Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
Traditional pyrometallurgy and hydrometallurgy processes primarily focus on the recovery of valuable metals(Co,Ni,etc.)from spent lithium-ion batteries.However,these methods are not economical for recycling cheap LiFe...Traditional pyrometallurgy and hydrometallurgy processes primarily focus on the recovery of valuable metals(Co,Ni,etc.)from spent lithium-ion batteries.However,these methods are not economical for recycling cheap LiFePO_(4).Herein,a synergistic thermal-decomposition and electric-drive strategy is proposed to recover the whole spent LiFePO_(4)electrode by in-situ recovering the inactive lithium(dead lithium and trapped interlayer lithium).Firstly,the organic components in the dense solid electrolyte interface(SEI)are effectively decomposed through thermal-decomposition processing,exposing the dead lithium encapsulated within the SEI and recovering the electron channels between the dead lithium and graphite.Leveraging the difference between the Gibbs free energy of the dead lithium and graphite as the driving force facilitates the dead lithium inserting into the anode.Then,fully utilizing the remaining discharge capacity of the spent LiFePO_(4)cell,the inactive lithium is reinserted into LiFePO_(4)lattice during the electric-drive process.Consequently,the reactivated lithium content increases by more than 16%,reaching a capacity of 134.2 mA h g^(-1)compared to 115.2 mA h g^(-1)from degraded LiFePO_(4),allowing for effective participation in the subsequent cycling.This work provides new perspectives on highly profitable cycles with low energy and material consumption and a low carbon footprint.展开更多
The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic framework...The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic frameworks(MOF)is incorporated into a polyethylene oxide(PEO)-based polymer solid electrolyte,leading to the insitu formation of LiF and other compounds at the electrolyte interface.This modification significantly improves lithium-ion transport capabilities and regulates lithium deposition behavior,suppressing the formation of lithium dendrites.展开更多
Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,saf...Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.展开更多
Anode-free lithium metal batteries are prone to capacity degradation and safety hazards due to the formation and growth of lithium dendrites.The interface between the current collector and deposited lithium plays a cr...Anode-free lithium metal batteries are prone to capacity degradation and safety hazards due to the formation and growth of lithium dendrites.The interface between the current collector and deposited lithium plays a critical role in preventing dendrite formation by regulating the thermodynamics and kinetics of lithium deposition.In this study,we develop a phase field model to investigate the influence of the current collector’s surface energy on lithium deposition morphology and its effect on the quality of the lithium metal film.It is demonstrated that a higher surface energy of the current collector promotes the growth of lithium metal along the surface of the current collector.Further,our simulation results show that a higher surface energy accelerates the formation of the lithium metal film while simultaneously reducing its surface roughness.By examining different contact angles and applied potentials,we construct a phase diagram of deposition morphology,illustrating that increased surface energy facilitates the dense and uniform deposition of lithium metal by preventing the formation of lithium filaments and voids.These findings provide new insights into the development and application of anode-free lithium metal batteries.展开更多
Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemica...Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.展开更多
All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The deve...All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.展开更多
Lithium metal has been considered the ultimate anode material in Li rechargeable batteries because of its exceptionally high theoretical specific capacity(3860 mAh g^(−1))and extremely low redox potential(−3.04 V vs.s...Lithium metal has been considered the ultimate anode material in Li rechargeable batteries because of its exceptionally high theoretical specific capacity(3860 mAh g^(−1))and extremely low redox potential(−3.04 V vs.standard hydrogen electrode).However,the uncontrollable formation of dendritic Li during Li plating/stripping cycling processes generates electrochemically disconnected Li chunks from the electrode,which consumes an active Li source in the electrolyte,thus degrading the electrolyte and leading to low Coulombic efficiency and safety concerns in Li rechargeable batteries.Therefore,the development of stable Li-metal anodes(LMAs)is required for highly reversible Li plating/stripping on the anode side.In this regard,magnesium metal and Mg-based alloys have attracted considerable attention as new LMAs because of their good compatibility with Li and high lithiophilicity.In this review,we introduce the recent advances and strategies for Mg-metal-and Mg-based alloy materials to achieve high durability in next-generation Li-ion batteries and all-solid-state batteries.In addition,we discuss the challenges in the development of Mg-based alloys and their future perspectives.The comprehensive understanding of Mg-metal-and Mg-based alloy materials for LMAs in this review will offer the reader the inspiration to establish an effective strategy for future research.展开更多
