Li plating behavior of the Li metal anode and its compatibility with electrolytes play a decisive role in the electrochemical performance of the Li metal batteries(LMBs),while the intrinsic highly reactive Li would in...Li plating behavior of the Li metal anode and its compatibility with electrolytes play a decisive role in the electrochemical performance of the Li metal batteries(LMBs),while the intrinsic highly reactive Li would induce serious results especially under deep Li plating/stripping depth and with lean electrolytes.Herein,we propose an innovative strategy to simultaneously regulate the bulk construction and the preferential orientation of Li deposition by introducing Li22Sn5/Li-Mg alloys to realize ultra-stable thin Li anodes with long lifespan.The alloys can form a continuous framework with high lithiophilicity and fast ion-diffusion to enable homogenous Li flux,and meanwhile tune the preferential orientation of Li from the conventional(110)plane to(200)to lower the Li reactivity with electrolytes and optimize Li deposition.Therefore,the thin Li-Sn-Mg alloy anode showcases ultra-stable cycling without volume changes and dendrites under a deep Li plating/stripping depth of 89.1%(5 mAh cm^(-2))for over 1200 h in commercial carbonate electrolytes.Moreover,a multilayered NCM811pouch cell with a high energy density of403.6 Wh kg^(-1)is achieved under the harsh conditions of low N/P ratio(0.769)and lean electrolytes(~2.1 g Ah^(-1)).Synchronously,the thin alloy anode shows improved air stability which benefits the manufacturing process and performance of LMBs,displaying the great application potential of these alloy anodes.展开更多
Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the L...Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the Li-S battery has been plagued by the rapid failure of the Li anode due to the Li dendrite growth and severe parasitic reactions between Li and lithium polysulfides.The physicochemical properties of the solid-electrolyte interphase have a profound impact on the performance of the Li anode.Herein,a lithium polyacrylic acid/lithium nitrate(LPL)-protective layer is developed to inhibit the dendrite Li growth and parasitic reactions by tailoring the spatial distribution and content of LiN_(x)O_(y) and Li_(3)N at the SEI.The modified SEI is thoroughly investigated for compositions,ion transport properties,and Li plating/stripping kinetics.Consequently,the Li-S cell with a high S loading cathode(5.0 mg cm^(−2)),LPL layer-protected thin Li anode(50μm),and 40μL electrolyte shows a long life span of 120 cycles.This work evokes the avenue for regulating the spatial distribution of inorganic nitride at the SEI to suppress the formation of Li dendrites and parasitic reactions in Li-S batteries and perhaps guiding the design of analogous battery systems.展开更多
The rechargeable Li-O_(2) battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode,espe...The rechargeable Li-O_(2) battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode,especially to moisture, usually leads to inferior electrochemical performance of Li-O_(2) battery in humid environments, hindering its widespread application. To settle the trouble of poor moisture tolerance, fabricating a water-proof layer on the Li-metal anode could be an effective tactic. Herein, a facile strategy for constructing an ibuprofen-based protective layer on the Li anode has been proposed to realize highly rechargeable Li-O_(2) battery in humid atmosphere. Due to the in-situ reaction between ibuprofen reagent and metallic Li, the protective layer with a thickness of ~30 μm has been uniformly deposited on the surface of Li anode. Particularly, the protective layer, consisting of a large amount of hydrophobic alkyl group and benzene ring, can significantly resist water ingress and enhance the electrochemical stability of Li anode. As a result, the Li-O_(2) battery based on the protected Li anode achieves a long cycle life of 210 h(21 cycles at 1000 m Ah/g, 200 m A/g) in highly moist atmosphere with relative humidity(RH) of68%. This convenient and efficient strategy offers novel design concept of water-resistant metal anode,and paves the way to the promising future prospect for the high-energy Li-O_(2) battery implementing in the ambient atmosphere.展开更多
Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degra...Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degradation at high current densities.We address these issues by a“killing two birds with one stone”O_(2)-pressure protocol.It first resolves efficient O_(2) mass transport at high rates..The accelerated reaction kinetics optimizes the composition and growth pathway of discharge products.This protocol secondly achieves protection of Li anodes via densifying corrosion layers on them.Consequently,the battery delivers both ultrahigh discharge capacity(>9,000 mAh g^(-1))at 3,000 mA g^(-1) and excellent cycling stability.Under a dual-strategy effect of high-pressure O_(2) and artificial protection layers,the battery actualizes over 11-fold increase in cycle life of 5,170 h(2,585 cycles).The strategy opens avenues for advancing Li-O_(2) batteries towards practical application and confers the extension to other gas-based batteries.展开更多
Ultrathin Li-rich Li-Cu binary alloy has become a competitive anode material for Li metal batteries of high energy density.However,due to the poor-lithiophilicity of the single skeleton structure of Li-Cu alloy,it has...Ultrathin Li-rich Li-Cu binary alloy has become a competitive anode material for Li metal batteries of high energy density.However,due to the poor-lithiophilicity of the single skeleton structure of Li-Cu alloy,it has limitations in inducing Li nucleation and improving electrochemical performance.Hence,we introduced Ag species to Li-Cu alloy to form a 30μm thick Li-rich Li-Cu-Ag ternary alloy(LCA)anode,with Li-Ag infinite solid solution as the active phase,and Cu-based finite solid solutions as three-dimensional(3D)skeleton.Such nano-wire networks with LiCu4 and CuxAgy finite solid solution phases were prepared through a facile melt coating technique,where Ag element can act as lithiophilic specie to enhance the lithiophilicity of built-in skeleton,and regulate the deposition behavior of Li effectively.Notably,the formation of CuxAgy solid solution can strengthen the structural stability of the skeleton,ensuring the geometrical integrity of Li anode,even at the fully delithiated state.Meanwhile,the Li-Ag infinite solid solution phase can promote the Li plating/stripping reversibility of the LCA anode with an improved coulombic efficiency(CE).The synergistic effect between infinite and finite solid solutions could render an enhanced electrochemical performance of Li metal batteries.The LCA|LCA symmetric cells showed a long lifespan of over 600 h with stable polarization voltage of 40 mV,in 1 mA·cm^(-2)/1 mAh·cm^(-2).In addition,the full cells matching our ultrathin LCA anode with 17.2 mg·cm^(-2)mass loading of LiFePO_(4) cathode,can continuously operate beyond 110 cycles at 0.5C,with a high capacity retention of 91.5%.Kindly check and confirm the edit made in the article title.展开更多
