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.

Bilayer separator enabling dendrite-free zinc anode with ultralong lifespan >5000 h

Aqueous zinc(Zn)batteries with Zn metal anodes are promising clean energy storage devices with intrinsic safety and low cost.However,Zn dendrite growth severely restricts the use of Zn anodes.To effectively suppress Zn dendrite growth,we propose a bilayer separator consisting of commercial butter paper and glassfiber membrane.The dense cellulose-based butter paper(BP)with low zincophilicity and high mechanical properties prevents the pore-filling behavior of deposited Zn and related separator piercing,effectively suppressing the Zn dendrite growth.As a result,the bilayer separators endow the ZnjjZn symmetrical batteries with a superlong cycling life of Zn anodes(over 5000 h)at 0.5 mA cm^(-2) and the full batteries enhanced capacity retention,demonstrating the advancement of the bilayer separator to afford excellent cyclability of aqueous metal batteries.

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.

Dual-Functional Electrode Promoting Dendrite-Free and CO_(2) Utilization Enabled High-Reversible Symmetric Na-CO_(2) Batteries

Sodium-carbon dioxide(Na-CO_(2))batteries are regarded as promising energy storage technologies because of their impressive theoretical energy density and CO_(2)reutilization,but their practical applications are restricted by uncontrollable sodium dendrite growth and poor electrochemical kinetics of CO_(2)cathode.Constructing suitable multifunctional electrodes for dendritefree anodes and kinetics-enhanced CO_(2)cathodes is considered one of the most important ways to advance the practical application of Na-CO_(2)batteries.Herein,RuO2 nanoparticles encapsulated in carbon paper(RuCP)are rationally designed and employed as both Na anode host and CO_(2)cathode in Na-CO_(2)batteries.The outstanding sodiophilicity and high catalytic activity of RuCP electrodes can simultaneously contribute to homogenous Na+distribution and dendrite-free sodium structure at the anode,as well as strengthen discharge and charge kinetics at the cathode.The morphological evolution confirmed the uniform deposition of Na on RuCP anode with dense and flat interfaces,delivering enhanced Coulombic efficiency of 99.5%and cycling stability near 1500 cycles.Meanwhile,Na-CO_(2)batteries with RuCP cathode demonstrated excellent cycling stability(>350 cycles).Significantly,implementation of a dendrite-free RuCP@Na anode and catalytic-site-rich RuCP cathode allowed for the construction of a symmetric Na-CO_(2)battery with long-duration cyclability,offering inspiration for extensive practical uses of Na-CO_(2)batteries.

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.

Unveiling the influence of dendrite characteristics on the slip/twinning activity and the strain hardening capacity of Mg-Sn-Li-Zn cast alloys

This work explores the correlation between the characteristics of the cast structure(dendrite growth pattern,dendrite morphology and macro-texture)and strain hardening capacity during high temperature deformation of Mg-5Sn-0.3Li-0 and 3Zn multi-component alloys.The three dimensional(3D)morphology of the dendrite structure demonstrates the transition of the growth directions from<1123>,<1120>and<1122>to<1123>and<1120>due to the addition of Zn.The simultaneous effects of growing tendency and the decrement of dendrite coarsening rate at the solidification interval lead to dendrite morphology transition from the globular-like to the hyper-branch structure.This morphology transition results in the variation of the solidification macro-texture,which has effectively influenced the dominant deformation mechanisms(slip/twin activity).The higher activity of the slip systems increases the tendency of the dendrite arms for bending along the deformation direction and fragmentation.Apart from this,the dendrite holding hyper-branch structure with an average thickness below 20μm are more favorable for fragmentation.The dendrite fragmentation leads to considerable softening fractions,and as an effective strain compensation mechanism increases the workability of dendritic structure.

