Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utiliz...Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.展开更多
The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the che...The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.展开更多
Aqueous Zn ion batteries(ZIBs)have received extensive attention due to their intrinsic safety,high abundance,and low cost.However,uncontrolled dendrite growth and water-induced side reactions at electrod e/electrolyte...Aqueous Zn ion batteries(ZIBs)have received extensive attention due to their intrinsic safety,high abundance,and low cost.However,uncontrolled dendrite growth and water-induced side reactions at electrod e/electrolyte interfaces hinder the advancement of ZIBs.Herein,density functional theory(DFT)calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn^(2+)deposition by leveraging the abundant zincophilic groups(e.g.,-COO^(-)and-CF)and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains.A Zn heptafluorobutyrate protective layer(denoted as ZFA)is constructed on the metallic Zn surface in situ by acid etching process to control Zn^(2+)desolvation and nucleation behaviors,ensuring enhanced reversibility and stability of Zn anodes.Consequently,the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm^(-2)and over 7300cycles at 40 mA cm^(-2),with high Coulombic efficiency of 99.8%over 1900 cycles at 5 mA cm^(-2).Impressively,Zn@ZFA‖VO_(2)full cell achieves exceptional cycle life(204 mA h g^(-1)after 750 cycles at 3 A g^(-1))and remarkable rate performance(236 mA g^(-1)at 10 A g^(-1)).This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.展开更多
Micron-sized silicon(μSi)is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity,low cost,and abundant reserves.However,the volume expansion that occurs during cyclin...Micron-sized silicon(μSi)is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity,low cost,and abundant reserves.However,the volume expansion that occurs during cycling leads to the accumulation of undesirable stresses,resulting in pulverization of silicon microparticles and shortened lifespan of the batteries.Herein,a composite film of Cu-PET-Cu is proposed as the current collector(CC)forμSi anodes to replace the conventional Cu CC.Cu-PET-Cu CC is prepared by depositing Cu on both sides of a polyethylene terephthalate(PET)film.The PET layer promises good ductility of the film,permitting the Cu-PET-Cu CC to accommodate the volumetric changes of silicon microparticles and facilitates the stress release through ductile deformation.As a result,theμSi electrode with Cu-PET-Cu CC retains a high specific capacity of 2181 mA h g^(-1),whereas theμSi electrode with Cu CC(μSi/Cu)exhibits a specific capacity of 1285 mA h g^(-1)after 80 cycles.The stress relieving effect of CuPET-Cu was demonstrated by in-situ fiber optic stress monitoring and multi-physics simulations.This work proposes an effective stress relief strategy at the electrode level for the practical implementation ofμSi anodes.展开更多
Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dua...Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.展开更多
Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evo...Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evolution reaction(HER),and corrosion side reactions.Herein,we propose a surface engineering modification strategy for coating the montmorillonite(MMT)layer onto the surface of the Zn anode to tackle these issues,thereby achieving high cycling stability for rechargeable AZIBs.The results reveal that the MMT layer on the surface of the Zn anode is able to provide ordered zincophilic channels for zinc ions migration,facilitating the reaction kinetics of zinc ions.Density functional theory(DFT)calculations and water contact angle(CA)tests prove that MMT@Zn anode exhibits superior adsorption capacity for Zn^(2+)and better hydrophobicity than the bare Zn anode,thereby achieving excellent cycling stability.Moreover,the MMT@Zn||MMT@Zn symmetric cell holds the stable cycling over 5600 h at 0.5 mA cm^(-2)and 0.125 m A h cm^(-2),even exceeding 1800 h long cycling under harsh conditions of 5 m A cm^(-2)and 1.25 m A h cm^(-2).The MMT@Zn||V_(2)O_(5)full cell reaches over 3000 cycles at 2 A g^(-1)with excellent rate capability.Therefore,this surface engineering modification strategy for enhancing the electrochemical performance of AZIBs represents a promising application.展开更多
Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a h...Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.展开更多
Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material...Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material pulverization and capacity degradation.Recent research on nanostructured Si aims to mitigate volume expansion and enhance electrochemical performance,yet still grapples with issues like pulverization,unstable solid electrolyte interface(SEI)growth,and interparticle resistance.This review delves into innovative strategies for optimizing Si anodes’electrochemical performance via structural engineering,focusing on the synthesis of Si/C composites,engineering multidimensional nanostructures,and applying non-carbonaceous coatings.Forming a stable SEI is vital to prevent electrolyte decomposition and enhance Li^(+)transport,thereby stabilizing the Si anode interface and boosting cycling Coulombic efficiency.We also examine groundbreaking advancements such as self-healing polymers and advanced prelithiation methods to improve initial Coulombic efficiency and combat capacity loss.Our review uniquely provides a detailed examination of these strategies in real-world applications,moving beyond theoretical discussions.It offers a critical analysis of these approaches in terms of performance enhancement,scalability,and commercial feasibility.In conclusion,this review presents a comprehensive view and a forward-looking perspective on designing robust,high-performance Si-based anodes the next generation of LIBs.展开更多
The performance of optical interconnection has improved dramatically in recent years.Silicon-based optoelectronic heterogeneous integration is the key enabler to achieve high performance optical interconnection,which ...The performance of optical interconnection has improved dramatically in recent years.Silicon-based optoelectronic heterogeneous integration is the key enabler to achieve high performance optical interconnection,which not only provides the optical gain which is absent from native Si substrates and enables complete photonic functionalities on chip,but also improves the system performance through advanced heterogeneous integrated packaging.This paper reviews recent progress of silicon-based optoelectronic heterogeneous integration in high performance optical interconnection.The research status,development trend and application of ultra-low loss optical waveguides,high-speed detectors,high-speed modulators,lasers and 2D,2.5D,3D and monolithic integration are focused on.展开更多
Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low re...Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of zinc(Zn) metal. However,several issues such as dendrite formation, hydrogen evolution, corrosion, and passivation of Zn metal anodes cause irreversible loss of the active materials. To solve these issues, researchers often use large amounts of excess Zn to ensure a continuous supply of active materials for Zn anodes. This leads to the ultralow utilization of Zn anodes and squanders the high energy density of AZMBs. Herein, the design strategies for AZMBs with high Zn utilization are discussed in depth, from utilizing thinner Zn foils to constructing anode-free structures with theoretical Zn utilization of 100%, which provides comprehensive guidelines for further research. Representative methods for calculating the depth of discharge of Zn anodes with different structures are first summarized. The reasonable modification strategies of Zn foil anodes, current collectors with pre-deposited Zn, and anode-free aqueous Zn metal batteries(AF-AZMBs) to improve Zn utilization are then detailed. In particular, the working mechanism of AF-AZMBs is systematically introduced. Finally, the challenges and perspectives for constructing high-utilization Zn anodes are presented.展开更多
Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic propert...Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic property and high electrical conductivity at the same time.Herein,originating from theoretical calculation,a zincophilic particle regulation strategy is proposed to address these limitations and carbon coated Na_(3)V_(2)(PO_(4))_(3)is taken as an example to be a protective layer on zinc metal(NVPC@Zn).Na_(3)V_(2)(PO_(4))_(3)(NVP)is a common cathode material for Zn-ion batteries,which is zincophilic.Carbon materials not only offer an electron pathway to help Zn deposition onto NVPC surface,but also enhance the zinc nucleophilicity of Na_(3)V_(2)(PO_(4))_(3).Hence,this hybrid coating layer can tune zinc deposition and resist side reactions such as hydrogen generation and Zn metal corrosion.Experimentally,a symmetrical battery with NVPC@Zn electrode displays highly reversible plating/stripping behavior with a long cycle lifespan over 1800 h at2 mA cm^(-2),much better than carbon and Na_(3)V_(2)(PO_(4))_(3)solely modified Zn electrodes.When the Na_(3)V_(2)(PO_(4))_(3)is replaced with zincophobic Al2O3or zincophilic V2O3,the stability of the modified zinc anodes is also prolonged.This strategy expands the option of zincophilic materials and provides a general and effective way to stabilize the Zn electrode.展开更多
Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,hi...Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.展开更多
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv...Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.展开更多
Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal ...Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal issues,a free-standing anode with a"corrugated paper"shape on micro-scale and a topological crosslinking network on the submicron and nano-scale is designed.Essentially,an integrated three-dimensional electrode structure is constructed based on robust carbon nanotubes network with firmly anchored SiNPs via forming interlocking junctions.In which,the hierarchical interlocking structure is achieved by directional induction of the binder,which ensures well integration during cycling so that significantly enhances mechanical stability as well as electronic and ionic conductivity of electrodes.Benefiting from it,this anode exhibits outsta nding performance under harsh service conditions including high Si loading,ultrahigh areal capacity(33.2 mA h cm^(-2)),and high/low temperatures(-15-60℃),which significantly extends its practical prospect.Furthermore,the optimization mechanism of this electrode is explored to verify the crack-healing and structure-integration maintaining along cycling via a unique self-stabilization process.Thus,from both the fundamental and engineering views,this strategy offers a promising path to produce high-performance free-standing electrodes for flexible device applications especially facing volume effect challenges.展开更多
Zn powder anodes have attracted much attention in aqueous Zn ion battery applications due to advantages such as low cost and processability.However,the high-activity Zn powder anode faces problems such as side reactio...Zn powder anodes have attracted much attention in aqueous Zn ion battery applications due to advantages such as low cost and processability.However,the high-activity Zn powder anode faces problems such as side reactions,hydrogen evolution,and dendrites,which limit the cycling stability of the cell.In this work,the high activity of Zn powder is weakened by introducing low-cost erythritol as a functional additive in the ZnSO_(4) electrolyte to improve the cycle life of the cell.Both theoretical calculations and empirical evidence demonstrate that the incorporation of erythritol alters the coordination sphere of Zn^(2+)and modifies the local molecular architecture of the electrolyte.This modification serves to diminish the reactivity of water molecules,thereby efficaciously suppressing dendrite formation and deleterious ancillary reactions on the zinc powder anode surfaces.Concurrently,erythritol functions as an interfacial cationic captor,enhancing reaction dynamics and facilitating the development of a favorable protective layer throughout the zinc plating/stripping process.Consequently,the symmetric cell paired with an erythritol-containing electrolyte manifests stable cycling performance for an extended duration of 850 h at a current density of 0.288 mA cm^(-2)and areal capacity of 0.144 mAh cm^(-2).Notably,it maintains a cycling life of 400 h even under intensified conditions (2.88 mA cm^(-2)/1.44 mA h cm^(-2)).Furthermore,the constructed Na_(2)V_(6)O_(16)·3H_(2)O full cell illustrated remarkable capacity retention of 155.8 mA h g^(-1)following 800 cycles at a high rate of 5 A g^(-1).展开更多
The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate ...The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate their useless components(mainly the degraded solid electrolyte interphase,SEI)and reconstruct their damaged structure.Herein,a facile and efficient strategy is proposed to recycle the spent graphite on the basis of the careful investigation of the composition of the cycled graphite anodes and the rational design of the regeneration processes.The regenerated graphite,which is revitalized by calcination treatment and acid leaching,delivers superb rate performance and a high specific capacity of 370 mAh g^(-1)(~99% of its theoretical capacity)after 100 cycles at 0.1 C,superior to the commercial graphite anodes.The improved electrochemical performance could be attributed to unchoked Li^(+) transport channels and enhanced charge transfer reaction due to the effective destruction of the degraded SEI and the full recovery of the damaged structure of the spent graphite.This work clarifies that the electrochemical performance of the regenerated graphite could be deteriorated by even a trace amount of the residual“impurity”and provides a facile method for the efficient regeneration of graphite anodes.展开更多
Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentrati...Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentration of the intercalated Li ions.In this work,we performed first-principles calculations to comprehensively address the energetics and dynamics of Li intercalation and Li vacancy diffusion near the no n-basal edges of graphite,namely the armchair and zigzag-edges,at high Li concentration.We find that surface effects persist in stage-Ⅱ that bind Li strongly at the edge sites.However,the pronounced effect previously identified at the zigzag edge of pristine graphite is reduced in LiC_(12),penetrating only to the subsurface site,and eventually disappearing in LiC_(6).Consequently,the distinctive surface state at the zigzag edge significantly impacts and restrains the charging rate at the initial lithiation of graphite anodes,whilst diminishes with an increasing degree of lithiation.Longer diffusion time for Li hopping to the bulk site from either the zigzag edge or the armchair edge in LiC_(6) was observed during high state of charge due to charge repulsion.Effectively controlling Li occupation and diffusion kinetics at this stage is also crucial for enhancing the charge rate.展开更多
The extreme volume expansion of the silicon(Si) anodes during repeated cycles seriously induces undesirable interfacial side reactions,forming an unstable solid electrolyte interphase(SEI) that degrades the electrode ...The extreme volume expansion of the silicon(Si) anodes during repeated cycles seriously induces undesirable interfacial side reactions,forming an unstable solid electrolyte interphase(SEI) that degrades the electrode integrity and cycle stability in lithium-ion batteries,limiting their practical applications.Despite considerable efforts to stabilize the SEI through surface modification,challenges persist in the development of high-performance Si anodes that effectively regulate intrinsic SEI properties and simultaneously facilitate electron/ion transport.Here,a highly conductive and organic electrolyte-compatible lamellar p-toluenesulfonic acid-doped polyaniline(pTAP) layer is proposed for constructing a robust artificial SEI on Si nanoparticles to achieve fast charging,lo ng-term cycle lifespan and high areal capacity.The spatially uniform pTAP layer,formed through a facile direct-encapsulation approach assisted by enriched hydrogen bonding,contributes to the effective formation of in situ SEI with an even distribution of the LiF-rich phase in its interlamination spaces.Furthermore,the integrated artificial SEI facilitates isotropic ion/electron transport,increased robustness,and effectively dissipates stress from volume changes.Consequently,a notably high rate performance of 570 mA h g^(-1),even at a substantially high current density of 10 A g^(-1),is achieved with excellent cyclic stability by showing a superior capacity over 1430 mA h g^(-1) at 1 A g^(-1) after 250 cycles and a high areal capacity of ca.2 mA h cm^(-2) at 0.5 C in a full cell system.This study demonstrates that the rational design of conductive polymers with SEI modulation for surface protection has great potential for use in high-energy-density Si anodes.展开更多
Aqueous zinc metal batteries (AZMBs) are hindered by uncontrolled dendrites and side reactions during commercialization,despite their advantages of safety and high capacity density.Herein,we propose the electrical fee...Aqueous zinc metal batteries (AZMBs) are hindered by uncontrolled dendrites and side reactions during commercialization,despite their advantages of safety and high capacity density.Herein,we propose the electrical feedback strategy to restrain the Zn dendrites resulting from the"tip effect"and optimize interfacial Zn^(2+)distribution to accelerate electrodeposition kinetics by using the lithium niobate (LNO) layer.Specifically,at the bumps of the zinc anode,the ferroelectric LNO is polarized by the locally strong electric field,which in turn counteracts the"tip effect".In this way,the dynamic polarization of LNO can repair the uneven tip electric field to achieve uniform and flat zinc deposition.In addition,owing to the interaction between Nb and Zn^(2+),a higher concentration of Zn^(2+)near the zincophilic LNO@Zn surface is obtained for the rapid electrochemical reaction kinetics of plating.Considering the aforementioned advantages,the LNO@Zn anode harvests stable cycling over 1200 h at 10 mA cm^(-2)with a superior cumulative capacity of 5800 mAh cm^(-2).Assembled with the a-MnO_(2) cathode,the full cell using LNO@Zn anode exhibits the slower capacity decay (0.054%per cycle) during 1000 cycles.This strategy provides a perspective for stabilizing zinc metal anodes through dynamic electrical response and interfacial ion redistribution effect.展开更多
Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume ch...Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume changes during lithium deposition/stripping processes lead to sustained accumulation of inactive lithium and poor cycling reversibility.Quantifying the formation and evolution of inactive lithium under different conditions and fully evaluating the complex failure modes are the key issues in this challenging field.This article comprehensively reviews recent research progress on the quantification of formation and evolution of inactive lithium detected by different quantitative techniques in rechargeable lithium metal batteries.The key research challenges such as failure mechanism,modification strategies and operando characterization of lithium metal anodes are systematically summarized and prospected.This review provides a new angle of view to understand failure mechanism of lithium metal anodes and inspiration and guidance for the future development of rechargeable lithium metal batteries.展开更多
基金supported by the National Natural Science Foundation of China (51673017)the National Natural Science Foundation of China (21404005)+1 种基金the Fundamental Research Funds for the Central Universities (XK1802-2)the Natural Science Foundation of Jiangsu Province (BK20150273)。
文摘Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI) is synthesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA) with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combination of rigid benzene rings and flexible oxygen groups(-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH) groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8 × 10^(-10) cm^(2) s^(-1) vs.16 × 10^(-10) cm^(2) s~(-1)).As expected,the SiO_x@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g^(-1).The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiO_x@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy-density batteries.
