Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)L...Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)LixSn combined with an inorganic-rich@polymer dual-layer structure was constructed on a Cu current collector,prepared via a galvanostatic process using a dual-lithium salt electrolyte in a Cu||Cu configuration.The polymer outer layer,initiated by LixSn,reinforces the solid electrolyte interphase(SEI),providing mechanical robustness and enabling stable cycling in an ether-based electrolyte.Furthermore,the Sn and LixSn particle sizes can be effectively tuned by adjusting the galvanostatic discharge current.The nanosized LixSn significantly lowers the nucleation overpotential and creates abundant lithiophilic nucleation sites,resulting in uniform,dense Li plating/stripping.The modified Cu collector demonstrates superior performance in ether-based electrolytes,achieving over 92%capacity retention after 100 cycles at a current density of 1.5 mA cm^(−2)and an area capacity of 1.1 mAh cm^(−2).This work provides a simple,eco-friendly,and scalable approach for fabricating high-performance anode-free current collectors for AFLMBs.展开更多
Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrol...Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.展开更多
To meet the demand for enhanced energy density and improved safety in batteries,anode-free aqueous zinc metal batteries(AF-AZMBs)have garnered significant research interest and attention.Compared with conventional aqu...To meet the demand for enhanced energy density and improved safety in batteries,anode-free aqueous zinc metal batteries(AF-AZMBs)have garnered significant research interest and attention.Compared with conventional aqueous Zn batteries,AF-AZMBs provide higher theoretical energy density,a more simplified structural design,and improved cost-effectiveness.However,AF-AZMBs are confronted with severe capacity degradation and lifespan reduction due to the absence of an excess zinc inventory.In recent years,extensive research efforts have been devoted to addressing these challenges,resulting in significant advancements.Therefore,there is highly warranted for a comprehensive discussion on AF-AZMBs.Herein,this review provides a thorough analysis and in-depth investigation of recent developments in AF-AZMBs from the perspectives of current collectors,electrolytes,and cathodes.Specifically,the working mechanisms and advantageous features of AF-AZMBs are summarized.The major scientific issues affecting capacity degradation and lifespan reduction are discussed,including inhomogeneous Zn deposition/stripping kinetics,unstable SEI layer,and irreversible cathode material loss.Furthermore,the corresponding strategies to address these issues are highlighted,such as anodic current collector design,electrolyte engineering,and cathodic modification.Finally,several promising directions are explored for the future advancement of AF-AZMBs,including developing high-performance Zn-rich cathodes,regulating solid-state electrolytes,and designing dual-electrode-free zinc-metal batteries.Additionally,exploring advanced characterization and analysis techniques and optimizing pouch cells under practical operating conditions are also mentioned,highlighting the urgent need for further research to address existing bottlenecks.展开更多
Metal foils have emerged as one of the promising materials for anode-free batteries due to their high energy density and scalability in production.The unclear lithium plating/stripping kinetics of metal foil current c...Metal foils have emerged as one of the promising materials for anode-free batteries due to their high energy density and scalability in production.The unclear lithium plating/stripping kinetics of metal foil current collectors in anode-free batteries was addressed by using the non-destructive distribution of relaxation times(DRT)analysis to systematically investigate the lithium transport behavior of 14 metal foils and its correlation with electrochemical performance.By integrating energy-dispersive spectro scopy(EDS),cyclic voltammetry(CV),and galvanostatic testing,the exceptional properties of indium(In),tin(Sn),and silver(Ag)were revealed:the Li-In alloying reaction exhibits high reversibility,Li-Sn alloys demonstrate outstanding cycling stability,and the Li-Ag solid-solution mechanism provides an ideal lithium deposition interface on the silver substrate.The DRT separates the polarization internal resistance of lithium ions passing through the SEI layer(R_(sei),τ2)and the polarization internal resistance of lithium ions undergoing charge transfer reaction at the electrolyte/electrode interface(R_(ct),τ3)by decoupling the electrochemical impedance spectroscopy(EIS).For the first time,the correlation betweenτ2,τ3,and the cycle life/Coulombic efficiency of alloy/solid-solution metals was established,while non-alloy metals are not suitable for this method due to differences in lithium deposition mechanisms.This study not only illuminates the structure-property relationship governing the lithium kinetics of metal foil electrodes but also provides a novel non-destructive analytical strategy and theoretical guidance for the rational design of stable anodes in high-energy-density batteries,facilitating the efficient screening and optimization of anode-free battery.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
