The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defect...The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defects in the solid-state electrolyte,leading to internal short circuits that hinder practical application of SSLMB.While conventional experimental and finite element methods provide valuable insights,they are often costly,time-consuming,and inefficient for capturing the complicated stress evolution inside solid-state electrolyte.In this study,we propose a novel machine learning strategy that integrates prior knowledge and physics-informed constraints to predict the von Mises stress distribution induced by the internal defects of solid-state electrolyte.High-quality training datasets generated using a multiphysics simulation framework and key findings from previous studies were incorporated as physicsguided constraints to enhance prediction reliability and physical consistency of machine learning models.By employing a modified UNet architecture with squeeze-and-excitation module,it demonstrates remarkably high accuracy in stress prediction and exhibits excellent robustness and generalization across a wide range of defect scenarios.This model allows us to efficiently obtain the electro-chemo-mechanical failure of solid-state electrolyte,thereby guiding micro structural modifications and facilitating the design of SSLMB for practical applications.展开更多
Garnet lithium lanthanum zirconium oxide(Li_(7)La_(3)Zr_(2)O_(12),LLZO)is a benchmark solid-state electrolyte(SSE)material receiving considerable attention owing to its high conductivity and chemical stability against...Garnet lithium lanthanum zirconium oxide(Li_(7)La_(3)Zr_(2)O_(12),LLZO)is a benchmark solid-state electrolyte(SSE)material receiving considerable attention owing to its high conductivity and chemical stability against Li metal.Although its electro-chemo-mechanical failure mechanisms have been much investigated,the equivocal roles of grain boundary strength and grain size of LLZO remain under-explored,hindering further performance improvements.Here we decoupled the effects of grain size and grain boundary strength of polycrystalline LLZO via the combination of electrochemical kinetics and the cohesive zone model.We discovered that the disintegration of LLZO is initiated by the accumulation of local displacements,which strongly relates to the changes in both grain size and grain boundary strength.However,variations in grain boundary strength affect the diffusion and propagation pathways of damage,while the failure of LLZO is determined by the grain size.Large LLZO grains facilitate transgranular damage under low grain boundary strength,which can alter local chemo-mechanics within the bulk of LLZO,leading to more extensive damage propagation.The results showcase the structure optimization pathways by preferentially controlling the growth of lithium dendrites at grain boundaries and their penetration in garnet-type SSE.展开更多
Flexible solid-state battery has several unique characteristics including high flexibility,easy portability,and high safety,which may have broad application prospects in new technology products such as rollup displays...Flexible solid-state battery has several unique characteristics including high flexibility,easy portability,and high safety,which may have broad application prospects in new technology products such as rollup displays,power implantable medical devices,and wearable equipments.The interfacial mechanical and electrochemical problems caused by bending deformation,resulting in the battery damage and failure,are particularly interesting.Herein,a fully coupled electro-chemo-mechanical model is developed based on the actual solid-state battery structure.Concentration-dependent material parameters,stress-dependent diffusion,and potential shift are considered.According to four bending forms(k=8/mm,0/mm,-8/mm,and free),the results show that the negative curvature bending is beneficial to reducing the plastic strain during charging/discharging,while the positive curvature is detrimental.However,with respect to the electrochemical performance,the negative curvature bending creates a negative potential shift,which causes the battery to reach the cut-off voltage earlier and results in capacity loss.These results enlighten us that suitable electrode materials and charging strategy can be tailored to reduce plastic deformation and improve battery capacity for different forms of battery bending.展开更多
Nickel-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) cathode material has been widely concerned due to its high voltage,high specific capacity and excellent rate performance,which is considered as one of the most promi...Nickel-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) cathode material has been widely concerned due to its high voltage,high specific capacity and excellent rate performance,which is considered as one of the most promising cathode materials for the next generation of high-energy-density solid-state lithium batteries.However,serious electro-chemo-mechanical degradation of Nickel-rich cathode during cycling,especially at a high voltage(over 4.5 V),constrains their large-scale application.Here,using the multiphysical simulation,highly-conductive polymer matrix