基金supported by the National Natural Science Foundation of China (21875107, U1802256, and 22209204)Leading Edge Technology of Jiangsu Province (BK20220009), the Natural Science Foundation of Jiangsu Province (BK20221140)+2 种基金the China Postdoctoral Science Foundation (2022M713364)Jiangsu Specially Appointed Professors ProgramPriority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘The solvation structure of Li^(+) in chemical prelithiation reagent plays a key role in improving the low initial Coulombic efficiency(ICE) and poor cycle performance of silicon-based materials. Never theless, the chemical prelithiation agent is difficult to dope active Li^(+) in silicon-based anodes because of their low working voltage and sluggish Li^(+) diffusion rate. By selecting the lithium–arene complex reagent with 4-methylbiphenyl as an anion ligand and 2-methyltetrahydrofuran as a solvent, the as-prepared micro-sized Si O/C anode can achieve an ICE of nearly 100%. Interestingly, the best prelithium efficiency does not correspond to the lowest redox half-potential(E_(1/2)), and the prelithiation efficiency is determined by the specific influencing factors(E_(1/2), Li^(+) concentration, desolvation energy, and ion diffusion path). In addition, molecular dynamics simulations demonstrate that the ideal prelithiation efficiency can be achieved by choosing appropriate anion ligand and solvent to regulate the solvation structure of Li^(+). Furthermore, the positive effect of prelithiation on cycle performance has been verified by using an in-situ electrochemical dilatometry and solid electrolyte interphase film characterizations.
基金supported by the National Natural Science Foundation of China(52372164,52302085,and 52172174)the Anhui Provincial Natural Science Foundation(2308085Y05 and 2308085QE143)+1 种基金the Key Natural Science Research Project of Anhui Provincial Education Department(2023AH050094)the startup grants from Anhui University(S020318031/001).
文摘Aqueous Zn ion batteries(ZIBs)have received extensive attention due to their intrinsic safety,high abundance,and low cost.However,uncontrolled dendrite growth and water-induced side reactions at electrod e/electrolyte interfaces hinder the advancement of ZIBs.Herein,density functional theory(DFT)calculation indicates that Zn heptafluorobutyrate can facilitate uniform Zn^(2+)deposition by leveraging the abundant zincophilic groups(e.g.,-COO^(-)and-CF)and inhibit water-induced side reactions due to the presence of hydrophobic carbon chains.A Zn heptafluorobutyrate protective layer(denoted as ZFA)is constructed on the metallic Zn surface in situ by acid etching process to control Zn^(2+)desolvation and nucleation behaviors,ensuring enhanced reversibility and stability of Zn anodes.Consequently,the Zn@ZFA anode demonstrates stable operation for more than 2200 h at 1 mA cm^(-2)and over 7300cycles at 40 mA cm^(-2),with high Coulombic efficiency of 99.8%over 1900 cycles at 5 mA cm^(-2).Impressively,Zn@ZFA‖VO_(2)full cell achieves exceptional cycle life(204 mA h g^(-1)after 750 cycles at 3 A g^(-1))and remarkable rate performance(236 mA g^(-1)at 10 A g^(-1)).This work provides an insightful guidance for constructing a protection layer of dendrite-free Zn anodes for high-performance ZIBs.
基金supported by the the National Key R&D Program of China(2022YFB3803500)the Natural Science Foundation of Hubei Province(2021CFA066).
文摘Micron-sized silicon(μSi)is a promising anode material for next-generation lithium-ion batteries due to its high specific capacity,low cost,and abundant reserves.However,the volume expansion that occurs during cycling leads to the accumulation of undesirable stresses,resulting in pulverization of silicon microparticles and shortened lifespan of the batteries.Herein,a composite film of Cu-PET-Cu is proposed as the current collector(CC)forμSi anodes to replace the conventional Cu CC.Cu-PET-Cu CC is prepared by depositing Cu on both sides of a polyethylene terephthalate(PET)film.The PET layer promises good ductility of the film,permitting the Cu-PET-Cu CC to accommodate the volumetric changes of silicon microparticles and facilitates the stress release through ductile deformation.As a result,theμSi electrode with Cu-PET-Cu CC retains a high specific capacity of 2181 mA h g^(-1),whereas theμSi electrode with Cu CC(μSi/Cu)exhibits a specific capacity of 1285 mA h g^(-1)after 80 cycles.The stress relieving effect of CuPET-Cu was demonstrated by in-situ fiber optic stress monitoring and multi-physics simulations.This work proposes an effective stress relief strategy at the electrode level for the practical implementation ofμSi anodes.
基金supported by the National Natural Science Foundation of China(21975091,22122902,and 52272208)the Fundamental Research Fund for the Central Universities of China(2662023LXPY001 and 2662021JC004).
