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.

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.

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.

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.

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.

The dynamic evolution of aggregated lithium dendrites in lithium metal batteries

Lithium(Li)metal anodes promise an ultrahigh theoretical energy density and low redox potential,thus being the critical energy material for next-generation batteries.Unfortunately,the formation of Li dendrites in Li metal anodes remarkably hinders the practical applications of Li metal anodes.Herein,the dynamic evolution of discrete Li dendrites and aggregated Li dendrites with increasing current densities is visualized by in-situ optical microscopy in conjunction with ex-situ scanning electron microscopy.As revealed by the phase field simulations,the formation of aggregated Li dendrites under high current density is attributed to the locally concentrated electric field rather than the depletion of Li ions.More specifically,the locally concentrated electric field stems from the spatial inhomogeneity on the Li metal surface and will be further enhanced with increasing current densities.Adjusting the above two factors with the help of the constructed phase field model is able to regulate the electrodeposited morphology from aggregated Li dendrites to discrete Li dendrites,and ultimately columnar Li morphology.The methodology and mechanistic understanding established herein give a significant step toward the practical applications of Li metal anodes.

Suppressing Li Dendrites via Electrolyte Engineering by Crown Ethers for Lithium Metal Batteries

Electrolyte engineering is considered as an effective strategy to establish stable solid electrolyte interface(SEI),and thus to suppress the growth of lithium dendrites.In a recent study reported in Advanced Functional Materials by Ma group,discovered that strong coordination force could be founded between 15-Crown-5 ether(15-C-5) and Li+,which facilitates the crown ether(15-C-1) to participate in the solvation structure of Li+ in the electrolyte for the same purpose.Such a novel strategy might impact the design of highperformance and safe lithium metal batteries(LMB s).

Structural changes in pyramidal cell dendrites and synapses in the unaffected side of the sensorimotor cortex following transcranial magnetic stimulation and rehabilitation training in a rat model of focal cerebral infarct

Very little is known about the effects of transcranial magnetic stimulation and rehabilitation training on pyramidal cell dendrites and synapses of the contralateral, unaffected sensorimotor cortex in a rat model of focal cerebral infarct. The present study was designed to explore the mechanisms underlying improved motor function via transcranial magnetic stimulation and rehabilitation training following cerebral infarction. Results showed that rehabilitation training or transcranial magnetic stimulation alone reduced neurological impairment in rats following cerebral infarction, as well as significantly increased synaptic curvatures and post-synaptic density in the non-injured cerebral hemisphere sensorimotor cortex and narrowed the synapse cleft width. In addition, the percentage of perforated synapses increased. The combination of transcranial magnetic stimulation and rehabilitation resulted in significantly increased total dendritic length, dendritic branching points, and dendritic density in layer V pyramidal cells of the non-injured cerebral hemisphere motor cortex. These results demonstrated that transcranial magnetic stimulation and rehabilitation training altered structural parameters of pyramidal cell dendrites and synapses in the non-injured cerebral hemisphere sensorimotor cortex, thereby improving the ability to compensate for neurological functions in rats following cerebral infarction.

Growth and microstructure of AlN whiskers and dendrites

AlN whiskers or dendrites were synthesized with asublimation-recrystallization method by using Al, AlN powders and some additives as raw materials.Whiskers with different sizes that featured high purity and good crystallinity were obtained bycontrolling temperature and gas supersaturation in the reaction container. The whiskers weredescribed as long and straight single crystals of approximately 1-30 mu m in diameter by thecentimeter range in length. However, AlN dendrites were about 1mm in diameter by 0.5cm in length,and showed an obviously preferential growth orientation, i.e., perpendicular to [21-bar1-bar1] and[101-bar1] planes. It is concluded that the whiskers or dendrites grow via the vapor-solidmechanism.

