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.

Construction of Phosphorus-Functionalized Multichannel Carbon Interlayers for Dendrite-Free Metallic Zn Anodes

Zn metal anodes are usually subject to grave dendrite growth during platting/stripping,which dramatically curtails the lifespan of aqueous Zn-ion batteries and capacitors.To address above problems,in our work,a novel phosphorus-functionalized multichannel carbon interlayer was designed and covered on Zn anodes.The results demonstrated that the multichannel structure combined with the three-dimensional meshy skeleton can provide more sufficient space for Zn deposition,thereby effectively inhibiting the growth of zinc dendrites.Meanwhile,theoretical calculations also confirmed that the P-C and P=O functional groups from phosphorus-functionalized multichannel carbon interlayer have the decisive influence in reducing the zinc nucleation potential and depositing uniformly zinc.Concretely,the symmetrical battery assembled with phosphorus-functionalized multichannel carbon interlayer-covered Zn anodes possessed a long lifetime of 3300 h at 2 mA cm^(-2)with 1 mAh cm^(-2).Furthermore,the full cell with activated carbon cathodes exhibited a high specific capacity of 80.5 mAh g^(-1)and outstanding cycling stability without capacity decay after 15000 cycles at a high current density of 5 A g^(-1).The superior electrochemical performance exceeded that of most reported papers.Consequently,our synthesized zincophilic interlayer with the unique structure has superior prospects for application in stabilizing zinc anodes and prolonging the lifespan of batteries.

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.

Facilely constructing ultrahigh lattice-matched CuZn_(5) epitaxial interface for dendrite-free Zn metal anode

Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions.Whereas most of protective layers are complex and costly,making commercial applications challenging.Herein,we introduce a facile method involving the addition of CuCl_(2) electrolyte additives to conventional electrolyte systems,which,through rapid displacement reactions and controlled electrochemical cycling,forms a CuZn_(5) alloy layer with 97.2%lattice matching to the(002)plane(CuZn_(5)@Zn),thus regulating the(002)plane epitaxial deposition.As a result,the symmetric cells with CuZn_(5)@Zn demonstrate an ultra-long cycle life of 3600 h at 1 mA cm^(-2).Under extreme conditions of high current density(20 m A cm^(-2))and high zinc utilization(DOD_(Zn)=50%),stable cycling performance is maintained for 220 and 350 h,respectively.Furthermore,the CuZn_(5)@Zn||NH_(4)V_(4)O_(10)full cell maintains a capacity of 120 m A h g^(-1)even after 10,000 cycles at a high current density of 10 A g^(-1).This work presents a facile and efficient strategy for constructing stable metal anode materials,with implications for the development of next-generation rechargeable 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.

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.

Phase field method simulation of faceted dendrite growth with arbitrary symmetries

A numerical simulation based on a regularized phase field model is developed to describe faceted dendrite growth morphology. The effects of mesh grid, anisotropy, supersaturation and fold symmetry on dendrite growth morphology were investigated, respectively. These results indicate that the nucleus grows into a hexagonal symmetry faceted dendrite. When the mesh grid is above 640×640, the size has no much effect on the shape. With the increase in the anisotropy value, the tip velocities of faceted dendrite increase and reach a balance value, and then decrease gradually. With the increase in the supersaturation value, crystal evolves from circle to the developed faceted dendrite morphology. Based on the Wulff theory and faceted symmetry morphology diagram, the proposed model was proved to be effective, and it can be generalized to arbitrary crystal symmetries.

Effect of sample diameter on primary and secondary dendrite arm spacings during directional solidification of Pb-26wt.%Bi hypo-peritectic alloy

The microstructure scales of dendrites, such as primary and secondary dendrite arm spacings, control the segregation profiles and the formation of secondary phases within interdendritic regions, which determine the properties of solidified structures. Investigations on primary and secondary dendrite arm spacings of primary a-phase during directionally solidified Pb-26wt%Bi hypo-peritectic alloy were carried out in this research, and systematic studies were conducted using cylindrical samples with different diameters （Ф = 1.8 and 7.0 mm） in order to analyze the effects of sample diameter on the primary and secondary dendrite arm spacings. In this work, the dependence of dendrite arm spacings on growth velocity was established. In addition, the experimental data concerning the primary and secondary dendrite ann spacings were compared with the main predictive dendritic models from the literatures. A comparison between experimental results for dendrite arm spacings of the 1.8-mm-diameter sample and 7.0-ram-diameter sample was also conducted.

Effects of physical parameters on the cell-to-dendrite transition in directional solidification

A quantitative cellular automaton model is used to study the cell-to-dendrite transition（CDT） in directional solidification. We give a detailed description of the CDT by carefully examining the influence of the physical parameters, including：the Gibbs–Thomson coefficient Γ, the solute diffusivity Dl, the solute partition coefficient k0, and the liquidus slope ml. It is found that most of the parameters agree with the Kurz and Fisher（KF） criterion, except for k0. The intrinsic relations among the critical velocity Vcd, the cellular primary spacing λc,max, and the critical spacing λcd are investigated.

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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.

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Numerical Modelling and Experimental Investigation of Microse-gregation in Al-4.45 wt pct Cu:Effect of Dendrite Joining

A numerical model Alloy/M has been applied to investigate the microsegregation in Al-4.45 wt pct Cu alloy. The calculated data were compared with the experimental measurements for samples solidified at different cooling rates. Discrepancies in solute concentration occur between the experimental observations and calculated results. Reasons for the discrepancies were discussed, and the effect of dendrite joining at a later stage of solidification on the microsegregation was investigated. Calculations that have included this effect showed a better fit with experimental results.

Porous LiF layer fabricated by a facile chemical method toward dendrite-free lithium metal anode

Lithium metal is supposed to be critical material for constructing next-generation batteries due to extremely high capacity and ultralow redox potential. However, the perplexing issue of lithium dendrite growth impedes the commercial application. The initial nucleation and low Li ions diffusion rate in the electrolyte/electrode interface dominate the deposition behavior. Therefore, a uniform and flexible interface is urgently needed. Here, a facile method is proposed to prepare a thin and porous LiF-rich layer (TPL) by the in-situ reaction of small amount of ammonium hydrogen difluoride (NH4HF2) and Li metal. The deposition morphology on Li metal anode with LiF layer is significantly flat and homogeneous owning to low lateral diffusion barrier on LiF crystals and the porous structure of TPL film. Additionally, the symmetrical cells made with such TPL Li anodes show significantly stable cycling over 100 cycles at high current density of 6 mA/cm^2. The TPL Li|LiFePO4 full cells keep over 99% capacity retention after 100 cycles at 2.0 C. This approach serves as a facile and controllable way of adjusting the protective layer on Li metal.