文摘Lithium plating/stripping occurs at the a node/electrolyte interface which involves the flow of electrons from the current collector and the migration of lithium ions from the solid-electrolyte interphase(SEI).The dual continuous rapid transport of interfacial electron/ion is required for homogeneous Li deposition.Herein,we propose a strategy to improve the Li metal anode performance by rationally regulating the interfacial electron density and Li ion transport through the SEI film.This key technique involves decreasing the interfacial oxygen density of biomass-derived carbon host by regulating the arrangement of the celluloses precursor fibrils.The higher specific surface area and lower interfacial oxygen density decrease the local current density and ensure the formation of thin and even SEI film,which stabilized Li^(+)transfer through the Li/electrolyte interface.Moreover,the improved graphitization and the interconnected conducting network enhance the surface electronegativity of carbon and enable uninterruptible electron conduction.The result is continuous and rapid coupled interfacial electron/ion transport at the anode/electrolyte reaction interface,which facilitates uniform Li deposition and improves Li anode performance.The Li/C anode shows a high initial Coulombic efficiency of 98%and a long-term lifespan of over 150cycles at a practical low N/P(negative-to-positive)ratio of 1.44 in full cells.
基金National Natural Science Foundation of China(Grant No.22005318,22379152)Western Young Scholars Foundations of Chinese Academy of Sciences+4 种基金Lanzhou Youth Science and Technology Talent Innovation Project(Grant No.2023-NQ-86,No.2023-QN-96)Lanzhou Chengguan District Science and Technology Plan Project(Grant No.2023-rc-4,2022-rc-4)Collaborative Innovation Alliance Fund for Young Science and Technology Worker(Grant No.HZJJ23-7)National Nature Science Foundations of Gansu Province(Grant No.21JR11RA020)Fundamental Research Funds for the Central Universities(Grant No.31920220073,31920230128)。
文摘Rechargeable aqueous zinc-ion batteries(AZIBs)exhibit appreciable potential in the domain of electrochemical energy storage.However,there are serious challenges for AZIBs,for instance zinc dendrite growth,hydrogen evolution reaction(HER),and corrosion side reactions.Herein,we propose a surface engineering modification strategy for coating the montmorillonite(MMT)layer onto the surface of the Zn anode to tackle these issues,thereby achieving high cycling stability for rechargeable AZIBs.The results reveal that the MMT layer on the surface of the Zn anode is able to provide ordered zincophilic channels for zinc ions migration,facilitating the reaction kinetics of zinc ions.Density functional theory(DFT)calculations and water contact angle(CA)tests prove that MMT@Zn anode exhibits superior adsorption capacity for Zn^(2+)and better hydrophobicity than the bare Zn anode,thereby achieving excellent cycling stability.Moreover,the MMT@Zn||MMT@Zn symmetric cell holds the stable cycling over 5600 h at 0.5 mA cm^(-2)and 0.125 m A h cm^(-2),even exceeding 1800 h long cycling under harsh conditions of 5 m A cm^(-2)and 1.25 m A h cm^(-2).The MMT@Zn||V_(2)O_(5)full cell reaches over 3000 cycles at 2 A g^(-1)with excellent rate capability.Therefore,this surface engineering modification strategy for enhancing the electrochemical performance of AZIBs represents a promising application.
基金Department of Education of Gansu Province: Industrial Support Plan Project (2022CYZC-23)National Natural Science Foundation of China (22269012)Gansu Key Research and Development Program (23YFGA0053)。
文摘Silicon is considered to be one of the most promising anode materials for lithium-ion batteries(LIBs),but its application is limited by the large volume expansion during alloying and dealloying.The constructing of a high-performance solid electrolyte interface(SEI) film on the surface of the anode material is considered to be one of the effective strategies to mitigate volume expansion of silicon-based anode.In this study,an intermittent discharge strategy which helps to improve the utilization efficiency of electrolyte additive of lithium difluorobisoxalate phosphate(LiDFBOP) is proposed to construct a highly conductive and dense SEI film.The results of electrochemical and physical characterization and theoretical calculations show that the intermittent discharge in the voltage range from open circuit voltage(OCV) to 1.8 V facilitates the diffusion of the soluble products,creates the conditions for the repeated direct contact between Si@C anode and LiDFBOP additive,increases the decomposition of LiDFBOP additive,and thus produces a uniform,dense and inorganics-rich(Li_(2)C_(2)O_(4),LiF and Li_(x)PO_yF_z) SEI film.Subsequently,this SEI film helps to ensure the even intercalation/de-intercalation of Li^(+) in the SEI film and the homogeneous diffusion of Li^(+) inside the Si particles,decreasing the internal stresses and anisotropic phase transitions,maintaining the integrity of Si particles,inhibiting the volume expansion and thu s improving the electrochemical performance of cells.This study not only improves the utilization efficiency of expensive additives through a simply and low-cost method,but also enriches the strategy to improve the electrochemical performance of Si@C anode through interfacial engineering.
基金financially supported by the Jiangsu Distinguished Professors Project(No.1711510024)the funding for Scientific Research Startup of Jiangsu University(Nos.4111510015,19JDG044)+3 种基金the Jiangsu Provincial Program for High-Level Innovative and Entrepreneurial Talents Introductionthe National Natural Science Foundation of China(No.22008091)Natural Science Foundation of Guangdong Province(2023A1515010894)the Open Project of Luzhou Key Laboratory of Fine Chemical Application Technology(HYJH-2302-A).
