of the primary arms occurs, together with the branching and coarsening of the secondary arms. When the diffusion fields of dendrite tips come into contact with those of the branches growing from the neighboring dendrites, the dendrites stop growing and being to ripen and thicken.

Effects of RE and Sr additions on dendrite growth and phase precipitation in AZ91D magnesium alloy

To develop AZ91D alloys with fine microstructure, effects of the addition of rare earth (RE), Sr and RE + Sr on the dendrite growth and phase precipitation in AZ91D magnesium alloy were studied, respectively. The results show that the microstructure is refined and the morphology of β-Mg17A112 phase is modified with RE or Sr addition, especially with the RE+Sr composite addition which can reduce the average grain size of AZ91D alloy obviously to 141 μm. The needle-like or block-like new phases adhering to β-Mg17A112 phase form at interdendrites during solidification. The enrichment of RE or/and Sr elements in front of the solidification interface, especially at the tips of α-Mg dendrite, which restricts the growth of α-Mg dendrite, changes the preferential growth of α-Mg and finally results in the grain refinement and the blunting of α-Mg dendrite.