The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commerci...The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.展开更多
Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herei...Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herein,we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs.The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes.Consequently,the alloy network-modulated zinc deposition interface realizes high coulombic efficiency of 99.2%and high stability.As proof,Zn//Zn symmetric cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 m A/cm^(2)and 1200 h at 5 m A/cm^(2),significantly superior to Zn//Zn symmetric cells with unmodified zinc deposition interface(whose operation lifetime is shorter than 50 h),and meanwhile,Zn3V3O8cathodebased ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes.As expected,the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8cathodes to deliver superior cycling stability,better than most currently-reported anode-free ZIBs.This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.展开更多
Anode-free Li-metal batteries are of significant interest to energy storage industries due to their intrinsically high energy.However,the accumulative Li dendrites and dead Li continuously consume active Li during cyc...Anode-free Li-metal batteries are of significant interest to energy storage industries due to their intrinsically high energy.However,the accumulative Li dendrites and dead Li continuously consume active Li during cycling.That results in a short lifetime and low Coulombic efficiency of anode-free Li-metal batteries.Introducing effective electrolyte additives can improve the Li deposition homogeneity and solid electrolyte interphase(SEI)stability for anode-free Li-metal batteries.Herein,we reveal that introducing dual additives,composed of LiAsF6 and fluoroethylene carbonate,into a low-cost commercial carbonate electrolyte will boost the cycle life and average Coulombic efficiency of NMC‖Cu anode-free Li-metal batteries.The NMC‖Cu anode-free Li-metal batteries with the dual additives exhibit a capacity retention of about 75%after 50 cycles,much higher than those with bare electrolytes(35%).The average Coulombic efficiency of the NMC‖Cu anode-free Li-metal batteries with additives can maintain 98.3%over 100 cycles.In contrast,the average Coulombic efficiency without additives rapidly decline to 97%after only 50 cycles.In situ Raman measurements reveal that the prepared dual additives facilitate denser and smoother Li morphology during Li deposition.The dual additives significantly suppress the Li dendrite growth,enabling stable SEI formation on anode and cathode surfaces.Our results provide a broad view of developing low-cost and high-effective functional electrolytes for high-energy and long-life anode-free Li-metal batteries.展开更多
Anode-free all-solid-state batteries(AFASSBs), composed of a fully lithiated cathode and a bare current collector(CC) that eliminates excess lithium, can maximize the energy density(because of a compact cell configura...Anode-free all-solid-state batteries(AFASSBs), composed of a fully lithiated cathode and a bare current collector(CC) that eliminates excess lithium, can maximize the energy density(because of a compact cell configuration) and improve the safety of solid-state systems. Although significant progress has been made by modifying CCs in liquid-based anode-free batteries, the role of CCs and the mechanism of Li formation on CCs in AFASSBs are still unexplored. Here, we systematically investigate the effect of the surface roughness of the CCs on the Li plating/stripping behavior in AFASSBs. The results show that the moderately roughened CC substantially improves the Coulombic efficiency and cycle stability of AFASSBs owing to the increased contact points between the solid electrolyte and the roughened CC. In contrast, the excessively roughened CC deteriorates the performance owing to the contact loss.Moreover, an ex situ interface analysis reveals that the roughened surface of the CC could suppress the interfacial degradation during the Li ion extraction from a sulfide solid electrolyte to a CC. This provides an indication to the origin that hinders the electrochemical performance of AFASSBs. These findings show the potential for the application of surface-engineered CCs in AFASSBs and provide guidelines for designing advanced CCs.展开更多