文摘Silicon(Si)has emerged as a potent anode material for lithium-ion batteries(LIBs),but faces challenges like low electrical conductivity and significant volume changes during lithiation/delithiation,leading to material pulverization and capacity degradation.Recent research on nanostructured Si aims to mitigate volume expansion and enhance electrochemical performance,yet still grapples with issues like pulverization,unstable solid electrolyte interface(SEI)growth,and interparticle resistance.This review delves into innovative strategies for optimizing Si anodes’electrochemical performance via structural engineering,focusing on the synthesis of Si/C composites,engineering multidimensional nanostructures,and applying non-carbonaceous coatings.Forming a stable SEI is vital to prevent electrolyte decomposition and enhance Li^(+)transport,thereby stabilizing the Si anode interface and boosting cycling Coulombic efficiency.We also examine groundbreaking advancements such as self-healing polymers and advanced prelithiation methods to improve initial Coulombic efficiency and combat capacity loss.Our review uniquely provides a detailed examination of these strategies in real-world applications,moving beyond theoretical discussions.It offers a critical analysis of these approaches in terms of performance enhancement,scalability,and commercial feasibility.In conclusion,this review presents a comprehensive view and a forward-looking perspective on designing robust,high-performance Si-based anodes the next generation of LIBs.
基金Project supported in part by the National Key Research and Development Program of China(Grant No.2021YFB2206504)the National Natural Science Foundation of China(Grant No.62235017)the China Postdoctoral Science Foundation(Grant No.2021M703125).
文摘The performance of optical interconnection has improved dramatically in recent years.Silicon-based optoelectronic heterogeneous integration is the key enabler to achieve high performance optical interconnection,which not only provides the optical gain which is absent from native Si substrates and enables complete photonic functionalities on chip,but also improves the system performance through advanced heterogeneous integrated packaging.This paper reviews recent progress of silicon-based optoelectronic heterogeneous integration in high performance optical interconnection.The research status,development trend and application of ultra-low loss optical waveguides,high-speed detectors,high-speed modulators,lasers and 2D,2.5D,3D and monolithic integration are focused on.
基金the financial support from the National Natural Science Foundation of China (Grant Nos. 52201201, 52372171)the State Key Lab of Advanced Metals and Materials (Grant No. 2022Z-11)+1 种基金the Fundamental Research Funds for the Central Universities (Grant No. 00007747, 06500205)the Initiative Postdocs Supporting Program (Grant No. BX20190002)。
文摘Aqueous zinc metal batteries(AZMBs)are promising candidates for next-generation energy storage due to the excellent safety, environmental friendliness, natural abundance, high theoretical specific capacity, and low redox potential of zinc(Zn) metal. However,several issues such as dendrite formation, hydrogen evolution, corrosion, and passivation of Zn metal anodes cause irreversible loss of the active materials. To solve these issues, researchers often use large amounts of excess Zn to ensure a continuous supply of active materials for Zn anodes. This leads to the ultralow utilization of Zn anodes and squanders the high energy density of AZMBs. Herein, the design strategies for AZMBs with high Zn utilization are discussed in depth, from utilizing thinner Zn foils to constructing anode-free structures with theoretical Zn utilization of 100%, which provides comprehensive guidelines for further research. Representative methods for calculating the depth of discharge of Zn anodes with different structures are first summarized. The reasonable modification strategies of Zn foil anodes, current collectors with pre-deposited Zn, and anode-free aqueous Zn metal batteries(AF-AZMBs) to improve Zn utilization are then detailed. In particular, the working mechanism of AF-AZMBs is systematically introduced. Finally, the challenges and perspectives for constructing high-utilization Zn anodes are presented.
基金financially supported by the National Key Research and Development Program of China(2022YFB3803600)the Fundamental Research Funds for the Central Universities(30106200463 and CCNU22CJ017)+1 种基金the National Natural Science Foundation of China(U20A20246)the Graduate Education Innovation Grant from Central China Normal University,China(20210407032)。
文摘Zincophilic property and high electrical conductivity are both very important parameters to design novel Zn anode for aqueous Zn-ion batteries(AZIBs).However,single material is difficult to exhibit zincophilic property and high electrical conductivity at the same time.Herein,originating from theoretical calculation,a zincophilic particle regulation strategy is proposed to address these limitations and carbon coated Na_(3)V_(2)(PO_(4))_(3)is taken as an example to be a protective layer on zinc metal(NVPC@Zn).Na_(3)V_(2)(PO_(4))_(3)(NVP)is a common cathode material for Zn-ion batteries,which is zincophilic.Carbon materials not only offer an electron pathway to help Zn deposition onto NVPC surface,but also enhance the zinc nucleophilicity of Na_(3)V_(2)(PO_(4))_(3).Hence,this hybrid coating layer can tune zinc deposition and resist side reactions such as hydrogen generation and Zn metal corrosion.Experimentally,a symmetrical battery with NVPC@Zn electrode displays highly reversible plating/stripping behavior with a long cycle lifespan over 1800 h at2 mA cm^(-2),much better than carbon and Na_(3)V_(2)(PO_(4))_(3)solely modified Zn electrodes.When the Na_(3)V_(2)(PO_(4))_(3)is replaced with zincophobic Al2O3or zincophilic V2O3,the stability of the modified zinc anodes is also prolonged.This strategy expands the option of zincophilic materials and provides a general and effective way to stabilize the Zn electrode.
