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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Overall clinical course of indeterminate dendritic cell tumor patients without skin lesions:A rare case report

BACKGROUND Indeterminate dendritic cell tumor(IDCT)is a rare tumor of immune cells,and IDCT patients without skin lesions are rarely reported.Therefore,the clinical course in this type of patient is unclear,and further research on the underlying pathological mechanisms and appropriate treatments is needed.CASE SUMMARY This study describes a female IDCT patient with bile duct lesions.The strong mimicry of IDCT lesions confused doctors,and consequently,this patient,who had no skin lesions,was first diagnosed with cholangiocarcinoma.Then,she presented with persistent abdominal distension without jaundice.Enlarged mesenteric lymph nodes along with massive ascites were observed in the subsequent imaging examination.However,no tumor cells or pathogens were found in the three subsequent ascites analyses.It took 2 years to reach the correct diagnosis,which was eventually obtained by performing surgery for biopsy of the patient’s abdominal lymph nodes.However,by then,she was already in a cachexic state.Finally,she received a cycle of cyclophosphamide therapy and was advised to visit a hospital specializing in rare diseases.CONCLUSION For IDCT patients without skin lesions,early biopsy is the key to obtaining a correct diagnosis.Moreover,the collective management of IDCT patients is important.Further histological and molecular biology studies based on human specimens are critical for understanding the pathological mechanism of dendritic cell tumors in the future.

Relationship between Phenotypic Changes of Dendritic Cell Subsets and the Onset of Plateau Phase during Intermittent Interferon Therapy in Patients with CHB

Objective This study aimed to evaluate whether the onset of the plateau phase of slow hepatitis B surface antigen decline in patients with chronic hepatitis B treated with intermittent interferon therapy is related to the frequency of dendritic cell subsets and expression of the costimulatory molecules CD40,CD80,CD83,and CD86.Method This was a cross-sectional study in which patients were divided into a natural history group(namely NH group),a long-term oral nucleoside analogs treatment group(namely NA group),and a plateau-arriving group(namely P group).The percentage of plasmacytoid dendritic cell and myeloid dendritic cell subsets in peripheral blood lymphocytes and monocytes and the mean fluorescence intensity of their surface costimulatory molecules were detected using a flow cytometer.Results In total,143 patients were enrolled(NH group,n=49;NA group,n=47;P group,n=47).The results demonstrated that CD141/CD1c double negative myeloid dendritic cell(DNmDC)/lymphocytes and monocytes(%)in P group(0.041[0.024,0.069])was significantly lower than that in NH group(0.270[0.135,0.407])and NA group(0.273[0.150,0.443]),and CD86 mean fluorescence intensity of DNmDCs in P group(1832.0[1484.0,2793.0])was significantly lower than that in NH group(4316.0[2958.0,5169.0])and NA group(3299.0[2534.0,4371.0]),Adjusted P all<0.001.Conclusion Reduced DNmDCs and impaired maturation may be associated with the onset of the plateau phase during intermittent interferon therapy in patients with chronic hepatitis B.

PCDH17 restricts dendritic spine morphogenesis by regulating ROCK2-dependent control of the actin cytoskeleton,modulating emotional behavior

Proper regulation of synapse formation and elimination is critical for establishing mature neuronal circuits and maintaining brain function.Synaptic abnormalities,such as defects in the density and morphology of postsynaptic dendritic spines,underlie the pathology of various neuropsychiatric disorders.Protocadherin 17(PCDH17)is associated with major mood disorders,including bipolar disorder and depression.However,the molecular mechanisms by which PCDH17 regulates spine number,morphology,and behavior remain elusive.In this study,we found that PCDH17 functions at postsynaptic sites,restricting the number and size of dendritic spines in excitatory neurons.Selective overexpression of PCDH17 in the ventral hippocampal CA1 results in spine loss and anxiety-and depression-like behaviors in mice.Mechanistically,PCDH17 interacts with actin-relevant proteins and regulates actin filament(F-actin)organization.Specifically,PCDH17 binds to ROCK2,increasing its expression and subsequently enhancing the activity of downstream targets such as LIMK1 and the phosphorylation of cofilin serine-3(Ser3).Inhibition of ROCK2 activity with belumosudil(KD025)ameliorates the defective F-actin organization and spine structure induced by PCDH17 overexpression,suggesting that ROCK2 mediates the effects of PCDH17 on F-actin content and spine development.Hence,these findings reveal a novel mechanism by which PCDH17 regulates synapse development and behavior,providing pathological insights into the neurobiological basis of mood disorders.