Phase-field numerical simulation of three-dimensional competitive growth of dendrites in a binary alloy

The normal vector of migration direction in the solid-liquid interface of dendrites was used to describe the phase-field governing equation. By using the three angles formed by the normal vector for the migration direction of the dendritic growth interface and the coordinate axes of the simulation region, the authors expressed the interfacial anisotropy equation, and built a phase-field model for the competitive growth of multiple grains. Taking a Al-2%mole-Cu binary alloy as an example, the competitive growth of multiple grains during isothermal solidification was simulated by applying parallel computing techniques. In addition, the phase field simulation results were verified by the experimental method. The simulation results show that the competitive growth of equiaxed dendrite is divided into two types: the first occurs during the process of competitive growth, the tips of primary dendrite on different grains taking part in the competition stop growing in their optimal growth direction; the second also occurs during competitive growth, the tips of primary dendrite which participate in the competition on different grains never stop growing in their optimal growth direction. The dendritic morphologies of the first competition growth type are divided into two types. Primary dendrites of grains taking part in the competition stop growing in their optimal growth direction and the competition plane enlarges when neither one wins the competition. However, when one wins the competition, the primary dendrites of grains with superiority go through the blocking grains and continue to grow in their optimal growth direction. The primary dendrites of inferior grains stop growing in their optimal growth direction and then instead grow in those areas without obstacles. The dendritic morphology of the second competition-growth type is shown to be the deformation of primary dendrites, which are mainly represented as the deflection and bending observed from different views. Compared with the metallographic picture, the simulation results can show the morphology of the competitive growth in all directions, so this simulation method can better characterize the competitive growth process.

Settling velocity of equiaxed dendrites in a tube

The settling velocity of equiaxed dendrites can cause macrosegregation and influence the structure of the equiaxed zone during the casting solidification process. So an understanding of the settling characteristics is needed to predict the structure and segregation in castings. The settling velocity of NH4Cl equiaxed dendrites of non-spherical geometry was studied experimentally in an NH4Cl-70wt.%H2O solution. A calculation formula was proposed to calculate the settling velocity of sediment equiaxed dendrites in a tube filled with saturated solution at a moderate Reynolds number region. The retardation effects of the wall and morphology of the equiaxed dendrite on the settling velocity were taken into account in the development of the calculation formula, and the correction function B of the drag coefficient with consideration of the retardation effects of the wall and morphology of the equiaxed dendrite on the settling velocity of the equiaxed dendrite was calibrated according to the experimental results. A comparison showed that the formula has a good accordance with the experimental results.

The Vesicle-containing Spines of the Dendrites in the Rat Hippocampus

The present article deals with the ultrastructure of the dendrites and their synapses in the rat hippocampus and the besicle-cotaining spines of the dendrites in the Ammon’s Horn were first recorded.Using glutaraldehyde-osmic acid as fixatives for present work.

EFFECT OF AUSTENITIC DENDRITES ON MECHANICAL PROPERTIES OF DUCTILE IRON

Impact toughness of ductile nodular cast iron loaded perpendicular to the austenitic dendrites is found to be 43% higher than that parallel to ones.Yet tensile strength and elongation of the former are 23% and 30% lower than the later respectively.It is belived that the dendritic segregation may cause such differences.

Morphological Heredity of Intermetallic Nb_(5)Si_(3)Dendrites in Hypereutectic Nb-Si Based Alloys via Non-Equilibrium Solidification

For hypereutectic Nb-Si based alloys,primary Nb_(5)Si_(3)phases typically grow in a faceted mode during equilibrium or near-equilibrium solidification,which damages the ductility and toughness.To address this issue,here we artificially manipulate the growth morphology of Nb_(5)Si_(3)using electron beam surface melting(EBSM)and subsequent annealing treatments.Results show that such a non-equilibrium solidification pathway enables the transition from faceted growth to non-faceted dendritic growth of Nb_(5)Si_(3),along with evident microstructure refinement,generation of metastableβ-Nb_(5)Si_(3)phases and elimination of chemical segregation.The transformation fromβ-Nb_(5)Si_(3)toα-Nb_(5)Si_(3)and Nb solid solution(Nbss)particles is triggered by the annealing treatment at 1450°C for 5 h.Also,we find the annealing-mediated formation of inherited Nb_(5)Si_(3)dendrites that maintain the dendritic morphology of the original as-solidifiedβ-Nb_(5)Si_(3)dendrites.This work thus provides a feasible routine to obtain thermally stable and refinedα-Nb_(5)Si_(3)dendrites in hypereutectic Nb-Si based alloys.