The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach t...The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach to the in-situ construction of high-quality SEI by applying synergistic additives of Li NO_(3)and ethylene sulfite(ES)in the electrolyte.The obtained SEI exhibits a high average Young’s modulus(9.02GPa)and exchanging current density(4.59 mA cm^(-2)),which are 3.0 and 1.2 times as large as those using the sole additive of LiNO_(3),respectively.With this improved SEI,Li-dendrite growth and side reactions are effectively suppressed,leading to an ultra-high Coulombic efficiency(CE)of 99.7%for Li plating and stripping.When applying this improved electrolyte in full cells,it achieves a high capacity retention of 89.7%for over 150 cycles in a LiFePO_(4)||Li battery(~12 mg cm^(-2)cathode,50μm Li)and of 44.5%over 100 cycles in a LiFePO_(4)||Cu anode-free battery.展开更多
Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs ...Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs suffer from an inherently finite Li reservoir and exhibit poor cycle stability,low Coulombic efficiency(CE)and severe dendrite growth.In this work,polydiallyl lithium disulfide(PDS-Li)was successfully synthesized and coated on Cu current collector by electrochemical polymerization.The PDS-Li acts as an additional lithium resource to compensate for the irreversible loss of lithium during cycling.In addition,the special structure and lithiophilicity of PDS-Li contribute to lower nucleation overpotential and uniform lithium deposition.When coupled with Li-rich manganese-based(LRM)cathode of Li1.2Mn0.54Ni0.13Co0.13O2,the anode-free full cell exhibits significantly improved cycle stability over 100 cycles and capacity retention of 63.3%and 57%after 80 and 100 cycles,respectively.We believe that PDS-Li can be used to ensure stable cycling performance and high-energy-density in AFLMBs.展开更多
Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay ...Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay in AF-SSLBs,either determined by dead Li or solid electrolyte interface(SEI),limits the proposal of effective strategies to prolong cycling life.To clarify the underlying mechanism,herein,the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance(ss-NMR)technology in a typical LiPF6-based polymer electrolyte.The results show that the initial capacity loss is attributed to the formation of SEI,while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm^(−2)cycle−1.To reduce the active Li loss,the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior,which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds,respectively.As a result,the initial Coulombic efficiency(ICE)and stable CE increase by 15.1%and 15.3%in Li-Cu cells,which guides the rational design of high-performance AF-SSLBs.展开更多
Lithium metal batteries(LMBs)and anode-free LMBs(AFLMBs)present a solution to the need for batteries with a significantly superior theoretical energy density.However,their adoption is hindered by low Coulombic efficie...Lithium metal batteries(LMBs)and anode-free LMBs(AFLMBs)present a solution to the need for batteries with a significantly superior theoretical energy density.However,their adoption is hindered by low Coulombic efficiency(CE)and rapid capacity fading,primarily due to the formation of unstable solid electrolyte interphase(SEI)layer and Li dendrite growth as a result of uneven Li plating.Here,we report on the use of a stoichiometric Ti_(3)C_(2)T_(x)(S-Ti_(3)C_(2)T_(x))MXene coating on the copper current collector to enhance the cyclic stability of an anode-free lithium metal battery.The S-Ti_(3)C_(2)T_(x)coating provides abundant nucleation sites,thereby lowering the overpotential for Li nucleation,and promoting uniform Li plating.Additionally,the fluorine(-F)termination of S-Ti_(3)C_(2)T_(x)participates in the SEI formation,producing a LiF-rich SEI layer,vital for stabilizing the SEI and improving cycle life.Batteries equipped with S-Ti_(3)C_(2)T_(x)@Cu current collectors displayed reduced Li consumption during stable SEI formation,resulting in a significant decrease in capacity loss.AFLMBs with S-Ti_(3)C_(2)T_(x)@Cu current collectors achieved a high initial capacity density of 4.2 mAh cm^(-2),70.9%capacity retention after 50 cycles,and an average CE of 98.19%in 100 cycles.This innovative application of MXenes in the energy field offers a promising strategy to enhance the performance of AFLMBs and could potentially accelerate their commercial adoption.展开更多
Anode-free all-solid-state batteries(AF-ASSBs)have received significant attention as a next-generation battery system due to their high energy density and safety.However,this system still faces challenges,such as poor...Anode-free all-solid-state batteries(AF-ASSBs)have received significant attention as a next-generation battery system due to their high energy density and safety.However,this system still faces challenges,such as poor Coulombic efficiency and short-circuiting caused by Li dendrite growth.In this study,the AF-ASSBs are demonstrated with reliable and robust electrochemical properties by employing Cu-Sn nanotube(NT)thin layer(~1μm)on the Cu current collector for regulating Li electrodeposition.Li_(x)Sn phases with high Li-ion diffusivity in the lithiated Cu-Sn NT layer enable facile Li diffusion along with its one-dimensional hollow geometry.The unique structure,in which Li electrodeposition takes place between the Cu-Sn NT layer and the