The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated...The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.展开更多
Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(L...Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(LMAs)is facing significant obstacles,such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface,leading to inferior Coulombic efficiency,unsatisfactory cycling stability and even serious safety issues.Introducing low-cost natural clay-based materials(NCBMs)in LMAs is deemed as one of the most effective methods to solve aforementioned issues.These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure,large specific surface areas,abundant surface groups,high mechanical strength,excellent thermal stability,and environmental friendliness.Considering the rapidly growing research enthusiasm for this topic in the last several years,here,we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs.The different structures and modification methods of natural clays are first summarized.In addition,the relationship between their modification methods and nano/microstructures,as well as their impact on the electrochemical properties of LMAs are systematically discussed.Finally,the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.展开更多
Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with t...Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.展开更多
Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling...Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling performance.Herein,a hybrid structure composed of 3 D carbon cloth and vesicleshaped hollow ZIF-8 modification shell(HZS@CC)was prepared as a smart host for guiding uniform Li deposition.The long-range interconnected 3 D carbon fiber network enables the reduced local current density with homogeneous electrons distribution.Synergistically,abundant surface polar groups and the ultrastructure on ZIF-8 particles effectively guide a well-distributed Li-ions flow to promote the uniform Li nucleation and growth.As a result,stable Li plating/stripping for 2000 h with a low overpotential(≈15 mV)at 1 mA cm^(-2) were achieved in symmetric cells.Coupling with LiFePO_(4) cathode,the full cell delivered long life over 1200 cycles at 6 C.This research demonstrated that a homogenization guiding of Li-ions is of great importance to better make use of the structural advantage of 3 D hosts and achieve improved electrochemical performance.展开更多
Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-clas...Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.展开更多
Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be a...Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.展开更多
Lithium(Li)metal is the most promising anode for improving the energy density of currently commercialized Li-ion batteries.However,its practical application is limited due to its high reactivity to electrolytes,which ...Lithium(Li)metal is the most promising anode for improving the energy density of currently commercialized Li-ion batteries.However,its practical application is limited due to its high reactivity to electrolytes,which induces severe electrolyte decomposition and Li-dendrite growth.Interphases are usually constructed on Li anode to address the above issue.Meanwhile,it is a big challenge to balance the stability and plating/stripping overpotential of Li anode.In this work,we report a novel strategy for constructing a highly stable and lowly polarized surface film on Li anode.A chemically and structurally unique film is formed by simply dropping a zinc trifluoromethanesulfonate[Zn(OTF)_(2)]and fluoroethylene carbonate(FEC)-containing solution onto Li anode.This unique film consists of inner nucleation sites and outer protection textures,mainly containing Li–Zn alloy and LiF/polymer,respectively.The former results from the preferential reduction of Zn(OTF)_(2),providing nucleation sites with low polarization for Li plating/stripping.In contrast,the latter arises from the subsequent reduction of FEC,providing protection for the underneath Li–Zn alloy and Li metal and ensuring the stability of Li anode.The Li anode with such a unique surface film exhibits excellent cycling stability and low plating/stripping overpotentials,which have been demonstrated using Li//Li symmetric and Li//LiFePO_(4)full cells.展开更多
Lithium metal is a promising candidate for the promotion of the next generation high energy density batteries.The employment of ultrathin Li metal anode with controllable thickness could enable a higher efficiency of ...Lithium metal is a promising candidate for the promotion of the next generation high energy density batteries.The employment of ultrathin Li metal anode with controllable thickness could enable a higher efficiency of Li utilization.Herein,a simple method to fabricate free-standing 10μm ultrathin Li metal anode is developed in this work.A three-dimensional MnO_(x)-coated CNT framework is constructed through a facile hydrothermal process,utilizing as a host for molten Li infusion,which could not only put forward a simple strategy to modulate the thickness of Li metal film but also restricts the volume expansion.The abundant MnO_(x)nanoparticles acting as lithiophilic sites reduce the Li nucleation barrier and optimize the electrochemical kinetics at the anode/electrolyte interface.As a result,the ultrathin Li composite anode exhibits a superior lifespan expanded to 2000 cycles in a symmetric cell,as well as a better capacity and rate capability than that of bare Li anode in full cell,fulfilling the requirements of high energy density and stable cycling life.Furthermore,a wave-shaped Li metal pouch cell based on the ultrathin Li composite anode is assembled that exhibits remarkable mechanical bending toleration and cyclic stability,demonstrating large potential application in the field of flexible wearable devices.展开更多