with spontaneous stress-buffering effect was uncovered theoretically for reinforcing the electrochemical performance of composited NCM81 1 cathode through the visualization of uniform concentration distribution of Li-ion coupled with improved stress field inside NCM811 cathode.Thereupon,polyacrylonitrile(PAN) and soft polyvinylidene fluoride(PVDF) were selected as the polymer matrix to fabricate the composited NCM811 cathode(PVDFPAN@NCM811) for improving the electrochemical performance of the solid-state NMC811|Li full cells,which can maintain high capacity over 146.2 mA h g^(-1)after 200 cycles at a high voltage of 4.5 V.Suggestively,designing a multifunctional polymer matrix with high ionic conductivity and mechanical property can buffer the stress and maintain the integrity of the structure,which can be regarded as the door-opening avenue to realize the high electrochemical performance of Ni-rich cathode for solidstate batteries.展开更多
Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the bat...Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the battery cycling.Here,we tracked phase transformations during(de)lithiation of Sb_(2)Se_(3) single crystals using in situ high-resolution transmission electron microscopy(HRTEM)technique,and revealed electro-chemo-mechanical evolution at the reaction interface.The effect of this electro-chemo-mechanical coupling has a complicated interplay on the lithiation kinetics and causes various types of defects at the reaction front,including dislocation dipoles,antiphase boundaries,and cracks.In return,the formed cracks and related defects build a path for fast diffusion of lithium ions and trigger a highly anisotropic lithiation at the twisted reaction front,giving rise to the formation of presumably "dead" Sb_(2)Se_(3) nanodomains in amorphous Li_(x)Sb_(2)Se_(3).The detailed mechanistic understanding may facilitate the rational design of high-capacity electrode materials for battery applications.展开更多
Lithium-ion batteries are limited by the low energy density of graphite anodes and are gradually becoming unable to meet the demand for energy storage development.A further increase in high capacity requires new batte...Lithium-ion batteries are limited by the low energy density of graphite anodes and are gradually becoming unable to meet the demand for energy storage development.A further increase in high capacity requires new battery materials and chemistry,such as the innovative lithium metal anodes(LMAs).However,the actual commercialization of LMAs is limited by the unstable Li/electrolyte interface,impeding their progress from the laboratory to industrial production.To address these problems,constructing a Li alloy/Li halide mixed layer upon a Li surface is considered to be an ideal direction because of the combined advantages of Li alloys and Li halides.In this context,by comparing the limitations of self-generated solid electrolyte interfaces,the unique merits of Li alloys and Li halides are discussed in depth with summaries of their respective advances.Accordingly,mixed layers of Li alloy/Li halides are introduced,and the mechanisms of Li deposition behaviors are clearly described,along with their manufacturing strategies and recent progress.Moreover,the emerging techniques for interface characterization are also comprehensively summarized.Furthermore,the necessary considerations and outlooks for the future design of Li alloy/Li halide mixed layers are highlighted,with the aim of elucidating the structure-property relationships and providing rational directions for the attainment of the next-generation high-performance batteries.展开更多
Solid-to-solid interfacial issues are one of the most intractable problems hindering the practical application of all-solid-state batteries(ASSBs).The interfacial instability behaviors caused by the rough interface be...Solid-to-solid interfacial issues are one of the most intractable problems hindering the practical application of all-solid-state batteries(ASSBs).The interfacial instability behaviors caused by the rough interface between lithium anode and solid electrolyte(SE)involve complicated electro-chemo-mechanics interplays and their quantitative relationships still remain unclear.The three-dimensional electro-chemomechanical coupled model with randomly generated rough lithium-SE interface is developed in this study to investigate the effects of interface roughness on the interfacial failure behaviors.Results demonstrate that the existence of a rough lithium-SE interface causes the highly concentrated strain,GPa-level stress,and localized current density at the protruding tips,probably inducing dendrite formation and interface cracking.The interface roughness effect is much more pronounced in lithium anode than graphite anode due to their different Li storage mechanisms,i.e.,surface deposition and Li intercalation.Excessive stack pressure(>50 MPa)magnifies the stress effect on overpotential to enlarge the current density localization and deteriorate the interfacial instability issues.Reducing interface roughness through surface treatment,together with regulation of external operation conditions,can effectively improve interfacial stability performance.The results provide an in-depth understanding of the underlying electro-chemo-mechanical coupling mechanism caused by the rough anode-SE interface and bring more insights into further improvement of ASSBs'enhanced reliability and longevity.展开更多