current collector by the Coble creep mechanism,improves cell durability by preventing solid electrolyte(SE)decomposition and Li dendrite growth.Furthermore,the large surface area of the Cu-Sn NT layer ensures close contact with the SE layer,leading to a reduced lithiation overpotential compared to that of a flat Cu-Sn layer.The Cu-Sn NT layer also maintains its structural integrity owing to its high mechanical properties and porous nature,which could further alleviate the mechanical stress.The LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM)|SE|Cu-Sn NT@Cu cell with a practical capacity of 2.9 mAh cm^(−2) exhibits 83.8%cycle retention after 150 cycles and an average Coulombic efficiency of 99.85%at room temperature.It also demonstrates a critical current density 4.5 times higher compared to the NCM|SE|Cu cell.展开更多
Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindere...Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindered the development of AFLMBs.Herein,for the first time,we establish the correlation between the electrochemical structural connectivity of Li deposits and the loss pathways of active Li.Li nucleation behavior is optimized via the self-driven formation of hydroxyl-modified lithiophilic Cu nanoparticles from CuOHF.Dense columnar Li stacks with stable bulk-phase electronic pathways and interfacial kinetic structures are achieved through a high-density spatial multidimensional nucleation mechanism,which restricts the quasi-linear accumulation of irreversible Li to only 0.003 mg per cycle.Meanwhile,the regulated Li growth process exhibits homogeneous and rapid interfacial mass transfer with extremely low concentration polarization.The anode-free LiFePO_(4) pouch cell retains 61.4%of its initial reversible capacity after 100 cycles.Insights into active Li utilization derived from this work will accelerate the development of high-performance AFLMBs.展开更多
Anode-free sodium-ion batteries(AFSIBs)achieve energy storage by completely eliminating traditional anode active materials and relying solely on the reversible plating and stripping of sodium from the anode source ont...Anode-free sodium-ion batteries(AFSIBs)achieve energy storage by completely eliminating traditional anode active materials and relying solely on the reversible plating and stripping of sodium from the anode source onto the current collector surface.This approach fundamentally addresses the limitations of energy density and safety inherent in conventional sodium batteries,positioning it as a promising candidate for high-energy“super-lithium”electrochemical storage technology.However,this innovative design also places unprecedentedly stringent demands on the current collector,making it a critical component in determining cell performance.This review systematically outlines the prevailing methodologies and research progress on modifying collectors for AFSIBs,with a focus on material sodophilicity engineering and structural modulation.By comprehensively reviewing the process of different sodium-friendly material modifications,interfacial functional modulation,porous structure configuration,and gradient engineering on the cell performance,the essential elements for enhancing the electrochemical performance of the current collector are outlined.Building on this,the paper discusses the challenges and opportunities in this field and suggests new research directions for developing high-performance AFSIBs.展开更多
The emerging Li//H_(2)battery is a promising candidate for energy storage systems to meet the demand for the worldwide transition to clean and sustainable energy.To leverage the H_(2)electrode’s advantages and decrea...The emerging Li//H_(2)battery is a promising candidate for energy storage systems to meet the demand for the worldwide transition to clean and sustainable energy.To leverage the H_(2)electrode’s advantages and decrease costs,a high areal capacity anode-free Li anode is ideal.Here we propose using a pseudocapacitive Cu(PC-Cu)substrate to accommodate the high areal capacity anode-free Li//H_(2)battery(AFLHB).The PC-Cu substrate exhibits intense electrochemical adsorption and intrinsic strong chemisorption to Li,which leads to aggregation of the Li salts so as to induce enrichment of interfacial lithiophilicity.This aids uniform Li nucleation,anion concentration,and robust SEI formation.The AFLHB displays stable cycling at a high areal capacity of 5 mAh cm^(-2)with an average coulombic efficiency of 98.80%for over 350 h.Notably,the PC-Cu substrate enables superdense Li deposition with only 7%thickness exceeding the theoretical value.Moreover,the modified substrate enables a reversible Li stripping/plating at an ultralarge areal capacity of 20 mAh cm^(-2).This work presents an interfacial lithiophilicity enrichment strategy to stabilize the cycling performance of high areal capacity AFLHB and advances this novel battery system one step closer to practical application.展开更多