Coexisting fast–slow dendritic traveling waves in a 3D-array electric field coupled neuronal network

Coexistence of fast and slow traveling waves without synaptic transmission has been found in hhhippocampal tissues,which is closely related to both normal brain activity and abnormal neural activity such as epileptic discharge. However, the propagation mechanism behind this coexistence phenomenon remains unclear. In this paper, a three-dimensional electric field coupled hippocampal neural network is established to investigate generation of coexisting spontaneous fast and slow traveling waves. This model captures two types of dendritic traveling waves propagating in both transverse and longitude directions: the N-methyl-D-aspartate(NMDA)-dependent wave with a speed of about 0.1 m/s and the Ca-dependent wave with a speed of about 0.009 m/s. These traveling waves are synaptic-independent and could be conducted only by the electric fields generated by neighboring neurons, which are basically consistent with the in vitro data measured experiments. It is also found that the slow Ca wave could trigger generation of fast NMDA waves in the propagation path of slow waves whereas fast NMDA waves cannot affect the propagation of slow Ca waves. These results suggest that dendritic Ca waves could acted as the source of the coexistence fast and slow waves. Furthermore, we also confirm the impact of cellular spacing heterogeneity on the onset of coexisting fast and slow waves. The local region with decreasing distances among neighbor neurons is more liable to promote the onset of spontaneous slow waves which, as sources, excite propagation of fast waves. These modeling studies provide possible biophysical mechanisms underlying the neural dynamics of spontaneous traveling waves in brain tissues.

Suppressing dendritic metallic Li formation on graphite anode under battery fast charging

Lithium-ion batteries(LIBs)with fast-charging capability are essential for enhancing consumer experience and accelerating the global market adoption of electric vehicles.However,achieving fast-charging capability without compromising energy density,cycling lifespan,and safety of LIBs remains a significant challenge due to the formation of dendritic Li metal on graphite anode under fast charging condition.In view of this,the fundamentals for the dendritic metallic Li formation and the strategies for suppressing metallic Li plating based on analyzing the entire Li^(+)transport pathway at the anode including electrolyte,pore structure of electrode,and surface and bulk of materials are summarized and discussed in this review.Besides,we highlight the importance of designing thick electrodes with fast Li^(+)transport kinetics and comprehensively understanding the interaction between solid electrolyte interphase(SEI)and Li^(+)migration in order to avoid the formation of dendritic Li metal in practical fast-charging batteries.Finally,the regulation of Li metal plating with plane morphology,instead of dendritic structure,on the surface of graphite electrode under fast-charging condition is analyzed as a future direction to achieve higher energy density of batteries without safety concerns.

Effect of applied electric fields on supralinear dendritic integration of interneuron

Evidences show that electric fields(EFs)induced by the magnetic stimulation could modulates brain activities by regulating the excitability of GABAergic interneuron.However,it is still unclear how and why the EF-induced polarization affects the interneuron response as the interneuron receives NMDA synaptic inputs.Considering the key role of NMDA receptor-mediated supralinear dendritic integration in neuronal computations,we suppose that the applied EFs could functionally modulate interneurons’response via regulating dendritic integration.At first,we build a simplified multi-dendritic circuit model with inhomogeneous extracellular potentials,which characterizes the relationship among EF-induced spatial polarizations,dendritic integration,and somatic output.By performing model-based singular perturbation analysis,it is found that the equilibrium point of fast subsystem can be used to asymptotically depict the subthreshold input–output(sI/O)relationship of dendritic integration.It predicted that EF-induced strong depolarizations on the distal dendrites reduce the dendritic saturation output by reducing driving force of synaptic input,and it shifts the steep change of sI/O curve left by reducing stimulation threshold of triggering NMDA spike.Also,the EF modulation prefers the global dendritic integration with asymmetric scatter distribution of NMDA synapses.Furthermore,we identify the respective contribution of EF-regulated dendritic integration and EF-induced somatic polarization to an action potential generation and find that they have an antagonistic effect on AP generation due to the varied NMDA spike threshold under EF stimulation.

The interaction between KIF21A and KANK1 regulates dendritic morphology and synapse plasticity in neurons

Morphological alterations in dendritic spines have been linked to changes in functional communication between neurons that affect learning and memory.Kinesin-4 KIF21A helps organize the microtubule-actin network at the cell cortex by interacting with KANK1;however,whether KIF21A modulates dendritic structure and function in neurons remains unknown.In this study,we found that KIF21A was distributed in a subset of dendritic spines,and that these KIF21A-positive spines were larger and more structurally plastic than KIF21A-negative spines.Furthermore,the interaction between KIF21A and KANK1 was found to be critical for dendritic spine morphogenesis and synaptic plasticity.Knockdown of either KIF21A or KANK1 inhibited dendritic spine morphogenesis and dendritic branching,and these deficits were fully rescued by coexpressing full-length KIF21A or KANK1,but not by proteins with mutations disrupting direct binding between KIF21A and KANK1 or binding between KANK1 and talin1.Knocking down KIF21A in the hippocampus of rats inhibited the amplitudes of long-term potentiation induced by high-frequency stimulation and negatively impacted the animals’cognitive abilities.Taken together,our findings demonstrate the function of KIF21A in modulating spine morphology and provide insight into its role in synaptic function.