The reviving of the“Holy Grail”lithium metal batteries(LMBs)is greatly hindered by severe parasitic reactions between Li anode and electrolytes.Herein,first,we comprehensively summarize the failure mechanisms and pr...The reviving of the“Holy Grail”lithium metal batteries(LMBs)is greatly hindered by severe parasitic reactions between Li anode and electrolytes.Herein,first,we comprehensively summarize the failure mechanisms and protection principles of the Li anode.Wherein,despite being in dispute,the formation of lithium hydride(LiH)is demonstrated to be one of the most critical factors for Li anode pulverization.Secondly,we trace the research history of LiH at electrodes of lithium batteries.In LMBs,LiH formation is suggested to be greatly associated with the generation of H_(2)from Li/electrolyte intrinsic parasitic reactions,and these intrinsic reactions are still not fully understood.Finally,density functional theory calculations reveal that H_(2)adsorption ability of representative Li anode protective species(such as LiF,Li_(3)N,BN,Li_(2)O,and graphene)is much higher than that of Li and LiH.Therefore,as an important supplement of well-known lithiophilicity theory/high interfacial energy theory and three key principles(mechanical stability,uniform ion transport,and chemical passivation),we propose that constructing an artificial solid electrolyte interphase layer enriched of components with much higher H_(2)adsorption ability than Li will serve as an effective principle for Li anode protection.In summary,suppressing formation of LiH and H_(2)will be very important for cycle life enhancement of practical LMBs.展开更多
Although lithium iodide(LiI)as a redox mediator(RM)can decrease the overpotential in Li-O_(2)batteries,the stability of the Li anode is still one critical issue due to the redox shuttling.Here,we firstly present a nov...Although lithium iodide(LiI)as a redox mediator(RM)can decrease the overpotential in Li-O_(2)batteries,the stability of the Li anode is still one critical issue due to the redox shuttling.Here,we firstly present a novel approach for generating Ag and LiTFSI enriched Li anode(designated as ALE@Li anode)via a spontaneous substitution between pure Li and bis(trifluoromethanesulfonyl)imide silver,in a LiI-participated Li-O_(2)cell.It can induce the generation of a lithiophilic solid electrolyte interphase(SEI)enriched with Ag,F,and N species(e.g.,Ag_(2)O,Li-Ag alloy,LiF,and Li_(3)N)during cell operation,which contributes to promoting the electrochemical performance through the shuttling inhibition.Compared to a cell with a bare Li anode,the one with as-prepared ALE@Li anode shows an enhanced cyclability,a considerable rate capability,and a good reversibility.In addition,a synchrotron X-ray computed tomography technique is employed to investigate the inhibition mechanism for shuttling effect by monitoring the morphological evolution on the cell interfaces.Therefore,this work highlights the deliberate design in the modified Li anode in an easy-to-operate and cost-effective way as well as providing guidance for the construction of artificial SEI layers to suppress the redox shuttling of RMs in Li-O_(2)batteries.展开更多
Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batt...Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batteries, lithium-oxygen batteries, solid-state lithium metal batter- ies）. However, the inherent bottleneck of Li metal anodes, especially the growth of Li dendrites and the related safety concerns, should be well addressed. Owing to their featured micro-/nano-porous structures and intriguing physical properties, nanocarbon materials have been applied as host materials for Li metal anodes. This review summarizes the recent progress in the development of porous nanocarbon materials for safe Li metal anodes. The perspectives regarding the challenges and future development of employing micro-/nano-porous carbon materials in Li metal anodes are also included.展开更多
Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including vi...Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.展开更多
With the rapid development of consumer electronics,electric vehicles and grid-scale stationary energy storage,high-energy batteries are urgently demanded at present.Lithium metal batteries(LMBs)are considered to be on...With the rapid development of consumer electronics,electric vehicles and grid-scale stationary energy storage,high-energy batteries are urgently demanded at present.Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy density energy storage devices at present and have received much attention due to their ultra-high theoretical capacity,extremely low electrochemical potential and light mass.However,critical issues,such as uncontrollable lithium dendrite growth,dynamic changes in volume,interfacial impedance,severe chemical and electrochemical corrosion,remain huge challenges for Li metal anodes,which not only lead to low Columbic efficiency of LMBs,but also pose the risk of internal short circuit,causing serious side reactions and safety concerns that hinder LMBs from practical applications.Nevertheless,lithium metal is gradually poised for a revival after decades of oblivion,due to the development of research tools and nanotechnologybased solutions.In this review,various recent material designs for lithium metal anodes are reviewed based on previous theoretical understanding and analysis.Suppressing Li dendrites and ensuring the long life span of practical batteries through limited Li metal anodes design are still challenges.Multi-scale modeling methods are concerned,requiring the application of electrode material development.Hybrid multi-scale modeling application methods with machine learning technology are proposed based on the cloud computing platform.Computational material designs for Li metal anodes on model information are integrated with artificial intelligence.Finally,this review provides a novel framework for next-generation lithium metal anode design methods with a digital solution based on multi-scale data-driven models and machine learning techniques.展开更多
Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capac...Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning.The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes.展开更多
Lithium(Li)is a promising candidate for nextgeneration battery anode due to its high theoretical specific capacity and low reduction potential.However,safety issues derived from the uncontrolled growth of Li dendrite ...Lithium(Li)is a promising candidate for nextgeneration battery anode due to its high theoretical specific capacity and low reduction potential.However,safety issues derived from the uncontrolled growth of Li dendrite and huge volume change of Li hinder its practical application.C onstructing dendrite-free composite Li anodes can significantly alleviate the above problems.Copper(Cu)-based materials have bee n widely used as substrates of the composite electrodes due to their chemical stability,excellent conductivity,and good mechanical strength.Copper/lithium(Cu/Li)composite anodes significantly regulate the local current density and decrease Li nucleation overp otential,realizing the uniform and dendrite-free Li deposition.In this review,Cu/Li composite methods including electrodeposition,melting infusion,and mechanical rolling are systematically summarized and discussed.Additionally,design strategies of Cu-based current collectors for high performance Cu/Li composite anodes are illustrated.General challenges and future development for Cu/Li composite anodes are presented and postulated.We hope that this review can provide a comprehensive understanding of Cu/Li composite methods of the latest development of Li metal anode and stimulate more research in the future.展开更多
基金supported by the Jilin Province Science and Technology Department Major Science and Technology project[grant numbers 20220301004GX,20220301005GX]Key Subject Construction of Physical Chemistry of Northeast Normal Universitythe Fundamental Research Funds for the Central Universities[grant number 2412023QD014]。
文摘Li plating behavior of the Li metal anode and its compatibility with electrolytes play a decisive role in the electrochemical performance of the Li metal batteries(LMBs),while the intrinsic highly reactive Li would induce serious results especially under deep Li plating/stripping depth and with lean electrolytes.Herein,we propose an innovative strategy to simultaneously regulate the bulk construction and the preferential orientation of Li deposition by introducing Li22Sn5/Li-Mg alloys to realize ultra-stable thin Li anodes with long lifespan.The alloys can form a continuous framework with high lithiophilicity and fast ion-diffusion to enable homogenous Li flux,and meanwhile tune the preferential orientation of Li from the conventional(110)plane to(200)to lower the Li reactivity with electrolytes and optimize Li deposition.Therefore,the thin Li-Sn-Mg alloy anode showcases ultra-stable cycling without volume changes and dendrites under a deep Li plating/stripping depth of 89.1%(5 mAh cm^(-2))for over 1200 h in commercial carbonate electrolytes.Moreover,a multilayered NCM811pouch cell with a high energy density of403.6 Wh kg^(-1)is achieved under the harsh conditions of low N/P ratio(0.769)and lean electrolytes(~2.1 g Ah^(-1)).Synchronously,the thin alloy anode shows improved air stability which benefits the manufacturing process and performance of LMBs,displaying the great application potential of these alloy anodes.
基金partially supported by grants from the National Natural Science Foundation of China(51772069 and 52072099).
文摘Among the alternatives to lithium-ion batteries,lithium-sulfur(Li-S)batteries are considered as an attractive option because of their high theoretical energy density of 2570 Wh kg^(−1).However,the application of the Li-S battery has been plagued by the rapid failure of the Li anode due to the Li dendrite growth and severe parasitic reactions between Li and lithium polysulfides.The physicochemical properties of the solid-electrolyte interphase have a profound impact on the performance of the Li anode.Herein,a lithium polyacrylic acid/lithium nitrate(LPL)-protective layer is developed to inhibit the dendrite Li growth and parasitic reactions by tailoring the spatial distribution and content of LiN_(x)O_(y) and Li_(3)N at the SEI.The modified SEI is thoroughly investigated for compositions,ion transport properties,and Li plating/stripping kinetics.Consequently,the Li-S cell with a high S loading cathode(5.0 mg cm^(−2)),LPL layer-protected thin Li anode(50μm),and 40μL electrolyte shows a long life span of 120 cycles.This work evokes the avenue for regulating the spatial distribution of inorganic nitride at the SEI to suppress the formation of Li dendrites and parasitic reactions in Li-S batteries and perhaps guiding the design of analogous battery systems.
基金financially supported by National Natural Science Foundation of China(No.22075171)。
文摘The rechargeable Li-O_(2) battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode,especially to moisture, usually leads to inferior electrochemical performance of Li-O_(2) battery in humid environments, hindering its widespread application. To settle the trouble of poor moisture tolerance, fabricating a water-proof layer on the Li-metal anode could be an effective tactic. Herein, a facile strategy for constructing an ibuprofen-based protective layer on the Li anode has been proposed to realize highly rechargeable Li-O_(2) battery in humid atmosphere. Due to the in-situ reaction between ibuprofen reagent and metallic Li, the protective layer with a thickness of ~30 μm has been uniformly deposited on the surface of Li anode. Particularly, the protective layer, consisting of a large amount of hydrophobic alkyl group and benzene ring, can significantly resist water ingress and enhance the electrochemical stability of Li anode. As a result, the Li-O_(2) battery based on the protected Li anode achieves a long cycle life of 210 h(21 cycles at 1000 m Ah/g, 200 m A/g) in highly moist atmosphere with relative humidity(RH) of68%. This convenient and efficient strategy offers novel design concept of water-resistant metal anode,and paves the way to the promising future prospect for the high-energy Li-O_(2) battery implementing in the ambient atmosphere.