基金the financial support from the Australian Research Council,Centre for Materials Science,Queensland University of Technologythe Supported by the Fundamental Research Funds for the Central Universities。
文摘Developing sustainable and clean energy sources(e.g.,solar,wind,and tide energy)is essential to achieve the goal of carbon neutrality.Due to the discontinuous and inco nsistent nature of common clean energy sources,high-performance energy storage technologies are a critical part of achieving this target.Aqueous zinc metal batteries(AZMBs)with inherent safety,low cost,and competitive performance are regarded as one of the promising candidates for grid-scale energy storage.However,zinc metal anodes(ZMAs)with irreversible problems of dendrite growth,hydrogen evolution reaction,self-corrosio n,and other side reactions have seriously hindered the development and commercialization of AZMBs.An increasing number of researchers are focusing on the stability of ZMAs,so assessing the effectiveness of existing research strategies is critical to the development of AZMBs.This review aims to provide a comprehensive overview of the fundamentals and challenges of AZMBs.Resea rch strategies for interfacial modification of ZMAs are systematically presented.The features of artificial interfacial coating and in-situ interfacial coating of ZMAs are compared and discussed in detail,as well as the effect of modified interfacial ZMA on the full-battery performance.Finally,perspectives are provided on the problems and challenges of ZMAs.This review is expected to offer a constructive reference for the further development and commercialization of AZMBs.
基金supported by the National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22379013 and 22209010)the Beijing Institute of Technology“Xiaomi Young Scholars”program。
文摘Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.
基金sponsored by the National Natural Science Foundation of China(21905221,21805221)the Suzhou Technological innovation of key industries-research and development of key technologies(SGC2021118)。
文摘Free-standing silicon anodes with high proportion of active materials have aroused great attention;however,the mechanical stability and electrochemical performance are severely suppressed.Herein,to resolve the appeal issues,a free-standing anode with a"corrugated paper"shape on micro-scale and a topological crosslinking network on the submicron and nano-scale is designed.Essentially,an integrated three-dimensional electrode structure is constructed based on robust carbon nanotubes network with firmly anchored SiNPs via forming interlocking junctions.In which,the hierarchical interlocking structure is achieved by directional induction of the binder,which ensures well integration during cycling so that significantly enhances mechanical stability as well as electronic and ionic conductivity of electrodes.Benefiting from it,this anode exhibits outsta nding performance under harsh service conditions including high Si loading,ultrahigh areal capacity(33.2 mA h cm^(-2)),and high/low temperatures(-15-60℃),which significantly extends its practical prospect.Furthermore,the optimization mechanism of this electrode is explored to verify the crack-healing and structure-integration maintaining along cycling via a unique self-stabilization process.Thus,from both the fundamental and engineering views,this strategy offers a promising path to produce high-performance free-standing electrodes for flexible device applications especially facing volume effect challenges.
基金supported by the Hunan Chenyu Fuji New Energy Technology Co. Ltd (2022zkhx501)the Hunan Province University Teaching Reform and Research Project (HNJG-20230364)the Ministry of Education’s Industry-University Cooperation and Collaborative Talent Development Program(231106707093309)。
文摘Zn powder anodes have attracted much attention in aqueous Zn ion battery applications due to advantages such as low cost and processability.However,the high-activity Zn powder anode faces problems such as side reactions,hydrogen evolution,and dendrites,which limit the cycling stability of the cell.In this work,the high activity of Zn powder is weakened by introducing low-cost erythritol as a functional additive in the ZnSO_(4) electrolyte to improve the cycle life of the cell.Both theoretical calculations and empirical evidence demonstrate that the incorporation of erythritol alters the coordination sphere of Zn^(2+)and modifies the local molecular architecture of the electrolyte.This modification serves to diminish the reactivity of water molecules,thereby efficaciously suppressing dendrite formation and deleterious ancillary reactions on the zinc powder anode surfaces.Concurrently,erythritol functions as an interfacial cationic captor,enhancing reaction dynamics and facilitating the development of a favorable protective layer throughout the zinc plating/stripping process.Consequently,the symmetric cell paired with an erythritol-containing electrolyte manifests stable cycling performance for an extended duration of 850 h at a current density of 0.288 mA cm^(-2)and areal capacity of 0.144 mAh cm^(-2).Notably,it maintains a cycling life of 400 h even under intensified conditions (2.88 mA cm^(-2)/1.44 mA h cm^(-2)).Furthermore,the constructed Na_(2)V_(6)O_(16)·3H_(2)O full cell illustrated remarkable capacity retention of 155.8 mA h g^(-1)following 800 cycles at a high rate of 5 A g^(-1).
基金supported by the National Key R&D Program of China(2021YFB2400300)Key R&D Program of Hubei Province of China(2020BAB088)+2 种基金National Natural Science Foundation of China(52002277)the Fundamental Research Funds for the Central Universities(2021GCRC001)Guangdong Basic and Applied Basic Reuter Foundation(2021A1515011748).
文摘The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate their useless components(mainly the degraded solid electrolyte interphase,SEI)and reconstruct their damaged structure.Herein,a facile and efficient strategy is proposed to recycle the spent graphite on the basis of the careful investigation of the composition of the cycled graphite anodes and the rational design of the regeneration processes.The regenerated graphite,which is revitalized by calcination treatment and acid leaching,delivers superb rate performance and a high specific capacity of 370 mAh g^(-1)(~99% of its theoretical capacity)after 100 cycles at 0.1 C,superior to the commercial graphite anodes.The improved electrochemical performance could be attributed to unchoked Li^(+) transport channels and enhanced charge transfer reaction due to the effective destruction of the degraded SEI and the full recovery of the damaged structure of the spent graphite.This work clarifies that the electrochemical performance of the regenerated graphite could be deteriorated by even a trace amount of the residual“impurity”and provides a facile method for the efficient regeneration of graphite anodes.