This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag ...This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag hollow spheres.The g-C_(3)N_(4)@Ag spheres provide a managed internal site for Li metal encapsulation and promote stable Li plating.The g-C_(3)N_(4) spheres are uniformly coated using polydopamine,which has an adhesive nature,to enhance lithium plating/stripping stability.The strategic presence of Ag nano-seeds eliminates the nucleation barrier,properly directing Li growth within the hollow spheres.This design facilitates highly reversible and consistent lithium deposition,offering a promising direction for the production of high-performance lithium metal anodes.These well-designed g-C_(3)N_(4)@Ag hollow spheres ensure stable Li plating/stripping kinetics over more than 500 cycles with a high coulombic efficiency of over 97%.Furthermore,a full cell made using LiNi_(0.90)Co_(0.07)Mn_(0.03)O_(2) and Li-g-C_(3)N_(4)@Ag host electrodes demonstrated highly competitive performance over 200 cycles,providing a guide for the implementation of this technology in advanced lithium metal batteries.展开更多
Lithium metal batteries are the most promising choices for next-generation high-energy–density batteries. However, there is little mechanism understanding on lithium dendrite growth during lithium plating and the dea...Lithium metal batteries are the most promising choices for next-generation high-energy–density batteries. However, there is little mechanism understanding on lithium dendrite growth during lithium plating and the dead lithium(the main component of inactive lithium) formation during lithium stripping. This work proposed a phase field model to describe the lithium stripping process with dead lithium formation.The coupling of galvanostatic conditions enables the phase field method to accurately match experimental results. The factors influencing the dead lithium formation on the increasing discharge polarization are revealed. Besides, the simulation of the battery polarization curve, the capacity loss peak, and the Coulomb efficiency is realized. This contribution affords an insightful understanding on dead lithium formation with phase field methods, which can contribute general principles on rational design of lithium metal batteries.展开更多
The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolyt...The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.展开更多
Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properti...Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.展开更多
Lithium metal anode is one of the ideal anode materials for the next generation of high-energy-density battery systems.Unfortunately,the uneven nucleation of Li leads to dendrite growth and volume changes during cycli...Lithium metal anode is one of the ideal anode materials for the next generation of high-energy-density battery systems.Unfortunately,the uneven nucleation of Li leads to dendrite growth and volume changes during cycling,resulting in poor electrochemical performance and potential safety hazards,which hinder its practical application.In this work,a low-cost chicken-bonederived carbon material(CBC)with a biomimetic structure was designed and synthesized using a simple one-step carbonization method.Combining theoretical calculations and experimental results,the self-doped N and S heteroatoms in CBC are demonstrated to effectively reduce the binding energy with Li atoms and lower the nucleation overpotential.After uniform nucleation,the Li metal grows in a spherical shape without dendrites,which is related to the reduction of the local current density inside the biomimetic crosslinking structure of CBC.Benefiting from this favorable Li growth behavior,the Li@CBC electrode achieves ultra-low nucleation overpotential(15.5 mV at 0.1 mA cm^(−2))and superdense lithium deposition(zero volume expansion rate at a capacity of 2 mAh cm^(−2))without introducing additional lithiophilic sites.The CBC retains a high Coulombic efficiency of over 98%in 479 cycles(1 mA cm^(−2)and 1 mAh cm^(−2))when applied in a half-cell with Li,and shows an excellent rate and cycling performance when applied in a full cell with LiFePO4 as the cathode.展开更多
The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additiv...The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.展开更多
The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-ri...The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.展开更多
Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li den...Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application.One efficient strategy is to construct a superior solid electrolyte interface.Herein,a stable interface enriched with Li3N and LiF is in-situ formed between Li anode and a terna ry salt electrolyte.This terna ry salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide(LiTFSI),lithium bis(fluorosulfonyl)imide(LiFSI),and LiNO_(3)to poly(ethylene oxide)matrix.Surface characterization indicates that LiNO3and LiFSI contribute to forming a Li3N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity.Theoretically,among various Li compound components,Li3N has high ionic conductivity,which is beneficial for reducing overpotential,while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites.The experimental results show that ASSLBs coupled with LiFePO4cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C,with a final and corresponding discharge specific capacity of 96.7 mA h g^(-1).Additionally,a schematic illustration of the working mechanism for the Li_(3)N-LiF interface is proposed.展开更多
Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges ...Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.展开更多
基金the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金supported by the Key Technologies R&D Program of Xiamen(No.3502Z20231057)the Natural Science Foundation of Fujian Province,China(No.2024J011210,No.2021J011214,No.2021J01685)+5 种基金the High-Level Talent Start-Up Foundation of Xiamen Institute of Technology for financial support(No.YKJ23017R)the Industry Leading Key Projects of Fujian Province(No.2022H0057)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2020R01002)the Fujian Young and Middle-aged Teachers Teacher Education Research Project(Science and Technology)(No.JAT200461)2023 Xiamen Overseas Students Scientific Research Project(Start-up)the National Natural Science Foundation of China(No.21975212,No.22101242,No.52002352,No.52071295)。
文摘Traditional pyrometallurgy and hydrometallurgy processes primarily focus on the recovery of valuable metals(Co,Ni,etc.)from spent lithium-ion batteries.However,these methods are not economical for recycling cheap LiFePO_(4).Herein,a synergistic thermal-decomposition and electric-drive strategy is proposed to recover the whole spent LiFePO_(4)electrode by in-situ recovering the inactive lithium(dead lithium and trapped interlayer lithium).Firstly,the organic components in the dense solid electrolyte interface(SEI)are effectively decomposed through thermal-decomposition processing,exposing the dead lithium encapsulated within the SEI and recovering the electron channels between the dead lithium and graphite.Leveraging the difference between the Gibbs free energy of the dead lithium and graphite as the driving force facilitates the dead lithium inserting into the anode.Then,fully utilizing the remaining discharge capacity of the spent LiFePO_(4)cell,the inactive lithium is reinserted into LiFePO_(4)lattice during the electric-drive process.Consequently,the reactivated lithium content increases by more than 16%,reaching a capacity of 134.2 mA h g^(-1)compared to 115.2 mA h g^(-1)from degraded LiFePO_(4),allowing for effective participation in the subsequent cycling.This work provides new perspectives on highly profitable cycles with low energy and material consumption and a low carbon footprint.
基金supported by the National Natural Science Foundation of China(Nos.52374302 and 51874099)the Natural Science Foundation of Fujian Province’s Key Project(No.2021J02031)+1 种基金support from the open fund from Academy of Carbon Neutrality of Fujian Normal University(No.TZH_(2)022-06)We also thank the Undergraduate Training Programs for Innovation and Entrepreneurship(No.cxx1-2024363)。
文摘The widespread application of solid-state polymer electrolytes(SPEs)is impeded due to their limited ionic conductivity,narrow electrochemical window and lithium dendrite problem.In this work,Mg-metal-organic frameworks(MOF)is incorporated into a polyethylene oxide(PEO)-based polymer solid electrolyte,leading to the insitu formation of LiF and other compounds at the electrolyte interface.This modification significantly improves lithium-ion transport capabilities and regulates lithium deposition behavior,suppressing the formation of lithium dendrites.
基金supported by Yunnan Natural Science Foundation Project(No.202202AG050003)Yunnan Fundamental Research Projects(Nos.202101BE070001-018 and 202201AT070070)+1 种基金the National Youth Talent Support Program of Yunnan Province China(No.YNQR-QNRC-2020-011)Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(No.2023-XMDJ-00617107)。
文摘Lithium metal has emerged as a highly promising anode material for enhancing the energy density of secondary batteries,attributed to its high theoretical specific capacity and low electrochemical potential.However,safety concerns related to lithium dendrite-induced short circuits and suboptimal electrochemical performance have impeded the commercial viability of lithium metal batteries.Current research efforts primarily focus on altering the solvated structure of Li+by modifying the current collector or introducing electrolyte additives to lower the nucleation barrier,expedite the desolvation process,and suppress the growth of lithium dendrites.Nevertheless,an integrated approach that combines the advantages of these two strategies remains elusive.In this study,we successfully employed metal-organic salt additives with lithophilic properties to accelerate the desolvation process,reduce the nucleation barrier of Li+,and modulate its solvated structure.This approach enhanced the inorganic compound content in the solid electrolyte interphase(SEI)on lithium foil surfaces,leading to stable Li+deposition and stripping.Specifically,Li||Cu cells demonstrated excellent cycle life and Coulombic efficiency(97.28%and 98.59%,respectively)at 0.5 m A/cm^(2)@0.5 m Ah/cm^(2)and 1 m A/cm^(2)@1 m Ah/cm^(2)for 410 and 240 cycles,respectively.Li||Li symmetrical cells showed no short circuit at 1 m A/cm^(2)@1 m Ah/cm^(2)for 1150 h,and Li||LFP full cells retained 68.9%of their capacity(104.6 m Ah/g)after 250 cycles at N/P(1.1:1.0)with a current density of 1C.