基金support from the Major basic research project of Natural Science Foundation of Shandong Province(No.ZR2023ZD12)Singapore National Research Foundation Investigatorship(No.NRFNRFI08-2022-0009)NUS R&G Postdoc Fellowship Program.
文摘Lithium-oxygen(Li-O_(2))battery is favored among“beyond lithiumion”technologies for sustainability because of its exceptional energy density.Major impediments are the poor cycle stability and grievous capacity degradation at high current densities.We address these issues by a“killing two birds with one stone”O_(2)-pressure protocol.It first resolves efficient O_(2) mass transport at high rates..The accelerated reaction kinetics optimizes the composition and growth pathway of discharge products.This protocol secondly achieves protection of Li anodes via densifying corrosion layers on them.Consequently,the battery delivers both ultrahigh discharge capacity(>9,000 mAh g^(-1))at 3,000 mA g^(-1) and excellent cycling stability.Under a dual-strategy effect of high-pressure O_(2) and artificial protection layers,the battery actualizes over 11-fold increase in cycle life of 5,170 h(2,585 cycles).The strategy opens avenues for advancing Li-O_(2) batteries towards practical application and confers the extension to other gas-based batteries.
基金supported by the National Natural Science Foundation of China(Nos.22379019,52172184)Sichuan Science and Technology Program(No.2024YFHZ0313)S&T Special Program of Huzhou(No.2023GZ03)。
文摘Ultrathin Li-rich Li-Cu binary alloy has become a competitive anode material for Li metal batteries of high energy density.However,due to the poor-lithiophilicity of the single skeleton structure of Li-Cu alloy,it has limitations in inducing Li nucleation and improving electrochemical performance.Hence,we introduced Ag species to Li-Cu alloy to form a 30μm thick Li-rich Li-Cu-Ag ternary alloy(LCA)anode,with Li-Ag infinite solid solution as the active phase,and Cu-based finite solid solutions as three-dimensional(3D)skeleton.Such nano-wire networks with LiCu4 and CuxAgy finite solid solution phases were prepared through a facile melt coating technique,where Ag element can act as lithiophilic specie to enhance the lithiophilicity of built-in skeleton,and regulate the deposition behavior of Li effectively.Notably,the formation of CuxAgy solid solution can strengthen the structural stability of the skeleton,ensuring the geometrical integrity of Li anode,even at the fully delithiated state.Meanwhile,the Li-Ag infinite solid solution phase can promote the Li plating/stripping reversibility of the LCA anode with an improved coulombic efficiency(CE).The synergistic effect between infinite and finite solid solutions could render an enhanced electrochemical performance of Li metal batteries.The LCA|LCA symmetric cells showed a long lifespan of over 600 h with stable polarization voltage of 40 mV,in 1 mA·cm^(-2)/1 mAh·cm^(-2).In addition,the full cells matching our ultrathin LCA anode with 17.2 mg·cm^(-2)mass loading of LiFePO_(4) cathode,can continuously operate beyond 110 cycles at 0.5C,with a high capacity retention of 91.5%.Kindly check and confirm the edit made in the article title.
基金financially supported by Jilin Province Science and Technology Department Program(Nos.YDZJ202201ZYTS304,20220201130GX and 20240101004JJ)the National Natural Science Foundation of China(Nos.52171210 and 52471229)the Science and Technology Project of Jilin Provincial Education Department(No.JJKH20220428KJ)
文摘The formation and evolution process of the solid electrolyte interphase(SEI)is critical for stable cycling of the lithium metal anode(LMA).The concept of regulating SEI components with additives is widely incorporated into electrolyte design,as these additives can alter the lithium ion(Li^(+))deposition behavior on the surface of LMA.However,conventional additives are limited in their ability to produce only loose and porous SEI.In this study,we propose an organic additive of methyl methacrylate(MMA)that facilitates in-situ polymerization on the surface of LMA by generating anions or free radicals from LiTFSI.The MMA and LiNO_(3) work in tandem to produce a polymer/inorganic SEI(PI-SEI)characterized by an outer layer enriched with PMMA-Li short-chain polymers and an inner layer enriched with Li_(2)O and Li3N inorganics.Unlike the SEI formed by conventional additives,this PI-SEI exhibits higher stability and better Li^(+)transfer properties.The presence of short-chain polymers in PI-SEI alters the transport uniformity of Li^(+),facilitating stable cycling of Li‖Li cell for over 2000 cycles with a capacity of 1 mAh cm^(-2).Furthermore,these PMMA-Li can chemically adsorb lithium poly sulfides(LiPSs),thereby inhibiting Li corrosion by LiPSs,and enabling the capacity of lithium-sulfur batteries to achieve 474.3 mAh g^(-1)after 500 cycles at 0.5C.This study presents a strategy for generating SEI through the in-situ polymerization,which supports the commercial development of LMA in future liquid/solid Li metal batteries.