基金financial support from the National Natural Science Foundation of China(52203303)the International Partnership Program of the Chinese Academy of Sciences(321GJHZ2023189FN)+2 种基金the Natural Science Foundation of Guangdong Province(2022A1515010076)the Shenzhen Science and Technology Program(SGDX20211123151002003)the Shenzhen International Cooperation Program(GJHZ20220913142812025)。
文摘Graphite interfaces are an important part of the anode in lithium-ion batteries(LIBs),significantly influencing Li intercalation kinetics.Graphite anodes adopt different stacking sequences depending on the concentration of the intercalated Li ions.In this work,we performed first-principles calculations to comprehensively address the energetics and dynamics of Li intercalation and Li vacancy diffusion near the no n-basal edges of graphite,namely the armchair and zigzag-edges,at high Li concentration.We find that surface effects persist in stage-Ⅱ that bind Li strongly at the edge sites.However,the pronounced effect previously identified at the zigzag edge of pristine graphite is reduced in LiC_(12),penetrating only to the subsurface site,and eventually disappearing in LiC_(6).Consequently,the distinctive surface state at the zigzag edge significantly impacts and restrains the charging rate at the initial lithiation of graphite anodes,whilst diminishes with an increasing degree of lithiation.Longer diffusion time for Li hopping to the bulk site from either the zigzag edge or the armchair edge in LiC_(6) was observed during high state of charge due to charge repulsion.Effectively controlling Li occupation and diffusion kinetics at this stage is also crucial for enhancing the charge rate.
基金National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) [NRF-2021R1A5A1084921]the “Human Resources Program in Energy Technology” of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea [No. 20204010600100]the Materials and Components Technology Development Program of the Ministry of Trade, Industry and Energy (MOTIE, Korea) and Korea Electronics Technology Institute (KETI) [20012224]。
文摘The extreme volume expansion of the silicon(Si) anodes during repeated cycles seriously induces undesirable interfacial side reactions,forming an unstable solid electrolyte interphase(SEI) that degrades the electrode integrity and cycle stability in lithium-ion batteries,limiting their practical applications.Despite considerable efforts to stabilize the SEI through surface modification,challenges persist in the development of high-performance Si anodes that effectively regulate intrinsic SEI properties and simultaneously facilitate electron/ion transport.Here,a highly conductive and organic electrolyte-compatible lamellar p-toluenesulfonic acid-doped polyaniline(pTAP) layer is proposed for constructing a robust artificial SEI on Si nanoparticles to achieve fast charging,lo ng-term cycle lifespan and high areal capacity.The spatially uniform pTAP layer,formed through a facile direct-encapsulation approach assisted by enriched hydrogen bonding,contributes to the effective formation of in situ SEI with an even distribution of the LiF-rich phase in its interlamination spaces.Furthermore,the integrated artificial SEI facilitates isotropic ion/electron transport,increased robustness,and effectively dissipates stress from volume changes.Consequently,a notably high rate performance of 570 mA h g^(-1),even at a substantially high current density of 10 A g^(-1),is achieved with excellent cyclic stability by showing a superior capacity over 1430 mA h g^(-1) at 1 A g^(-1) after 250 cycles and a high areal capacity of ca.2 mA h cm^(-2) at 0.5 C in a full cell system.This study demonstrates that the rational design of conductive polymers with SEI modulation for surface protection has great potential for use in high-energy-density Si anodes.
基金supported by the National Natural Science Foundation of China (52172159)the Postdoctoral Fellowship Program of CPSF (GZB20230631)。
文摘Aqueous zinc metal batteries (AZMBs) are hindered by uncontrolled dendrites and side reactions during commercialization,despite their advantages of safety and high capacity density.Herein,we propose the electrical feedback strategy to restrain the Zn dendrites resulting from the"tip effect"and optimize interfacial Zn^(2+)distribution to accelerate electrodeposition kinetics by using the lithium niobate (LNO) layer.Specifically,at the bumps of the zinc anode,the ferroelectric LNO is polarized by the locally strong electric field,which in turn counteracts the"tip effect".In this way,the dynamic polarization of LNO can repair the uneven tip electric field to achieve uniform and flat zinc deposition.In addition,owing to the interaction between Nb and Zn^(2+),a higher concentration of Zn^(2+)near the zincophilic LNO@Zn surface is obtained for the rapid electrochemical reaction kinetics of plating.Considering the aforementioned advantages,the LNO@Zn anode harvests stable cycling over 1200 h at 10 mA cm^(-2)with a superior cumulative capacity of 5800 mAh cm^(-2).Assembled with the a-MnO_(2) cathode,the full cell using LNO@Zn anode exhibits the slower capacity decay (0.054%per cycle) during 1000 cycles.This strategy provides a perspective for stabilizing zinc metal anodes through dynamic electrical response and interfacial ion redistribution effect.
基金financially supported by the National Key R&D Program of China, Grant No. 2021YFB2401800
文摘Lithium metal is considered as the ultimate anode material for the next generation of high-energy density batteries.However,non-uniform lithium dendrite growth,serious electrolyte consumption,and significant volume changes during lithium deposition/stripping processes lead to sustained accumulation of inactive lithium and poor cycling reversibility.Quantifying the formation and evolution of inactive lithium under different conditions and fully evaluating the complex failure modes are the key issues in this challenging field.This article comprehensively reviews recent research progress on the quantification of formation and evolution of inactive lithium detected by different quantitative techniques in rechargeable lithium metal batteries.The key research challenges such as failure mechanism,modification strategies and operando characterization of lithium metal anodes are systematically summarized and prospected.This review provides a new angle of view to understand failure mechanism of lithium metal anodes and inspiration and guidance for the future development of rechargeable lithium metal batteries.