Health management for commercial batteries is crowded with a variety of great issues,among which reliable cycle-life prediction tops.By identifying the cycle life of commercial batteries with different charging histor...Health management for commercial batteries is crowded with a variety of great issues,among which reliable cycle-life prediction tops.By identifying the cycle life of commercial batteries with different charging histories in fast-charging mode,we reveal that the average charging rate c and the resulted cycle life N of batteries obey c=c_(0)N^(b),where c_(0) is a limiting charging rate and b is an electrode-dependent constant.This c-N law,resembling the classic stress versus cycle number relationship(the S-N curve or Wohler curve)of solids subject to cyclic loading,could be applicable to most batteries.Such a scaling law,in combination with a physics-augmented machine-learning algorithm,could foster the predictability of battery life with high fidelity.The scaling of charging rate and cycle number may pave the way for cycle-life prediction and the directions of optimization of advanced batteries.展开更多
Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),a...Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.展开更多
Diffusion-induced stress(DIS)originates from the shrinkage/expand during Li extraction/insertion from/into the active particle for the Li-ion battery(LIB).Till today,the two-way coupled mechanical-electrochemical mech...Diffusion-induced stress(DIS)originates from the shrinkage/expand during Li extraction/insertion from/into the active particle for the Li-ion battery(LIB).Till today,the two-way coupled mechanical-electrochemical mechanism is still unclear.The above challenge can be decomposed into 2W+lH as follows:(i)Why need to reveal the two-way coupled mechanical-electrochemical mechanism?(ii)What is the two-way coupled mechanical-electrochemical mechanism?(iii)How to reveal the two-way coupled mechanical-electrochemical mechanism.In the process of answering the above 2W+lH,the following contributions have been made in this work:(i)An electro-chemo-mechanical(ECM)model is established for the LIB,in which the mechanical-electrochemical coupling is two-way;(ii)The mechanical-electrochemical responses are solved for the ECM model in the time/frequency domain,respectively;(iii)The time-domain analysis shows that DIS enhances Li diffusion at the early and middle stages of discharge,while DIS inhibits Li diffusion at the end of discharge;(iv)The frequency domain analysis shows that stress mainly affects solid-phase diffusion instead of electrolyte-phase diffusion.In a word,the multi-scale analysis quantitatively analyzes the impact of DIS on Li diffusion on the particle scale and reveals the two-way coupled mechanical-electrochemical mechanism on the electrode scale.The above results provide theoretical support for the battery manufacture and stress monitoring.展开更多
Lithium metal batteries(LMBs)are candidates for next-generation energy storage due to their potential to increase energy density.However,the nonuniform electrodeposition of Li during cycling,plus the growth of Li dend...Lithium metal batteries(LMBs)are candidates for next-generation energy storage due to their potential to increase energy density.However,the nonuniform electrodeposition of Li during cycling,plus the growth of Li dendrites and the side reactions between Li metal and the electrolyte,hinder the practical deployment of LMBs.The plating/stripping behavior of Li is an electro-chemo-mechanical process,and gaining a thorough understanding of its mechanisms is a cornerstone of LMB development.In this review,the current understanding of electro-chemo-mechanical processes on Li metal anodes is systematically summarized from the perspectives of Li plating/stripping in liquid-and solid-state electrolytes,the important role of the solid-electrolyte interphase,and the methodologies for understanding the electro-chemo-mechanics of the Li metal anode.The aim is to promote the development of LMBs through the optimization of Li metal anodes,which is based on understanding the fundamental processes occurring during electrochemical plating and stripping.展开更多
Here we review the persisting conceptual discrepancies between different research groups working on artificial muscles based on conducting polymers and other electroactive material.The basic question is if they can be...Here we review the persisting conceptual discrepancies between different research groups working on artificial muscles based on conducting polymers and other electroactive material.The basic question is if they can be treated as traditional electro-mechanical(physical)actuators driven by electric fields and described by some adaptation of their physical models or if,replicating natural muscles,they are electro-chemo-mechanical actuators driven by electrochemical reaction of the constitutive molecular machines:the polymeric chains.In that case the charge consumed by the reaction will control the volume variation of the muscular material and the motor displacement,following the basic and single Faraday’s laws:the charge consumed by the reaction determines the number of exchanged ions and solvent,the film volume variation to lodge/expel them and the amplitude of the movement.Deviations from the linear relationships are due to the osmotic exchange of solvent and to the presence of parallel reactions from the electrolyte,which originate creeping effects.Challenges and limitations are underlined.展开更多