Overdischarge-induced evolution of Cu dendrites and degradation of mechanical properties in lithium-ion batteries

The degradation of mechanical properties of overdischarge battery materials manifests as a significant effect on the energy density,safety,and cycle life of the batteries.However,establishing the correlation between depth of overdischarge and mechanical properties is still a significant challenge.Studying the correlation between depth of overdischarge and mechanical properties is of great significance to improving the energy density and the ability to resist abuse of the batteries.In this paper,the mechanical properties of the battery materials during the whole process of overdischarge from discharge to complete failure were studied.The effects of depth of overdischarge on the elastic modulus and hardness of the cathode of the battery,the tensile strength and the thermal shrinkage rate of the separator,and the performance of binder were investigated.The precipitation of Cu dendrites on the separator and cathode after dissolution of anode copper foil is a key factor affecting the performance of battery materials.The Cu dendrites attached to the cathode penetrate the separator,causing irreversible damage to the coating and base film of the separator,which leads to a sharp decline in the tensile strength,thermal shrinkage rate and other properties of the separator.In addition,the Cu dendrites wrapping the cathode active particles reduce the adhesion of the active particles binder.Meanwhile,the active particles are damaged,resulting in a significant decrease in the elastic modulus and hardness of the cathode.

The mechanism of external pressure suppressing dendrites growth in Li metal batteries

Li metal is considered an ideal anode material for application in the next-generation secondary batteries.However,the commercial application of Li metal batteries has not yet been achieved due to the safety concern caused by Li dendrites growth.Despite the fact that many recent experimental studies found that external pressure suppresses the Li dendrites growth,the mechanism of the external pressure effect on Li dendrites remains poorly understood on the atomic scale.Herein,the large-scale molecular dynamics simulations of Li dendrites growth under different external pressure were performed with a machine learning potential,which has the quantum-mechanical accuracy.The simulation results reveal that the external pressure promotes the process of Li self-healing.With the increase of external pressure,the hole defects and Li dendrites would gradually fuse and disappear.This work provides a new perspective for understanding the mechanism for the impact of external pressure on Li dendrites.

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.

Emerging Carbon Nanotube-Based Nanomaterials for Stable and Dendrite-Free Alkali Metal Anodes:Challenges,Strategies,and Perspectives

Alkali metals(Li,Na,and K)are promising candidates for high-performance rechargeable alkali metal battery anodes due to their high theoretical specific capacity and low electrochemical potential.However,the actual application of alkali metal anodes is impeded by the challenges of alkali metals,including their high chemical reactivity,uncontrolled dendrite growth,unstable solid electrolyte interphase,and infinite volume expansion during cycling processes.Introducing carbon nanotube-based nanomaterials in alkali metal anodesis an effective solution to these issues.These nanomaterials have attracted widespread attention owing to their unique properties,such as their high specific surface area,superior electronic conductivity,and excellent mechanical stability.Considering the rapidly growing research enthusiasm for this topic in the last several years,we review recent progress on the application of carbon nanotube-based nanomaterials in stable and dendrite-free alkali metal anodes.The merits and issues of alkali metal anodes,as well as their stabilizing strategies are summarized.Furthermore,the relationships among methods of synthesis,nano-or microstructures,and electrochemical properties of carbon nanotube-based alkali metal anodes are systematically discussed.In addition,advanced characterization technologies on the reaction mechanism of carbon nanotube-based nanomaterials in alkali metal anodes are also reviewed.Finally,the challenges and prospects for future study and applications of carbon nanotube-based AMAs in high-performance alkali metal batteries are discussed.

Simulation of inclined dendrites under natural convection by KKS phase field model based on CUDA

In this work,Al-4.5wt.%Cu was selected as the research object,and a phase field-lattice Boltzmann method(PF-LBM)model based on compute unified device architecture(CUDA)was established to solve the problem of low serial computing efficiency of a traditional CPU and achieve significant acceleration.This model was used to explore the evolution of dendrite growth under natural convection.Through the study of the tip velocities,it is found that the growth of the dendrite arms at the bottom is inhibited while the growth of the dendrite arms at the top is promoted by natural convection.In addition,research on the inclined dendrite under natural convection was conducted.It is observed that there is a deviation between the actual growth direction and the preferred angle of the inclined dendrite.With the increase of the preferred angle of the seed,the difference between the actual growth direction and the initial preferred angle of the inclined dendrite shows a trend of increasing at first and then decreasing.In the simulation area,the relative deflection directions of the primary dendrite arms in the top right corner and the bottom left corner of the same dendrite are almost counterclockwise,while the relative deflection directions of the other two primary dendrite arms are clockwise.