Aqueous Zn batteries(AZBs)suffer from poor Zn anode reversibility.To address this issue,excess Zn foil is often utilized to prolong the cycle life,but it reduces the actual battery energy density.In this work,we use m...Aqueous Zn batteries(AZBs)suffer from poor Zn anode reversibility.To address this issue,excess Zn foil is often utilized to prolong the cycle life,but it reduces the actual battery energy density.In this work,we use methylurea molecules to in situ form a solid electrolyte interphase(SEI)layer on the Zn anode,achieving reversible Zn plating/stripping with a maximal Coulombic efficiency(CE)of 99.99%and extending the anode's lifespan to 4500 cycles.Leveraging this highly reversible chemistry,we fabricate and test various anode-free Zn batteries.An anode-free Zn-AC cell exhibits stable cycling for exceeding 5000 cycles,an anode-free Zn-I_(2) battery with high specific capacities achieves a stable cycle life of 1000 cycles,and an anode-free Zn-Br_(2) battery with a high areal capacity of 4 mAh cm^(-2) demonstrates a stable cycle life of 450 cycles.Characterization of the SEI using TEM and DFT calculations reveal the formation mechanisms of the ZnCO_(3)-and ZnS-rich amorphous SEI layer.These results indicate that the design of desirable SEI compositions could pave the way for developing low-cost,high-performance anode-free AZBs.展开更多
Anode-free sodium batteries(AFSBs)have attracted increasing attention for their high energy density.However,they suffer from rapid capacity decline resulting from sodium dendrite growth at the sodium/host interface an...Anode-free sodium batteries(AFSBs)have attracted increasing attention for their high energy density.However,they suffer from rapid capacity decline resulting from sodium dendrite growth at the sodium/host interface and irreversible side reactions at the electrolyte/sodium interface.Herein,a GaInSn-coated Cu foil(G-Cu),prepared by a simple brush coating method,was applied as the sodiophilic current collector to regulate sodium nucleation behavior.In addition,a nonexpendable functional electrolyte additive,hexamethyldisiloxane(HMDSO),was introduced,which could be absorbed on the sodium surface and serve as a protective layer against corrosion side reactions at the electrolyte/sodium interface.It is interesting to note that this additive barely participated in forming the solid electrolyte interphase.The synergetic effects of sodiophilic interface design and electrolyte regulation enable reversible sodium plating and stripping.Ultimately,the AFSB assembled using G-Cu and HMDSO electrolyte with a highly loaded Na_(3)V_(2)(PO_(4))_(3) cathode(≈12.5 mg cm^(−2))delivers a discharge capacity of 84.5 mAh g^(−1) after 200 cycles with a high capacity retention of 87.6%,significantly extending its operation lifespan.展开更多
The zinc(Zn)batteries have challenges include uncontrollable dendritic growth,unreasonable negative to positive ratio and limited areal capacity.This highlight presents the latest development to resolve the uncontroll...The zinc(Zn)batteries have challenges include uncontrollable dendritic growth,unreasonable negative to positive ratio and limited areal capacity.This highlight presents the latest development to resolve the uncontrollable Zn dendrite formation at high areal capacities of 200 mAh·cm^(-2) through a two-dimensional metal/metal-Zn alloy heterostructured interface.The anode-free Zn batteries with an attractive and practical pouch cell energy density of 62 Wh·kg^(-1) enlighten an arena towards their commercialization.展开更多
基金supported by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIT)(No. 2020R1A5A1019131)supported by a Korea Institute of Energy Technology Evaluation and Planning (KETEP)grant funded by the Korean government (MOTIE)(RS-2022-KP002703, Sector coupling energy industry advancement manpower training program)+1 种基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE) of the Republic of Korea (RS-2024-00469587)
文摘Anode-free lithium-metal batteries(AFLMBs)offer high energy density.However,lithium dendrite growth and interfacial instability remain critical obstacles to their commercialization.Here,lithiophilic nanosized(∼5 nm)LixSn combined with an inorganic-rich@polymer dual-layer structure was constructed on a Cu current collector,prepared via a galvanostatic process using a dual-lithium salt electrolyte in a Cu||Cu configuration.The polymer outer layer,initiated by LixSn,reinforces the solid electrolyte interphase(SEI),providing mechanical robustness and enabling stable cycling in an ether-based electrolyte.Furthermore,the Sn and LixSn particle sizes can be effectively tuned by adjusting the galvanostatic discharge current.The nanosized LixSn significantly lowers the nucleation overpotential and creates abundant lithiophilic nucleation sites,resulting in uniform,dense Li plating/stripping.The modified Cu collector demonstrates superior performance in ether-based electrolytes,achieving over 92%capacity retention after 100 cycles at a current density of 1.5 mA cm^(−2)and an area capacity of 1.1 mAh cm^(−2).This work provides a simple,eco-friendly,and scalable approach for fabricating high-performance anode-free current collectors for AFLMBs.