O3-type layered oxide cathodes,such as NaNi_(0.5)Mn_(0.5)O_(2),have garnered significant attention due to their high theoretical specific capacity while using abundant and low-cost sodium as intercalation species.Unli...O3-type layered oxide cathodes,such as NaNi_(0.5)Mn_(0.5)O_(2),have garnered significant attention due to their high theoretical specific capacity while using abundant and low-cost sodium as intercalation species.Unlike the lithium analog(LiNiO_(2)),NaNiO_(2)(NNO)exhibits poor electrochemical performance resulting from structural instability and inferior Coulomb efficiency.To enhance its cyclability for practical application,NNO was modified by titanium substitution to yield the O3-type NaNi_(0.9)Ti_(0.1)O_(2)(NNTO),which was successfully synthesized for the first time via a solid-state reaction.The mechanism behind its superior performance in comparison to that of similar materials is examined in detail using a variety of characterization techniques.NNTO delivers a specific discharge capacity of∼190 mAh g^(−1)and exhibits good reversibility,even in the presence of multiple phase transitions during cycling in a potential window of 2.0−4.2 V vs.Na^(+)/Na.This behavior can be attributed to the substituent,which helps maintain a larger interslab distance in the Na-deficient phases and to mitigate Jahn–Teller activity by reducing the average oxidation state of nickel.However,volume collapse at high potentials and irreversible lattice oxygen loss are still detrimental to the NNTO.Nevertheless,the performance can be further enhanced through coating and doping strategies.This not only positions NNTO as a promising next-generation cathode material,but also serves as inspiration for future research directions in the field of high-energy-density Na-ion batteries.展开更多
Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery(ASSLB).Homogeneous and fast lithium-ion(Li^(+))interfacial transport of cathode is the overriding premise for hig...Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery(ASSLB).Homogeneous and fast lithium-ion(Li^(+))interfacial transport of cathode is the overriding premise for high capability of ASSLBs.However,the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material(CAM)/sulfide solid electrolyte(SSE)interfacial issues result in high interfacial imped-ance,decreasing the Li^(+)transfer kinetics.In this review,we outline the Li^(+)transport properties of CAMs and SSEs,followed by a discussion of their interfacial electro-chemo-mechanical issues.Commentary is also provided on the solutions to the multiple-scale interfacial Li^(+)transport failure.Furthermore,the underlying interdependent mechanisms between electrodes are summarized and overviewed.Finally,we suggest future paths to better comprehend and promote the interfacial Li^(+)transport in ASSLBs.This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.展开更多
基金financially supported by the National Natural Science Foundation of China(22479067)Yunnan Young Talents Program for“Xingdian Talent Support Plan”(KKXX202551007)。
文摘The electro-chemo-mechanical mechanism is critical for understanding the initiation and propagation of lithium(Li)dendrites in solid-state lithium metal battery(SSLMB).Li dendrites often nucleate within surface defects in the solid-state electrolyte,leading to internal short circuits that hinder practical application of SSLMB.While conventional experimental and finite element methods provide valuable insights,they are often costly,time-consuming,and inefficient for capturing the complicated stress evolution inside solid-state electrolyte.In this study,we propose a novel machine learning strategy that integrates prior knowledge and physics-informed constraints to predict the von Mises stress distribution induced by the internal defects of solid-state electrolyte.High-quality training datasets generated using a multiphysics simulation framework and key findings from previous studies were incorporated as physicsguided constraints to enhance prediction reliability and physical consistency of machine learning models.By employing a modified UNet architecture with squeeze-and-excitation module,it demonstrates remarkably high accuracy in stress prediction and exhibits excellent robustness and generalization across a wide range of defect scenarios.This model allows us to efficiently obtain the electro-chemo-mechanical failure of solid-state electrolyte,thereby guiding micro structural modifications and facilitating the design of SSLMB for practical applications.
基金the financial support from the National Natural Science Foundation of China(12102328,52104312,22278329)the Qin Chuangyuan Talent Project of Shaanxi Province(2021QCYRC4-43,QCYRCXM-2022-308)the Fundamental Research Funds for the Central Universities,China.