基金supported by the Henan Province Science and Technology Research Project(No.232102241006)the National Key Research and Development Program of China(No.2020YFB1713500)+2 种基金Opening Project of National Joint Engineering Research Center for Abrasion Control and Molding of Metal Materials&Henan Key Laboratory of High-temperature Structural and Functional Materials,Henan University of Science and Technology(No.HKDNM2019013)the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Major Science and Technology Projects of Henan Province(No.221100230200)。
文摘Lithium metal is one of the most promising anodes for lithium batteries because of their high theoretical specific capacity and the low electrochemical potential.However,the commercialization of lithium metal anodes(LMAs)is facing significant obstacles,such as uncontrolled lithium dendrite growth and unstable solid electrolyte interface,leading to inferior Coulombic efficiency,unsatisfactory cycling stability and even serious safety issues.Introducing low-cost natural clay-based materials(NCBMs)in LMAs is deemed as one of the most effective methods to solve aforementioned issues.These NCBMs have received considerable attention for stabilizing LMAs due to their unique structure,large specific surface areas,abundant surface groups,high mechanical strength,excellent thermal stability,and environmental friendliness.Considering the rapidly growing research enthusiasm for this topic in the last several years,here,we review the recent progress on the application of NCBMs in stable and dendrite-free LMAs.The different structures and modification methods of natural clays are first summarized.In addition,the relationship between their modification methods and nano/microstructures,as well as their impact on the electrochemical properties of LMAs are systematically discussed.Finally,the current challenges and opportunities for application of NCBMs in stable LMAs are also proposed to facilitate their further development.
基金financial supports from the National Natural Science Foundation of China(Nos.22279116 and U20A20253)the Natural Science Foundation of Zhejiang Province(Nos.LQ24E020012 and LD22E020006)Jianbing Science and Technology Project of Zhejiang Province(No.2023C01127)
文摘Lithium(Li) metal anodes(LMAs) that employ three-dimensional lithiophilic frameworks are among the most promising options for constructing high-energy-density rechargeable batteries.Herein,hollow ZnS nanosheets with the coating of N-doped carbon are modified on the surface of carbon cloth(NCHZS@CC) to serve as the host material for Li metal.It is revealed that the high surface area of NCHZS@CC can significantly reduce local current density and mitigate volume change during cycling.More importantly,the lithiated product of ZnS,confined within the carbon cage,facilitates the uniform deposition of Li metal on carbon fibers and promotes the formation of a stable solid electrolyte interphase enriched with Li_(2)S,thereby improving long-term performance as the cycling progresses.Consequently,the LMAs based on NCHZS@CC demonstrate an impressive cycle life beyond560 h with an ultralow overpotential of 38 mV at a current density of 5 mA cm^(-2)with a capacity of 1 mAh cm^(-2)in the symmetric cell.In addition,when matched with a high mass loading cathode of LiFePO_(4)(11.5 mg cm^(-2)),the assembled full cell displays outstanding performance,achieving 900 cycles at a rate of 2C.
基金financially supported by the National Key Research and Development Program of China(2017YFA0206703)the National Natural Science Foundation of China(21671183)。
文摘Lithium metal has aroused extensive research interests as the anode for next-generation rechargeable batteries.However,the well-known dendritic Li growth and consequent safety issues still impair the long-term cycling performance.Herein,a hybrid structure composed of 3 D carbon cloth and vesicleshaped hollow ZIF-8 modification shell(HZS@CC)was prepared as a smart host for guiding uniform Li deposition.The long-range interconnected 3 D carbon fiber network enables the reduced local current density with homogeneous electrons distribution.Synergistically,abundant surface polar groups and the ultrastructure on ZIF-8 particles effectively guide a well-distributed Li-ions flow to promote the uniform Li nucleation and growth.As a result,stable Li plating/stripping for 2000 h with a low overpotential(≈15 mV)at 1 mA cm^(-2) were achieved in symmetric cells.Coupling with LiFePO_(4) cathode,the full cell delivered long life over 1200 cycles at 6 C.This research demonstrated that a homogenization guiding of Li-ions is of great importance to better make use of the structural advantage of 3 D hosts and achieve improved electrochemical performance.
基金B.Tian acknowledges the financial support from the Science and Technology Project of Shenzhen(No.JCYJ20210324094206019)X.Huang acknowledges the financial support from the National Natural Science Foundation of China(No.52102284)+2 种基金Z.Yu acknowledges Department of Science and Technology of Guangxi Province(Nos.AB21220027,AD19110077)Guangxi Key Laboratory of Manufacturing Systems Foundation(No.20-065-40-005Z)Engineering Research Center Foundation of Electronic Information Materials and Devices(No.EIMD-AA202005).
文摘Li_(2)ZrCl_(6)(LZC) solid-state electrolytes(SSEs) have been recognized as a candidate halide SSEs for allsolid-state Li batteries(ASSLBs) with high energy density and safety due to its great compatibility with4V-class cathodes and low bill-of-material(BOM) cost.However,despite the benefits,the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface,which has a detrimental inhibition on Li^(+) transport in ASSLBs.Herein,we report a composite SSE combining by LZC and argyrodite buffer layer(Li_(6)PS_(5)Cl,LPSC) that prevent the unfavorable interaction between LZC and Li metal.The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm^(2)(0.15mAh/cm^(2)) and has a high critical current density(CCD) value of 2.1 mA/cm^(2)at 25 ℃,Under high temperature(60℃) which promotes the reaction between Li and LZC,symmetric cell fabricated with composite SSE also display stable cycling performance over 1200h at 0.3 mAh/cm^(2).Especially,the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency,as well as superior cycling and rate performance.This simple and efficient strategy will be instrumental in the development of halidebased high-performance ASSLBs.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22269013,22263009)the Natural Science Foundation of Jiangxi Province(Nos.20224ACB213001,20202ACB202004,20213BCJ22024,20212BBE53051)the Key Laboratory of Jiangxi Province for Environment and Energy Catalysis(No.20181BCD40004).