基金supports by Central South University Innovation-Driven Research Programme(2023CXQD038)the Fundamental Research Funds for the Central Universities of Central South University(2025ZZTS0089)supported by the High Performance Computing Center of Central South University.
文摘Anode-free sodium metal batteries(AFSMBs)have gained attention as next-generation storage systems with high energy density and cost-effectiveness.However,non-uniform sodium(Na)deposition and an unsteady solid electrolyte interphase(SEI)lead to dendrite-related issues and severe irreversible Na^(+)plating/stripping,greatly aggravating their cycle deterioration.In this study,we effectively modified the 3D current collector's electronic structure by introducing Zn-N_(x)active sites(Zn-CNF),which enhances lateral Na^(+)diffusion and the Na planar growth,enabling uniform deep Na deposition at an exceptionally high capacity of 10 mA h cm^(-2).Furthermore,the Zn-N_(x)bonds enhance the adsorption capacity of PF6and contribute to forming a stable inorganic-rich SEI layer.Consequently,Zn-CNF with the electronic structure regulation endows an ultra-low nucleation overpotential(8 mV)and ultra-high Coulombic efficiency of 99.94%over 1,600 cycles.Symmetric cells demonstrate stable Na^(+)plating/stripping behavior for more than 4,400 h at 1 mA cm^(-2).Moreover,under high cathode loading(7.97 mg cm^(-2)),the AFSMBs achieve a high energy density of 374 W h kg^(-1)and retain a high discharge capacity of 82.49 mA h g^(-1)with a capacity retention of 80.4%after 120 cycles.This work proposes a viable strategy to achieving high-energy-density AFSMBs.
基金supported by the National Natural Science Foundation of China(22209006)the Fundamental Research Funds for the Central Universities(buctrc202307)the Natural Science Foundation of Shandong Province(ZR2022QE009)。
文摘To meet the demand for enhanced energy density and improved safety in batteries,anode-free aqueous zinc metal batteries(AF-AZMBs)have garnered significant research interest and attention.Compared with conventional aqueous Zn batteries,AF-AZMBs provide higher theoretical energy density,a more simplified structural design,and improved cost-effectiveness.However,AF-AZMBs are confronted with severe capacity degradation and lifespan reduction due to the absence of an excess zinc inventory.In recent years,extensive research efforts have been devoted to addressing these challenges,resulting in significant advancements.Therefore,there is highly warranted for a comprehensive discussion on AF-AZMBs.Herein,this review provides a thorough analysis and in-depth investigation of recent developments in AF-AZMBs from the perspectives of current collectors,electrolytes,and cathodes.Specifically,the working mechanisms and advantageous features of AF-AZMBs are summarized.The major scientific issues affecting capacity degradation and lifespan reduction are discussed,including inhomogeneous Zn deposition/stripping kinetics,unstable SEI layer,and irreversible cathode material loss.Furthermore,the corresponding strategies to address these issues are highlighted,such as anodic current collector design,electrolyte engineering,and cathodic modification.Finally,several promising directions are explored for the future advancement of AF-AZMBs,including developing high-performance Zn-rich cathodes,regulating solid-state electrolytes,and designing dual-electrode-free zinc-metal batteries.Additionally,exploring advanced characterization and analysis techniques and optimizing pouch cells under practical operating conditions are also mentioned,highlighting the urgent need for further research to address existing bottlenecks.
基金supported by the Quzhou Science and Technology Bureau Project(2023D023,2023D030,2023D002,and2024D028)the Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(LZY23B030002)+3 种基金the Shijiazhuang Shangtai Technology Co.,Ltd.Hebei Provincial Department of Science and Technology(24291101Z)the International Cooperation Projects of Sichuan Provincial Department of Science and Technology(2021YFH0126)the Sichuan Provincial Science and Technology Department's key research project(2023YFG0203)。
文摘Metal foils have emerged as one of the promising materials for anode-free batteries due to their high energy density and scalability in production.The unclear lithium plating/stripping kinetics of metal foil current collectors in anode-free batteries was addressed by using the non-destructive distribution of relaxation times(DRT)analysis to systematically investigate the lithium transport behavior of 14 metal foils and its correlation with electrochemical performance.By integrating energy-dispersive spectro scopy(EDS),cyclic voltammetry(CV),and galvanostatic testing,the exceptional properties of indium(In),tin(Sn),and silver(Ag)were revealed:the Li-In alloying reaction exhibits high reversibility,Li-Sn alloys demonstrate outstanding cycling stability,and the Li-Ag solid-solution mechanism provides an ideal lithium deposition interface on the silver substrate.The DRT separates the polarization internal resistance of lithium ions passing through the SEI layer(R_(sei),τ2)and the polarization internal resistance of lithium ions undergoing charge transfer reaction at the electrolyte/electrode interface(R_(ct),τ3)by decoupling the electrochemical impedance spectroscopy(EIS).For the first time,the correlation betweenτ2,τ3,and the cycle life/Coulombic efficiency of alloy/solid-solution metals was established,while non-alloy metals are not suitable for this method due to differences in lithium deposition mechanisms.This study not only illuminates the structure-property relationship governing the lithium kinetics of metal foil electrodes but also provides a novel non-destructive analytical strategy and theoretical guidance for the rational design of stable anodes in high-energy-density batteries,facilitating the efficient screening and optimization of anode-free battery.