文摘Garnet lithium lanthanum zirconium oxide(Li_(7)La_(3)Zr_(2)O_(12),LLZO)is a benchmark solid-state electrolyte(SSE)material receiving considerable attention owing to its high conductivity and chemical stability against Li metal.Although its electro-chemo-mechanical failure mechanisms have been much investigated,the equivocal roles of grain boundary strength and grain size of LLZO remain under-explored,hindering further performance improvements.Here we decoupled the effects of grain size and grain boundary strength of polycrystalline LLZO via the combination of electrochemical kinetics and the cohesive zone model.We discovered that the disintegration of LLZO is initiated by the accumulation of local displacements,which strongly relates to the changes in both grain size and grain boundary strength.However,variations in grain boundary strength affect the diffusion and propagation pathways of damage,while the failure of LLZO is determined by the grain size.Large LLZO grains facilitate transgranular damage under low grain boundary strength,which can alter local chemo-mechanics within the bulk of LLZO,leading to more extensive damage propagation.The results showcase the structure optimization pathways by preferentially controlling the growth of lithium dendrites at grain boundaries and their penetration in garnet-type SSE.
基金the National Natural Science Foundation of China(No.11902144)the Postgraduate Research&Practice Innovation Program of Jiangsu Province of China(No.KYCX201074)+1 种基金the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.19KJB430022)the Guizhou Provincial General Undergraduate Higher Education Technology Supporting Talent Support Program(No.KY(2018)043)。
文摘Flexible solid-state battery has several unique characteristics including high flexibility,easy portability,and high safety,which may have broad application prospects in new technology products such as rollup displays,power implantable medical devices,and wearable equipments.The interfacial mechanical and electrochemical problems caused by bending deformation,resulting in the battery damage and failure,are particularly interesting.Herein,a fully coupled electro-chemo-mechanical model is developed based on the actual solid-state battery structure.Concentration-dependent material parameters,stress-dependent diffusion,and potential shift are considered.According to four bending forms(k=8/mm,0/mm,-8/mm,and free),the results show that the negative curvature bending is beneficial to reducing the plastic strain during charging/discharging,while the positive curvature is detrimental.However,with respect to the electrochemical performance,the negative curvature bending creates a negative potential shift,which causes the battery to reach the cut-off voltage earlier and results in capacity loss.These results enlighten us that suitable electrode materials and charging strategy can be tailored to reduce plastic deformation and improve battery capacity for different forms of battery bending.
基金financially supported by the Natural Science Foundation of Hunan Province(2020JJ5653)the National Natural Science Foundation of China(21875282,22102212)+1 种基金the Ministry of Science and Higher Education of the Russian Federation(07515-2022-1150)the National University of Defense Technology Scientific Research Project(ZK20-44)。
文摘Nickel-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) cathode material has been widely concerned due to its high voltage,high specific capacity and excellent rate performance,which is considered as one of the most promising cathode materials for the next generation of high-energy-density solid-state lithium batteries.However,serious electro-chemo-mechanical degradation of Nickel-rich cathode during cycling,especially at a high voltage(over 4.5 V),constrains their large-scale application.Here,using the multiphysical simulation,highly-conductive polymer matrix with spontaneous stress-buffering effect was uncovered theoretically for reinforcing the electrochemical performance of composited NCM81 1 cathode through the visualization of uniform concentration distribution of Li-ion coupled with improved stress field inside NCM811 cathode.Thereupon,polyacrylonitrile(PAN) and soft polyvinylidene fluoride(PVDF) were selected as the polymer matrix to fabricate the composited NCM811 cathode(PVDFPAN@NCM811) for improving the electrochemical performance of the solid-state NMC811|Li full cells,which can maintain high capacity over 146.2 mA h g^(-1)after 200 cycles at a high voltage of 4.5 V.Suggestively,designing a multifunctional polymer matrix with high ionic conductivity and mechanical property can buffer the stress and maintain the integrity of the structure,which can be regarded as the door-opening avenue to realize the high electrochemical performance of Ni-rich cathode for solidstate batteries.