文摘Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.
基金supported by the National Key Research and Development Project of China(2018YFE0124800)。
文摘Lithium(Li)metal is the most promising anode for improving the energy density of currently commercialized Li-ion batteries.However,its practical application is limited due to its high reactivity to electrolytes,which induces severe electrolyte decomposition and Li-dendrite growth.Interphases are usually constructed on Li anode to address the above issue.Meanwhile,it is a big challenge to balance the stability and plating/stripping overpotential of Li anode.In this work,we report a novel strategy for constructing a highly stable and lowly polarized surface film on Li anode.A chemically and structurally unique film is formed by simply dropping a zinc trifluoromethanesulfonate[Zn(OTF)_(2)]and fluoroethylene carbonate(FEC)-containing solution onto Li anode.This unique film consists of inner nucleation sites and outer protection textures,mainly containing Li–Zn alloy and LiF/polymer,respectively.The former results from the preferential reduction of Zn(OTF)_(2),providing nucleation sites with low polarization for Li plating/stripping.In contrast,the latter arises from the subsequent reduction of FEC,providing protection for the underneath Li–Zn alloy and Li metal and ensuring the stability of Li anode.The Li anode with such a unique surface film exhibits excellent cycling stability and low plating/stripping overpotentials,which have been demonstrated using Li//Li symmetric and Li//LiFePO_(4)full cells.
基金supported by the Beijing Natural Science Foundation(JQ19012)the National Science Foundation for Excel ent Young Scholars of China(51822706)+2 种基金the National Natural Science Foundation of China(Youth Program)(52107234,and 52207250)the DNL Cooperation Fund,CAS(DNL201912 and DNL201915)Youth Innovation Promotion Association,CAS(Y2021052)
文摘Lithium metal is a promising candidate for the promotion of the next generation high energy density batteries.The employment of ultrathin Li metal anode with controllable thickness could enable a higher efficiency of Li utilization.Herein,a simple method to fabricate free-standing 10μm ultrathin Li metal anode is developed in this work.A three-dimensional MnO_(x)-coated CNT framework is constructed through a facile hydrothermal process,utilizing as a host for molten Li infusion,which could not only put forward a simple strategy to modulate the thickness of Li metal film but also restricts the volume expansion.The abundant MnO_(x)nanoparticles acting as lithiophilic sites reduce the Li nucleation barrier and optimize the electrochemical kinetics at the anode/electrolyte interface.As a result,the ultrathin Li composite anode exhibits a superior lifespan expanded to 2000 cycles in a symmetric cell,as well as a better capacity and rate capability than that of bare Li anode in full cell,fulfilling the requirements of high energy density and stable cycling life.Furthermore,a wave-shaped Li metal pouch cell based on the ultrathin Li composite anode is assembled that exhibits remarkable mechanical bending toleration and cyclic stability,demonstrating large potential application in the field of flexible wearable devices.
基金Taishan Scholars of Shandong Province,Grant/Award Number:ts201511063National Natural Science Foundation of China,Grant/Award Numbers:22102206,U22A20440+2 种基金Strategic Priority Research Program of Chinese Academy of Sciences,Grant/Award Number:XDA22010600Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2021QB030Key-Area Research and Development Program of Guangdong Province,Grant/Award Number:2020B090919005。
文摘The reviving of the“Holy Grail”lithium metal batteries(LMBs)is greatly hindered by severe parasitic reactions between Li anode and electrolytes.Herein,first,we comprehensively summarize the failure mechanisms and protection principles of the Li anode.Wherein,despite being in dispute,the formation of lithium hydride(LiH)is demonstrated to be one of the most critical factors for Li anode pulverization.Secondly,we trace the research history of LiH at electrodes of lithium batteries.In LMBs,LiH formation is suggested to be greatly associated with the generation of H_(2)from Li/electrolyte intrinsic parasitic reactions,and these intrinsic reactions are still not fully understood.Finally,density functional theory calculations reveal that H_(2)adsorption ability of representative Li anode protective species(such as LiF,Li_(3)N,BN,Li_(2)O,and graphene)is much higher than that of Li and LiH.Therefore,as an important supplement of well-known lithiophilicity theory/high interfacial energy theory and three key principles(mechanical stability,uniform ion transport,and chemical passivation),we propose that constructing an artificial solid electrolyte interphase layer enriched of components with much higher H_(2)adsorption ability than Li will serve as an effective principle for Li anode protection.In summary,suppressing formation of LiH and H_(2)will be very important for cycle life enhancement of practical LMBs.
基金supported by Science and Technology Project of Jilin Provincial Education Department(grant no.JJKH20221160KJ)Jilin Province Science and Technology Department(grant no.20230402059GH)+1 种基金The Swedish Foundation for International Cooperation in Research and Higher Education(grant no.KO2017-7351)Swedish Energy Agency(Project no.P2020-90216).