基金supported by the National Key Research and Development Program of China(2022YFA1203602)the National Natural Science Foundation of China(Grant No.12025206)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0620101)the National Natural Science Foundations of China(Grant No.12202366).
文摘Anode-free lithium metal batteries are prone to capacity degradation and safety hazards due to the formation and growth of lithium dendrites.The interface between the current collector and deposited lithium plays a critical role in preventing dendrite formation by regulating the thermodynamics and kinetics of lithium deposition.In this study,we develop a phase field model to investigate the influence of the current collector’s surface energy on lithium deposition morphology and its effect on the quality of the lithium metal film.It is demonstrated that a higher surface energy of the current collector promotes the growth of lithium metal along the surface of the current collector.Further,our simulation results show that a higher surface energy accelerates the formation of the lithium metal film while simultaneously reducing its surface roughness.By examining different contact angles and applied potentials,we construct a phase diagram of deposition morphology,illustrating that increased surface energy facilitates the dense and uniform deposition of lithium metal by preventing the formation of lithium filaments and voids.These findings provide new insights into the development and application of anode-free lithium metal batteries.
基金supported by the Qingdao Jiuhuanxinyue New Energy Technology Co.,Ltd.the Guangdong Basic and Applied Basic Research Foundation(Grant No.2021B1515120071)+2 种基金the 21C Innovation Laboratory,Contemporary Amperex Technology Ltd.(Grant No.21C-OP-202112)the financial support from the Guangdong Basic and Applied Basic Research Foundation(Grant No.2024A1515011873)the Shenzhen Science and Technology Program(Grant No.JCYJ20220531095212027).
文摘Li metal is widely recognized as the desired anode for next-generation energy storage,Li metal batteries,due to its highest theoretical capacity and lowest potential.Nonetheless,it suffers from unstable electrochemical behaviors like dendrite growth and side reactions in practical application.Herein,we report a highly stable anode with collector,Li_(5)Mg@Cu,realized by the melting-rolling process.The Li_(5)Mg@Cu anode delivers ultrahigh cycle stability for 2000 and 1000 h at the current densities of 1 and 2 mA cm^(-2),respectively in symmetric cells.Meanwhile,the Li_(5)Mg@Cu|LFP cell exhibits a high-capacity retention of 91.8% for 1000 cycles and 78.8% for 2000 cycles at 1 C.Moreover,we investigate the suppression effects of Mg on the dendrite growth by studying the performance of Li_(x)Mg@Cu electrodes with different Mg contents(2.0-16.7 at%).The exchange current density,surface energy,Li^(+)diffusion coefficient,and chemical stability of Li_(x)Mg@Cu concretely reveal this improving suppression effect when Mg content becomes higher.In addition,a Mg-rich phase with“hollow brick”morphology forming in the high Mg content Li_(x)Mg@Cu guides the uniform deposition of Li.This study reveals the suppression effects of Mg on Li dendrites growth and offers a perspective for finding the optimal component of Li-Mg alloys.
文摘All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.
基金supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2022-NR070534)funded by the Ministry of Education(RS-2020-NR049594).
文摘Lithium metal has been considered the ultimate anode material in Li rechargeable batteries because of its exceptionally high theoretical specific capacity(3860 mAh g^(−1))and extremely low redox potential(−3.04 V vs.standard hydrogen electrode).However,the uncontrollable formation of dendritic Li during Li plating/stripping cycling processes generates electrochemically disconnected Li chunks from the electrode,which consumes an active Li source in the electrolyte,thus degrading the electrolyte and leading to low Coulombic efficiency and safety concerns in Li rechargeable batteries.Therefore,the development of stable Li-metal anodes(LMAs)is required for highly reversible Li plating/stripping on the anode side.In this regard,magnesium metal and Mg-based alloys have attracted considerable attention as new LMAs because of their good compatibility with Li and high lithiophilicity.In this review,we introduce the recent advances and strategies for Mg-metal-and Mg-based alloy materials to achieve high durability in next-generation Li-ion batteries and all-solid-state batteries.In addition,we discuss the challenges in the development of Mg-based alloys and their future perspectives.The comprehensive understanding of Mg-metal-and Mg-based alloy materials for LMAs in this review will offer the reader the inspiration to establish an effective strategy for future research.