基金supported by the National Key R&D Program of China(2018YFB1304902)the National Natural Science Foundation of China(11904372,U1813211,and 12004034)+2 种基金Beijing Institute of Technology Research Fund Program for Young ScholarsBeijing Institute of Technology Laboratory Research Project(2019BITSYA03)China Postdoctoral Science Foundation Funded Project(2021M690386)。
文摘Harvesting the promising high energy density of advanced electrode materials in lithium-ion batteries is critically dependent on a mechanistic understanding on how the materials function and degrade along with the battery cycling.Here,we tracked phase transformations during(de)lithiation of Sb_(2)Se_(3) single crystals using in situ high-resolution transmission electron microscopy(HRTEM)technique,and revealed electro-chemo-mechanical evolution at the reaction interface.The effect of this electro-chemo-mechanical coupling has a complicated interplay on the lithiation kinetics and causes various types of defects at the reaction front,including dislocation dipoles,antiphase boundaries,and cracks.In return,the formed cracks and related defects build a path for fast diffusion of lithium ions and trigger a highly anisotropic lithiation at the twisted reaction front,giving rise to the formation of presumably "dead" Sb_(2)Se_(3) nanodomains in amorphous Li_(x)Sb_(2)Se_(3).The detailed mechanistic understanding may facilitate the rational design of high-capacity electrode materials for battery applications.
基金supported by National Key Research and Development Program of China(2019YFA0705702)National Natural Science Foundation of China(22075328,22379168,2209213)Guangdong Basic and Applied Basic Research Foundation(2021B1515120002).
文摘Lithium-ion batteries are limited by the low energy density of graphite anodes and are gradually becoming unable to meet the demand for energy storage development.A further increase in high capacity requires new battery materials and chemistry,such as the innovative lithium metal anodes(LMAs).However,the actual commercialization of LMAs is limited by the unstable Li/electrolyte interface,impeding their progress from the laboratory to industrial production.To address these problems,constructing a Li alloy/Li halide mixed layer upon a Li surface is considered to be an ideal direction because of the combined advantages of Li alloys and Li halides.In this context,by comparing the limitations of self-generated solid electrolyte interfaces,the unique merits of Li alloys and Li halides are discussed in depth with summaries of their respective advances.Accordingly,mixed layers of Li alloy/Li halides are introduced,and the mechanisms of Li deposition behaviors are clearly described,along with their manufacturing strategies and recent progress.Moreover,the emerging techniques for interface characterization are also comprehensively summarized.Furthermore,the necessary considerations and outlooks for the future design of Li alloy/Li halide mixed layers are highlighted,with the aim of elucidating the structure-property relationships and providing rational directions for the attainment of the next-generation high-performance batteries.
基金financial support from National Science Foundation of China(Grant No.52402445)the Natural Science Foundation of Jiangsu Province(Grant No.BK20241325)the startup support from Southeast University(Grant No.RF1028623337)。
文摘Solid-to-solid interfacial issues are one of the most intractable problems hindering the practical application of all-solid-state batteries(ASSBs).The interfacial instability behaviors caused by the rough interface between lithium anode and solid electrolyte(SE)involve complicated electro-chemo-mechanics interplays and their quantitative relationships still remain unclear.The three-dimensional electro-chemomechanical coupled model with randomly generated rough lithium-SE interface is developed in this study to investigate the effects of interface roughness on the interfacial failure behaviors.Results demonstrate that the existence of a rough lithium-SE interface causes the highly concentrated strain,GPa-level stress,and localized current density at the protruding tips,probably inducing dendrite formation and interface cracking.The interface roughness effect is much more pronounced in lithium anode than graphite anode due to their different Li storage mechanisms,i.e.,surface deposition and Li intercalation.Excessive stack pressure(>50 MPa)magnifies the stress effect on overpotential to enlarge the current density localization and deteriorate the interfacial instability issues.Reducing interface roughness through surface treatment,together with regulation of external operation conditions,can effectively improve interfacial stability performance.The results provide an in-depth understanding of the underlying electro-chemo-mechanical coupling mechanism caused by the rough anode-SE interface and bring more insights into further improvement of ASSBs'enhanced reliability and longevity.
基金support from the National Natural Science Foundation of China(NSFC)Basic Science Center for“Multiscale Problems in Nonlinear Mechanics”(Grant No.11988102)Jici Wen thanks for support from NSFC(Grant No.12002343).