Novel single-ion conducting polymer electrolytes with high toughness and high resistance against lithium dendrites

Solid-state polymer electrolytes are considered as an alternative to classic liquid electrolytes,particularly for application in highenergy lithium metal batteries.With respect to common dual-ion conductors,single-ion conducting polymer electrolytes(SICPEs)are less affected by lithium dendrites growth and thus are particularly interesting for application in lithium metal batteries.In this work,novel SIC-PEs are developed,based on an ionomer having poly(ethylene-alt-maleimide)backbone and lithium phenylsulfonyl(trifluoromethanesulfonyl)imide pendant moieties,further blended with poly(ethylene oxide)(PEO)and poly(ethylene glycol)dimethyl ether(PEGDME).These SIC-PEs exhibit ionic conductivity around~7×10^(−6)S·cm^(−1) at 70℃,lithium transference number close to unity,and excellent mechanical properties,with fracture toughness over 30 J·cm^(−3).Additionally,the electrolytes show very high resistance against lithium dendrites growth,by cycling for more than 1200 h in Li°symmetric cells at a current density of 0.1 mA·cm^(−2).LiFePO4||Li°cells with these SIC-PEs were cycled at 70℃ and C/10,showing initial capacity of almost 160 mAh·g^(−1)and residual capacity of 45%after 100 cycles.This work shows that single-ion conducting polymer electrolytes based on poly(ethylene-alt-maleimide)backbone are promising materials for application as electrolytes or catholytes in lithium metal polymer batteries.

Laser irradiation constructing all-in-one defective graphenepolyimide separator for effective restraint of lithium dendrites and shuttle effect

The commercialization of lithium-sulfur(Li-S)batteries faces several bottlenecks,and the major two of which are the shuttle effect of polysulfides and the wild growth of Li dendrites,responsible for fast capacity decay and severe safety issues.As an essential component of Li-S batteries,the structure and properties of the separators are closely related to the above problems,and the exploration of multifunctional separators is highly sought-after.Herein,an integrated separator composited of defective graphene and polyimide(DG-PI)was innovatively fabricated by electrospinning combined with the laser-induced carbonization strategy.The all-in-one compact architecture with well-interconnected channels shows superior mechanical and thermal stability and wettability.More importantly,the PI nanofibers containing N–/O–functional groups can induce the uniform deposition of lithium on the anode surface,while the DG framework with abundant pentagonal/heptagonal rings and vacancies can strongly trap polysulfides and accelerate polysulfide transformation on the cathode side.The strong chemical interaction between the insulative PI layer and the conductive DG layer modulates the surface charge distribution of each other,leading to more prominent contributions to restraining lithium dendrites and shuttle effect.Therefore,the Li-S batteries based on the integrated DG-PI separators afford an excellent performance in protecting lithium anode(stable cycles of 200 h at 5 mA·cm^(−2))and good cycling stability with a low capacity decay of 0.05%per cycle after 700 cycles at 1 C.This work offers a new design concept of multifunctional Li-S battery separators and broadens the application scope of laser micro-nano fabrication technology.