基金supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(No.GTL24011-000)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00272863)supported by Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(P0012748,HRD Program for Industrial Innovation)。
文摘This study presents a novel Li metal host material with a unique hollow nano-spherical structure that incorporates Ag nano-seeds into a graphitic carbon nitride(g-C_(3)N_(4))shell layer,referred to as g-C_(3)N_(4)@Ag hollow spheres.The g-C_(3)N_(4)@Ag spheres provide a managed internal site for Li metal encapsulation and promote stable Li plating.The g-C_(3)N_(4) spheres are uniformly coated using polydopamine,which has an adhesive nature,to enhance lithium plating/stripping stability.The strategic presence of Ag nano-seeds eliminates the nucleation barrier,properly directing Li growth within the hollow spheres.This design facilitates highly reversible and consistent lithium deposition,offering a promising direction for the production of high-performance lithium metal anodes.These well-designed g-C_(3)N_(4)@Ag hollow spheres ensure stable Li plating/stripping kinetics over more than 500 cycles with a high coulombic efficiency of over 97%.Furthermore,a full cell made using LiNi_(0.90)Co_(0.07)Mn_(0.03)O_(2) and Li-g-C_(3)N_(4)@Ag host electrodes demonstrated highly competitive performance over 200 cycles,providing a guide for the implementation of this technology in advanced lithium metal batteries.
基金supported by the National Natural Scientific Foundation of China(22109011)the China Postdoctoral Science Foundation(BX20200047,2021M690380)。
文摘Lithium metal batteries are the most promising choices for next-generation high-energy–density batteries. However, there is little mechanism understanding on lithium dendrite growth during lithium plating and the dead lithium(the main component of inactive lithium) formation during lithium stripping. This work proposed a phase field model to describe the lithium stripping process with dead lithium formation.The coupling of galvanostatic conditions enables the phase field method to accurately match experimental results. The factors influencing the dead lithium formation on the increasing discharge polarization are revealed. Besides, the simulation of the battery polarization curve, the capacity loss peak, and the Coulomb efficiency is realized. This contribution affords an insightful understanding on dead lithium formation with phase field methods, which can contribute general principles on rational design of lithium metal batteries.
文摘The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.
基金supported by the Australian Research Council Centre of Excellence in Optical Microcombs for Breakthrough Science COMBS(CE230100006)the Australian Research Council grants DP220100488 and DE230100964funded by the Australian Government.
文摘Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.
基金National Natural Science Foundation of China,Grant/Award Numbers:22179005,92372207。
文摘Lithium metal anode is one of the ideal anode materials for the next generation of high-energy-density battery systems.Unfortunately,the uneven nucleation of Li leads to dendrite growth and volume changes during cycling,resulting in poor electrochemical performance and potential safety hazards,which hinder its practical application.In this work,a low-cost chicken-bonederived carbon material(CBC)with a biomimetic structure was designed and synthesized using a simple one-step carbonization method.Combining theoretical calculations and experimental results,the self-doped N and S heteroatoms in CBC are demonstrated to effectively reduce the binding energy with Li atoms and lower the nucleation overpotential.After uniform nucleation,the Li metal grows in a spherical shape without dendrites,which is related to the reduction of the local current density inside the biomimetic crosslinking structure of CBC.Benefiting from this favorable Li growth behavior,the Li@CBC electrode achieves ultra-low nucleation overpotential(15.5 mV at 0.1 mA cm^(−2))and superdense lithium deposition(zero volume expansion rate at a capacity of 2 mAh cm^(−2))without introducing additional lithiophilic sites.The CBC retains a high Coulombic efficiency of over 98%in 479 cycles(1 mA cm^(−2)and 1 mAh cm^(−2))when applied in a half-cell with Li,and shows an excellent rate and cycling performance when applied in a full cell with LiFePO4 as the cathode.
基金supported by the National Natural Science Foundation of China(U21A20311)Researchers Supporting Project Number(RSP2025R304),King Saud University,Riyadh,Saudi Arabia。
文摘The performance of lithium metal batteries(LMBs)is greatly hampered by the unstable solid electrolyte interphase(SEI)and uncontrollable growth of Li dendrites.To address this question,we developed a weak polar additive strategy to develop stable and dendrite-free electrolyte for LMBs.In this paper,the effects of additives on the Li^(+)solvation kinetics and the electrode-electrolyte interphases(EEI)formation are discussed.The function of synergistically boosting the superior Li^(+)kinetics and alleviating solvent decomposition on the electrodes is confirmed.From the thermodynamic view,the exothermic process of defluorination reaction for 3,5-difluoropyridine(3,5-DFPy)results in the formation of LiF-rich SEI layer for promoting the uniform Li nucleation and deposition.From the dynamic view,the weakened Li^(+)solvation structure induced by weak polar 3,5-DFPy contributes to better Li^(+)kinetics through the easier Li^(+)desolvation.As expected,Li||Li cell with 1.0 wt%3,5-DFPy exhibits 400 cycles at 1.0 mA cm^(-2)with a deposition capacity of 0.5 mAh cm^(-2),and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)batteries delivers the highly reversible capacity after 200 cycles.