文摘Health management for commercial batteries is crowded with a variety of great issues,among which reliable cycle-life prediction tops.By identifying the cycle life of commercial batteries with different charging histories in fast-charging mode,we reveal that the average charging rate c and the resulted cycle life N of batteries obey c=c_(0)N^(b),where c_(0) is a limiting charging rate and b is an electrode-dependent constant.This c-N law,resembling the classic stress versus cycle number relationship(the S-N curve or Wohler curve)of solids subject to cyclic loading,could be applicable to most batteries.Such a scaling law,in combination with a physics-augmented machine-learning algorithm,could foster the predictability of battery life with high fidelity.The scaling of charging rate and cycle number may pave the way for cycle-life prediction and the directions of optimization of advanced batteries.
基金the National Natural Science Foundation of China(12102328)for supporting this work。
文摘Owing to the utilization of lithium metal as anode with the ultrahigh theoretical capacity density of 3860 mA h g^(-1)and oxide-based ceramic solid-state electrolytes(SE),e.g.,garnet-type Li7La_(3)Zr_(2)O_(12)(LLZO),all-state-state lithium metal batteries(ASLMBs)have been widely accepted as the promising alternatives for providing the satisfactory energy density and safety.However,its applications are still challenged by plenty of technical and scientific issues.In this contribution,the co-sintering temperature at 500℃is proved as a compromise method to fabricate the composite cathode with structural integrity and declined capacity fading of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)(NCM).On the other hand,it tends to form weaker grain boundary(GB)inside polycrystalline LLZO at inadequate sintering temperature for LLZO,which can induce the intergranular failure of SE during the growth of Li filament inside the unavoidable defect on the interface of SE.Therefore,increasing the strength of GB,refining the grain to 0.4μm,and precluding the interfacial defect are suggested to postpone the electro-chemo-mechanical failure of SE with weak GB.Moreover,the advanced sintering techniques to lower the co-sintering temperature for both NCM-LLZO composite cathode and LLZO SE can be posted out to realize the viability of state-of-the-art ASLMBs with higher energy density as well as the guaranteed safety.
基金supported by the National Natural Science Foundation of China(No.22479092,22078190 and 12002196).
文摘Diffusion-induced stress(DIS)originates from the shrinkage/expand during Li extraction/insertion from/into the active particle for the Li-ion battery(LIB).Till today,the two-way coupled mechanical-electrochemical mechanism is still unclear.The above challenge can be decomposed into 2W+lH as follows:(i)Why need to reveal the two-way coupled mechanical-electrochemical mechanism?(ii)What is the two-way coupled mechanical-electrochemical mechanism?(iii)How to reveal the two-way coupled mechanical-electrochemical mechanism.In the process of answering the above 2W+lH,the following contributions have been made in this work:(i)An electro-chemo-mechanical(ECM)model is established for the LIB,in which the mechanical-electrochemical coupling is two-way;(ii)The mechanical-electrochemical responses are solved for the ECM model in the time/frequency domain,respectively;(iii)The time-domain analysis shows that DIS enhances Li diffusion at the early and middle stages of discharge,while DIS inhibits Li diffusion at the end of discharge;(iv)The frequency domain analysis shows that stress mainly affects solid-phase diffusion instead of electrolyte-phase diffusion.In a word,the multi-scale analysis quantitatively analyzes the impact of DIS on Li diffusion on the particle scale and reveals the two-way coupled mechanical-electrochemical mechanism on the electrode scale.The above results provide theoretical support for the battery manufacture and stress monitoring.
基金supported by the National Natural Science Foundation of China(22479067).
文摘Lithium metal batteries(LMBs)are candidates for next-generation energy storage due to their potential to increase energy density.However,the nonuniform electrodeposition of Li during cycling,plus the growth of Li dendrites and the side reactions between Li metal and the electrolyte,hinder the practical deployment of LMBs.The plating/stripping behavior of Li is an electro-chemo-mechanical process,and gaining a thorough understanding of its mechanisms is a cornerstone of LMB development.In this review,the current understanding of electro-chemo-mechanical processes on Li metal anodes is systematically summarized from the perspectives of Li plating/stripping in liquid-and solid-state electrolytes,the important role of the solid-electrolyte interphase,and the methodologies for understanding the electro-chemo-mechanics of the Li metal anode.The aim is to promote the development of LMBs through the optimization of Li metal anodes,which is based on understanding the fundamental processes occurring during electrochemical plating and stripping.