Initiation of dendritic NMDA spikes co-regulated via distance-dependent and dynamic distribution of the spine number and morphology in neuron dendrites

Dendritic spines are small membranous protrusions that receive synaptic inputs from other neurons,enabling the initiation of dendritic N-methyl-D-aspartic(NMDA)spikes and somatic action potentials.During learning and memory processes,both the number of spines on a dendrite and the morphology of individual spines are constantly changing.The individual influence of spine number and morphology on dendritic NMDA spikes has already been revealed,but the functional significance of the coregulation of spine number and morphology on NMDA spikes remains elusive.Here,we systematically investigated the initiation of local dendritic NMDA spikes by the dynamic distributions of the spine number and morphology on single dendrites in reconstructed neuron models.Different from the traditional cognition,we found the threshold number of spines required to generate local dendrite NMDA spikes on distal dendrites is fewer than that on proximal ones,because the thinner distal dendrites own higher impedance.As for the spine morphology,the presence of moreα-amino-3-hydroxy-5-methyl-4-isoxazole-propionic acid(AMPA)receptors on the spine leads to larger NMDA spikes rather than an increase in the spine dimension alone.Furthermore,we first suggested that a single dendrite containing spines with gradually increasing head diameters away from the soma could generate larger NMDA spikes than that irrational distribution of spine morphology containing spines with decreasing head diameters,which can be compensated by the increasing spine number.Complementarily,the distance-dependent distribution of spine number and morphology co-regulate the intension of dendritic NMDA spikes.These findings about the threshold for NMDA spikes provide novel insights into the role of the irrational dynamic distribution of the spine number and morphology in senescence and disease processes such as Alzheimer’s disease,schizophrenia,and Parkinson’s disease,which causes abnormal neuron firing.

Determining the Critical Fracture Stress of Al Dendrites near the Melting Point via Synchrotron X-ray Imaging

Dendrites are the most common microstructural features in the cast metals,significantly affecting the structure integrity and mechanical properties of the castings.In this study,the in situ synchrotron X-ray radiographic and tomographic imaging techniques were combined to evaluate the critical fracture stress of the growing dendrite tip during the solidification of an Al-15 wt%Cu alloy under an external electromagnetic force.Two dendritic 3D models have been proposed to simulate the dendrite 3D morphologic characteristics and thus revealed that the critical fracture stresses of the Al dendrites at temperatures close to its melting point were in the range of 0.5 kPa–0.05 MPa.The present results demonstrate the feasibility of measuring the high-temperature mechanical properties of the metallic dendrites.

Carbon-based interface engineering and architecture design for high-performance lithium metal anodes

Metallic lithium(Li)is considered the“Holy Grail”anode material for the nextgeneration of Li batteries with high energy density owing to the extraordinary theoretical specific capacity and the lowest negative electrochemical potential.However,owing to inhomogeneous Li-ion flux,Li anodes undergo uncontrollable Li deposition,leading to limited power output and practical applications.Carbon materials and their composites with controllable structures and properties have received extensive attention to guide the homogeneous growth of Li to achieve high-performance Li anodes.In this review,the correlation between the behavior of Li anode and the properties of carbon materials is proposed.Subsequently,we review emerging strategies for rationally designing high-performance Li anodes with carbon materials,including interface engineering(stabilizing solid electrolyte interphase layer and other functionalized interfacial layer)and architecture design of host carbon(constructing three-dimension structure,preparing hollow structure,introducing lithiophilic sites,optimizing geometric effects,and compositing with Li).Based on the insights,some prospects on critical challenges and possible future research directions in this field are concluded.It is anticipated that further innovative works on the fundamental chemistry and theoretical research of Li anodes are needed.

Recent progress about transmission electron microscopy characterizations on lithium-ion batteries

With the rapid development of portable electronics,new energy vehicles,and smart grids,ion batteries are becoming one of the most widely used energy storage devices,while the safety concern of ion batteries has always been an urgent problem to be solved.To develop a safety-guaranteed battery,the characterization of the internal structure is indispensable,where electron microscopy plays a crucial role.Based on this,this paper summarizes the application of transmission electron microscopy(TEM)in battery safety,further concludes and analyzes the aspects of dendrite growth and solid electrolyte interface(SEI)formation that affect the safety of ion batteries,and emphasizes the importance of electron microscopy in battery safety research and the potential of these techniques to promote the future development of this field.These advanced electron microscopy techniques and their prospects are also discussed.