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This work was financially supported by Shaanxi Yanchang Petroleum CO.,Ltd(18529)Yiwu Research Institute of Fudan University(21557),the National Science Foundation of China(22075048)the Shanghai International Collaboration Research Project(19520713900).
文摘The anode-free design is a promising strategy to increase the energy density of aqueous Zn metal batteries(AZMBs).However,the scarcity of Zn-rich cathodes and the rapid loss of limited Zn greatly hinder their commercial applications.To address these issues,a novel anode-free Zniodine battery(AFZIB)was designed via a simple,low-cost and scalable approach.Iodine plays bifunctional roles in improving the AFZIB overall performance:enabling high-performance Zn-rich cathode and modulating Zn deposition behavior.On the cathode side,the ZnI_(2) serves as Zn-rich cathode material.The graphene/polyvinyl pyrrolidone heterostructure was employed as an efficient host for ZnI_(2) to enhance electron conductivity and suppress the shuttle effect of iodine species.On the anode side,trace I_(3)^(−) additive in the electrolyte creates surface reconstruction on the commercial Cu foil.The in situ formed zincophilic Cu nanocluster allows ultralow-overpotential and uniform Zn deposition and superior reversibility(average coulombic efficiency>99.91% over 7,000 cycles).Based on such a configuration,AFZIB exhibits significantly increased energy density(162 Wh kg^(−1)) and durable cycle stability(63.8% capacity retention after 200 cycles)under practical application conditions.Considering the low cost and simple preparation methods of the electrode materials,this work paves the way for the practical application of AZMBs.
基金financial support provided by the National Natural Science Foundation of China(52002149)the Guangdong Basic and Applied Basic Research Foundation(2020A1515111202)+1 种基金the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds)(pdjh2022a0056)the Fundamental Research Funds for the Central Universities。
文摘Newly-proposed anode-free zinc-ion batteries(ZIBs)are promising to remarkably enhance the energy density of ZIBs,but are restricted by the unfavorable zinc deposition interface that causes poor cycling stability.Herein,we report a Cu-Zn alloy network-modulated zinc deposition interface to achieve stable anode-free ZIBs.The alloy network can not only stabilize the zinc deposition interface by suppressing 2D diffusion and corrosion reactions but also enhance zinc plating/stripping kinetics by accelerating zinc desolvation and nucleation processes.Consequently,the alloy network-modulated zinc deposition interface realizes high coulombic efficiency of 99.2%and high stability.As proof,Zn//Zn symmetric cells with the alloy network-modulated zinc deposition interface present long operation lifetimes of 1900 h at 1 m A/cm^(2)and 1200 h at 5 m A/cm^(2),significantly superior to Zn//Zn symmetric cells with unmodified zinc deposition interface(whose operation lifetime is shorter than 50 h),and meanwhile,Zn3V3O8cathodebased ZIBs with the alloy network-modified zinc anodes show notably enhanced rate capability and cycling performance than ZIBs with bare zinc anodes.As expected,the alloy network-modulated zinc deposition interface enables anode-free ZIBs with Zn3V3O8cathodes to deliver superior cycling stability,better than most currently-reported anode-free ZIBs.This work provides new thinking in constructing high-performance anode-free ZIBs and promotes the development of ZIBs.