基金supported by the National Natural Science Foundation of China(No.51972066)the Natural Science Foundation of Guangdong Province of China(No.2024A1515012499)。
文摘The uneven deposition and high reactivity of lithium-metal anode(LMA)lead to uncontrollable dendrite growth,low Coulombic efficiency,and safety concerns,hindering their commercialization.Here,a representative polar-rich-group triazine-based covalent organic framework(COF-TzDha)with a desolvation effect is designed as an interlayer for stable,dendrite-free LMA.The abundant triazine rings in COFTzDha as a donor effectively attract lithium ions,while the one-dimensional nanopore structure facilitates lithium-ion migration.The periodic arrangement of polar groups(-OH)in the backbone interacts with electrolyte components(DOL,DME,TFSI-)to form a hydrogen bonding network that slows solvent molecules transport.Therefore,COF-TzDha effectively desolvates lithium ions from the solvent sheath,promoting uniform lithium ion flux and Li plating/stripping.Theoretical calculations verify that COFTzDha with abundant adsorption sites and strong adsorption energy facilitates lithium ion desolvation.Consequently,the introduction of COF-TzDha obtains a high ion mobility(0.75).The Li|COF@PP|Li symmetric cell cycles stably for over 1200 h at 4 mA cm^(-2)/4.0 mA h cm^(-2).The Li|COF@PP|LiFePO_(4)full cell also displays highly stable cycling performance with 600 cycles(75.5%capacity retention,~100% Coulombic efficiency)at 1 C.This work verifies an effective strategy for inducing uniform Li deposition and achieving dendrite-free,stable LMA using a polar-rich-group COF interlayer with a desolvation effect.
基金supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Natural Science Foundation of Hebei Province(no.E2022501014)+3 种基金the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)the Fundamental Research Funds for the Central Universities(no.N2423054)the 2023 Hebei Provincial Doctoral Candidate Innovation Ability Training Funding Project(no.CXZZBS2023159)the Performance Subsidy Fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H).
文摘Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries(ASSLBs)have received widespread attention due to their low cost,good process ability,and high energy density.Nevertheless,the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application.One efficient strategy is to construct a superior solid electrolyte interface.Herein,a stable interface enriched with Li3N and LiF is in-situ formed between Li anode and a terna ry salt electrolyte.This terna ry salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide(LiTFSI),lithium bis(fluorosulfonyl)imide(LiFSI),and LiNO_(3)to poly(ethylene oxide)matrix.Surface characterization indicates that LiNO3and LiFSI contribute to forming a Li3N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity.Theoretically,among various Li compound components,Li3N has high ionic conductivity,which is beneficial for reducing overpotential,while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites.The experimental results show that ASSLBs coupled with LiFePO4cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C,with a final and corresponding discharge specific capacity of 96.7 mA h g^(-1).Additionally,a schematic illustration of the working mechanism for the Li_(3)N-LiF interface is proposed.
基金support from The Hong Kong Polytechnic University(U-CDCA)and Innovation and Technology Fund(ITS-322-23FP)。
文摘Developing advanced polymer electrolytes in lithium metal batteries(LMBs)has gained significant attention because of their inherent safety advantages over liquid electrolytes,while still encountering great challenges in mitigating uneven lithium plating/stripping and dendrite growth.Previous efforts primarily focused on passive approaches to mechanically constrain lithium dendrite growth.Recent studies have revealed the significance and effectiveness of regulating supramolecular interactions between polymer chains and other electrolyte components for homogenizing lithium deposition and enhancing the interfacial stability.This report provides a timely critical review to cover recent inspiring advancements in this direction.We first summarize the origins of supramolecular interaction origins,strength-determining factors,and structure–property relationships to establish quantitative correlations between polymer composition and supramolecular interaction properties.Then the recent advances in regulating supramolecular interaction chemistry are comprehensively discussed,focusing on those towards accelerated mass transport and stabilized anode-electrolyte interface.Finally,the remaining challenges are highlighted,and potential future directions in supramolecular interaction regulation of polymer electrolytes are prospected for the practical application of LMBs.