Motor neuron-specific RhoA knockout delays degeneration and promotes regeneration of dendrites in spinal ventral horn after brachial plexus injury

Dendrites play irreplaceable roles in the nerve conduction pathway and are vulnerable to various insults.Peripheral axotomy of motor neurons results in the retraction of dendritic arbors,and the dendritic arbor can be re-expanded when reinnervation is allowed.RhoA is a target that regulates the cytoskeleton and promotes neuronal survival and axon regeneration.However,the role of RhoA in dendrite degeneration and regeneration is unknown.In this study,we explored the potential role of RhoA in dendrites.A line of motor neuronal conditional knockout mice was developed by crossbreeding HB9~(Cre+)mice with RhoA~(flox/flox)mice.We established two models for assaying dendrite degeneration and regeneration,in which the brachial plexus was transection or crush injured,respectively.We found that at 28 days after brachial plexus transection,the density,complexity,and structural integrity of dendrites in the ventral horn of the spinal cord of RhoA conditional knockout mice were slightly decreased compared with that in Cre mice.Dendrites underwent degeneration at 7 and 14 days after brachial plexus transection and recovered at 28–56 days.The density,complexity,and structural integrity of dendrites in the ventral horn of the spinal cord of RhoA conditional knockout mice recovered compared with results in Cre mice.These findings suggest that RhoA knockout in motor neurons attenuates dendrite degeneration and promotes dendrite regeneration after peripheral nerve injury.

Chemical surface tuning of zinc metal anode toward stable,dendrite-less aqueous zinc-ion batteries

The commercialization of Zn batteries is confronted with urgent challenges in the metal anode,such as dendrite formation,capacity loss,and cracking or dissolution.Here,surface interfacial engineering of the Zn anode is introduced for achieving safety and dendritic-free cycling for high-performance aqueous Zn batteries through a simple but highly effective chemical etching-substitution method.The chemical modification induces a rough peak-valley surface with a thin fluorine-rich interfacial layer on the Zn anode surface,which regulates the growth orientation via guiding uniform Zn plating/stripping,significantly enhances accessibility to aqueous electrolytes and improves wettability by reducing surface energy.As a result,such a synergetic surface effect enables uniform Zn plating/stripping with low polarization of 29 m V at a current density of 0.5 m A cm^(-2) with stable cyclic performance up to 1000 h.Further,a full cell composed of a fluorine-substituted Zn anode coupled with aβ-MnO_(2)or Ba-V_(6)O_(13)cathode demonstrates improved capacity retention to 1000 cycles compared to the pristine-Zn cells.The proposed valley deposition model provides the practical direction of surface-modified interfacial chemistries for improving the electrochemical properties of multivalent metal anodes via surface tuning.

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.

Elucidating the suppression of lithium dendrite growth with a void-reduced anti-perovskite solid-state electrolyte pellet for stable lithium metal anodes

Solid-state lithium-metal batteries,with their high theoretical energy density and safety,are highly promising as a next-generation battery contender.Among the alternatives proposed as solid-state electrolyte,lithium-rich anti-perovskite(Li RAP)materials have drawn the most interest because of high theoretical Li^(+)conductivity,low cost and easy processing.Although solid-state electrolytes are believed to have the potential to physically inhibit the lithium dendrite growth,lithium-metal batteries still suffer from the lithium dendrite growth and thereafter the short circuiting.The voids in practical Li RAP pellets are considered as the root cause.Herein,we show that reducing the voids can effectively suppress the lithium dendrite growth.The voids in the pellet resulted in an irregular Li^(+)flux distribution and a poor interfacial contact with lithium metal anode;and hence the ununiform lithium dendrites.Consequently,the lithium-metal symmetric cell with void-reduced Li_(2)OHCl-HT pellet was able to display excellent cycling performance(750 h at 0.4 m A cm^(-2))and stability at high current density(0.8 m A cm^(-2)for 120 h).This study provides not only experimental evidence for the impact of the voids in Li RAP pellets on the lithium dendrite growth,but also a rational pellet fabrication approach to suppress the lithium dendrite growth.