基金This work was supported by the Fundación Séneca[19253/PI/14].
文摘Here we review the persisting conceptual discrepancies between different research groups working on artificial muscles based on conducting polymers and other electroactive material.The basic question is if they can be treated as traditional electro-mechanical(physical)actuators driven by electric fields and described by some adaptation of their physical models or if,replicating natural muscles,they are electro-chemo-mechanical actuators driven by electrochemical reaction of the constitutive molecular machines:the polymeric chains.In that case the charge consumed by the reaction will control the volume variation of the muscular material and the motor displacement,following the basic and single Faraday’s laws:the charge consumed by the reaction determines the number of exchanged ions and solvent,the film volume variation to lodge/expel them and the amplitude of the movement.Deviations from the linear relationships are due to the osmotic exchange of solvent and to the presence of parallel reactions from the electrolyte,which originate creeping effects.Challenges and limitations are underlined.
基金supported by BASF SEfunding by the German Research Foundation(DFG)under project ID 390874152(POLiS Cluster of Excellence)。
文摘O3-type layered oxide cathodes,such as NaNi_(0.5)Mn_(0.5)O_(2),have garnered significant attention due to their high theoretical specific capacity while using abundant and low-cost sodium as intercalation species.Unlike the lithium analog(LiNiO_(2)),NaNiO_(2)(NNO)exhibits poor electrochemical performance resulting from structural instability and inferior Coulomb efficiency.To enhance its cyclability for practical application,NNO was modified by titanium substitution to yield the O3-type NaNi_(0.9)Ti_(0.1)O_(2)(NNTO),which was successfully synthesized for the first time via a solid-state reaction.The mechanism behind its superior performance in comparison to that of similar materials is examined in detail using a variety of characterization techniques.NNTO delivers a specific discharge capacity of∼190 mAh g^(−1)and exhibits good reversibility,even in the presence of multiple phase transitions during cycling in a potential window of 2.0−4.2 V vs.Na^(+)/Na.This behavior can be attributed to the substituent,which helps maintain a larger interslab distance in the Na-deficient phases and to mitigate Jahn–Teller activity by reducing the average oxidation state of nickel.However,volume collapse at high potentials and irreversible lattice oxygen loss are still detrimental to the NNTO.Nevertheless,the performance can be further enhanced through coating and doping strategies.This not only positions NNTO as a promising next-generation cathode material,but also serves as inspiration for future research directions in the field of high-energy-density Na-ion batteries.
基金supported by the National Natural Science Foundation of China(Nos.22379155,52037006)the Postdoctoral Fellowship Program of CPSF(No.GZC20241810)+5 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA22010600)the Youth Innovation Promotion Association of CAS(No.2021210)the Key Scientific and Technological Innovation Project of Shandong(Nos.2022CXGC020301,2023CXGC010302)the Emerging Industry Cultivation Plan of Qingdao Future Industry Culti-vation Project(No.24-1-4-xxgg-7-gx)the Qingdao New Energy Shan-dong Laboratory(No.QIBEBT/SEI/QNESLS202304)the Taishan Scholars Program(Nos.ts201511063,tsqn202306308).
文摘Interface is a necessary channel of carrier permeation in sulfide-based all-solid-state lithium battery(ASSLB).Homogeneous and fast lithium-ion(Li^(+))interfacial transport of cathode is the overriding premise for high capability of ASSLBs.However,the inherent transport heterogeneity of crystalline materials in cathode and the cathode active material(CAM)/sulfide solid electrolyte(SSE)interfacial issues result in high interfacial imped-ance,decreasing the Li^(+)transfer kinetics.In this review,we outline the Li^(+)transport properties of CAMs and SSEs,followed by a discussion of their interfacial electro-chemo-mechanical issues.Commentary is also provided on the solutions to the multiple-scale interfacial Li^(+)transport failure.Furthermore,the underlying interdependent mechanisms between electrodes are summarized and overviewed.Finally,we suggest future paths to better comprehend and promote the interfacial Li^(+)transport in ASSLBs.This review provides an in-depth understanding of cathodal interfacial issues and the proposed improvement strategies will provide guidance for further advancement of high-performance ASSLBs.