文摘Although lithium iodide(LiI)as a redox mediator(RM)can decrease the overpotential in Li-O_(2)batteries,the stability of the Li anode is still one critical issue due to the redox shuttling.Here,we firstly present a novel approach for generating Ag and LiTFSI enriched Li anode(designated as ALE@Li anode)via a spontaneous substitution between pure Li and bis(trifluoromethanesulfonyl)imide silver,in a LiI-participated Li-O_(2)cell.It can induce the generation of a lithiophilic solid electrolyte interphase(SEI)enriched with Ag,F,and N species(e.g.,Ag_(2)O,Li-Ag alloy,LiF,and Li_(3)N)during cell operation,which contributes to promoting the electrochemical performance through the shuttling inhibition.Compared to a cell with a bare Li anode,the one with as-prepared ALE@Li anode shows an enhanced cyclability,a considerable rate capability,and a good reversibility.In addition,a synchrotron X-ray computed tomography technique is employed to investigate the inhibition mechanism for shuttling effect by monitoring the morphological evolution on the cell interfaces.Therefore,this work highlights the deliberate design in the modified Li anode in an easy-to-operate and cost-effective way as well as providing guidance for the construction of artificial SEI layers to suppress the redox shuttling of RMs in Li-O_(2)batteries.
基金financially supported by the National Key Research and Development Program(Nos.2016YFA0202500,2015CB932500)the National Natural Scientific Foundation of China(Nos.21676160,21561130151)
文摘Owing to their very high theoretical capacity, lithium （Li） metal anodes regain widespread attentions for their promising applications for next-generation high-energy-density Li batteries （e.g., lithium-sulfur batteries, lithium-oxygen batteries, solid-state lithium metal batter- ies）. However, the inherent bottleneck of Li metal anodes, especially the growth of Li dendrites and the related safety concerns, should be well addressed. Owing to their featured micro-/nano-porous structures and intriguing physical properties, nanocarbon materials have been applied as host materials for Li metal anodes. This review summarizes the recent progress in the development of porous nanocarbon materials for safe Li metal anodes. The perspectives regarding the challenges and future development of employing micro-/nano-porous carbon materials in Li metal anodes are also included.
基金support from the Federal Ministry of Education and Research(BMBF)under project“KaSiLi”(03XP0254D)in the competence cluster“ExcellBattMat.”。
文摘Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.
基金the National Key R&D Program of China(No.2017YFB0103700)National Natural Science Foundation of China(No.U1864213)。
文摘With the rapid development of consumer electronics,electric vehicles and grid-scale stationary energy storage,high-energy batteries are urgently demanded at present.Lithium metal batteries(LMBs)are considered to be one of the most promising high-energy density energy storage devices at present and have received much attention due to their ultra-high theoretical capacity,extremely low electrochemical potential and light mass.However,critical issues,such as uncontrollable lithium dendrite growth,dynamic changes in volume,interfacial impedance,severe chemical and electrochemical corrosion,remain huge challenges for Li metal anodes,which not only lead to low Columbic efficiency of LMBs,but also pose the risk of internal short circuit,causing serious side reactions and safety concerns that hinder LMBs from practical applications.Nevertheless,lithium metal is gradually poised for a revival after decades of oblivion,due to the development of research tools and nanotechnologybased solutions.In this review,various recent material designs for lithium metal anodes are reviewed based on previous theoretical understanding and analysis.Suppressing Li dendrites and ensuring the long life span of practical batteries through limited Li metal anodes design are still challenges.Multi-scale modeling methods are concerned,requiring the application of electrode material development.Hybrid multi-scale modeling application methods with machine learning technology are proposed based on the cloud computing platform.Computational material designs for Li metal anodes on model information are integrated with artificial intelligence.Finally,this review provides a novel framework for next-generation lithium metal anode design methods with a digital solution based on multi-scale data-driven models and machine learning techniques.
基金kindly supported by the National Natural Science Foundation of China (No. U1864213)the EPSRC Joint UK-India Clean Energy center (JUICE) (EP/P003605/1)+2 种基金the EPSRC Multi-Scale Modelling project (EP/S003053/1)the Innovate UK for Advanced Battery Lifetime Extension (ABLE) projectthe EPSRC for funding under EP/S000933/1。
文摘Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithiumair, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning.The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes.
基金supported by the National Key Research and Development Program of China(No.2021YFB2500200)the National Natural Science Foundation of China(No.52302243)China Postdoctoral Science Foundation(Nos.2022M721029 and 2022M721030)。
文摘Lithium(Li)is a promising candidate for nextgeneration battery anode due to its high theoretical specific capacity and low reduction potential.However,safety issues derived from the uncontrolled growth of Li dendrite and huge volume change of Li hinder its practical application.C onstructing dendrite-free composite Li anodes can significantly alleviate the above problems.Copper(Cu)-based materials have bee n widely used as substrates of the composite electrodes due to their chemical stability,excellent conductivity,and good mechanical strength.Copper/lithium(Cu/Li)composite anodes significantly regulate the local current density and decrease Li nucleation overp otential,realizing the uniform and dendrite-free Li deposition.In this review,Cu/Li composite methods including electrodeposition,melting infusion,and mechanical rolling are systematically summarized and discussed.Additionally,design strategies of Cu-based current collectors for high performance Cu/Li composite anodes are illustrated.General challenges and future development for Cu/Li composite anodes are presented and postulated.We hope that this review can provide a comprehensive understanding of Cu/Li composite methods of the latest development of Li metal anode and stimulate more research in the future.