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.

Effects of direct current electric field on corrosion behaviour of copper, Cl- ion migration behaviour and dendrites growth under thin electrolyte layer

Effect of direct current electric field （DCEF） on corrosion behaviour of copper printed circuit board （PCB-Cu）, Cl-ion migration behaviour, dendrites growth under thin electrolyte layer was investigated using potentiodynamic polarization and scanning electron microscopy （SEM） with energy dispersive spectrometer （EDS）. Results indicate that DCEF decreases the corrosion of PCB-Cu;Cl-ions directionally migrate from the negative pole to the positive pole, and enrich on the surface of the positive pole, which causes serious localized corrosion; dendrites grow on the surface of the negative pole, and the rate and scale of dendrite growth become faster and greater with the increase of external voltage and exposure time, respectively.

Effect of melt convection on primary dendrite arm spacing in directionally solidified Pb-26%Bi hypo-peritectic alloys

Primary dendrite arm spacing（PDAS） of α phase in directionally solidified Pb-26%Bi（mass fraction） hypo-peritectic alloys was measured by considering the effect of melt convection in cylindrical samples with different diameters.The experimental results show the measured PDAS increases with increasing diameter of the sample.At the growth velocity of 5 μm/s,its value changes from 161.5 μm for the sample with 1.8 mm in diameter to 240.4 μm for the sample with 7 mm in diameter.The strong melt convection in large diameter samples causes a high bulk alloy composition and a high concentration gradient in peritectic β phase,resulting in a larger PDAS.Simultaneously,the high concentration gradient could effectively promote the peritectic transformation,enhancing the dissolution of the thin α dendrite.

Kinetic nucleation of primary α(Al) dendrites in Al-7%Si-Mg cast alloys with Ce and Sr additions

Nucleation of dendritic primaryα（Al） phase with addition of element Ce and Sr in hypoeutectic Al-7%Si-Mg cast alloy was investigated by using differential scanning calorimetry （DSC） and scanning electron microscopy. DSC results were used to calculate the activation energy and nucleation work of primaryα（Al） phase. The results show that the values of activation energy and nucleation work are decreased and the nucleation frequency is increased with the additions of Ce and Sr to the alloys. Moreover, the grain size of dendriticα（Al） phase is well refined, and the nucleation temperatures of primaryα（Al） dendrites are decreased with the additions of Ce and Sr. The effects of elements Ce and Sr additions on kinetic nucleation of primary α（Al） phases were also discussed in hypoeutectic Al-7%Si-Mg cast alloy.

Directional growth behavior of a(Al) dendrites during concentration-gradientcontrolled solidification process in static magnetic field

The large and small sized Cu（solid）/Al（liquid） couples were prepared to investigate the directional growth behavior of primary a（Al） phase during a concentration-gradient-controlled solidification process under various static magnetic fields（SMFs）.The results show that in the large couples,the α（Al） dendrites reveal a directional growth character whether without or with the SMF.However,the 12 T magnetic field induces regular growth,consistent deflection and the decrease of secondary arm spacing of the dendrites.In the small couples,the α（Al） dendrites still reveal a directional growth character to some extent with a SMF of ≤5 T.However,an 8.8 T SMF destroys the directional growth and induces severe random deflections of the dendrites.When the SMF increases to 12 T,the a（Al） dendrites become quite regular despite of the consistent deflection.The directional growth arises from the continuous long-range concentration gradient field built in the melt.The morphological modification is mainly related to the suppression of natural convections and the induction of thermoelectric magnetic convection by the SMF.