基金fellowship support from the China Scholarship Council
文摘Anode-free Li-metal batteries are of significant interest to energy storage industries due to their intrinsically high energy.However,the accumulative Li dendrites and dead Li continuously consume active Li during cycling.That results in a short lifetime and low Coulombic efficiency of anode-free Li-metal batteries.Introducing effective electrolyte additives can improve the Li deposition homogeneity and solid electrolyte interphase(SEI)stability for anode-free Li-metal batteries.Herein,we reveal that introducing dual additives,composed of LiAsF6 and fluoroethylene carbonate,into a low-cost commercial carbonate electrolyte will boost the cycle life and average Coulombic efficiency of NMC‖Cu anode-free Li-metal batteries.The NMC‖Cu anode-free Li-metal batteries with the dual additives exhibit a capacity retention of about 75%after 50 cycles,much higher than those with bare electrolytes(35%).The average Coulombic efficiency of the NMC‖Cu anode-free Li-metal batteries with additives can maintain 98.3%over 100 cycles.In contrast,the average Coulombic efficiency without additives rapidly decline to 97%after only 50 cycles.In situ Raman measurements reveal that the prepared dual additives facilitate denser and smoother Li morphology during Li deposition.The dual additives significantly suppress the Li dendrite growth,enabling stable SEI formation on anode and cathode surfaces.Our results provide a broad view of developing low-cost and high-effective functional electrolytes for high-energy and long-life anode-free Li-metal batteries.
基金supported by the Institutional Program(2E31852)of Korea Institute of Science and Technology(KIST)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT,2022R1C1C1006019)。
文摘Anode-free all-solid-state batteries(AFASSBs), composed of a fully lithiated cathode and a bare current collector(CC) that eliminates excess lithium, can maximize the energy density(because of a compact cell configuration) and improve the safety of solid-state systems. Although significant progress has been made by modifying CCs in liquid-based anode-free batteries, the role of CCs and the mechanism of Li formation on CCs in AFASSBs are still unexplored. Here, we systematically investigate the effect of the surface roughness of the CCs on the Li plating/stripping behavior in AFASSBs. The results show that the moderately roughened CC substantially improves the Coulombic efficiency and cycle stability of AFASSBs owing to the increased contact points between the solid electrolyte and the roughened CC. In contrast, the excessively roughened CC deteriorates the performance owing to the contact loss.Moreover, an ex situ interface analysis reveals that the roughened surface of the CC could suppress the interfacial degradation during the Li ion extraction from a sulfide solid electrolyte to a CC. This provides an indication to the origin that hinders the electrochemical performance of AFASSBs. These findings show the potential for the application of surface-engineered CCs in AFASSBs and provide guidelines for designing advanced CCs.
基金supported by the National Natural Science Foundation of China(21975207,52202303)the Westlake Education Foundation,and the Zhejiang Provincial Natural Science Foundation of China(LQ21B030006)。
文摘The solid electrolyte interphase(SEI)with strong mechanical strength and high ion conductivity is highly desired for Li metal batteries,especially for harsh anode-free batteries.Herein,we report a pragmatic approach to the in-situ construction of high-quality SEI by applying synergistic additives of Li NO_(3)and ethylene sulfite(ES)in the electrolyte.The obtained SEI exhibits a high average Young’s modulus(9.02GPa)and exchanging current density(4.59 mA cm^(-2)),which are 3.0 and 1.2 times as large as those using the sole additive of LiNO_(3),respectively.With this improved SEI,Li-dendrite growth and side reactions are effectively suppressed,leading to an ultra-high Coulombic efficiency(CE)of 99.7%for Li plating and stripping.When applying this improved electrolyte in full cells,it achieves a high capacity retention of 89.7%for over 150 cycles in a LiFePO_(4)||Li battery(~12 mg cm^(-2)cathode,50μm Li)and of 44.5%over 100 cycles in a LiFePO_(4)||Cu anode-free battery.
基金financially supported by the National Natural Science Foundations of China(Nos.52071226,51872193 and U21A20332)the Natural Science Foundations of Jiangsu Province(Nos.BK20181168,BK20201171 and BK20220061)+2 种基金the Key R&D Project funded by Department of Science and Technology of Jiangsu Province(No.BE2020003-3)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.19KJA210004)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs suffer from an inherently finite Li reservoir and exhibit poor cycle stability,low Coulombic efficiency(CE)and severe dendrite growth.In this work,polydiallyl lithium disulfide(PDS-Li)was successfully synthesized and coated on Cu current collector by electrochemical polymerization.The PDS-Li acts as an additional lithium resource to compensate for the irreversible loss of lithium during cycling.In addition,the special structure and lithiophilicity of PDS-Li contribute to lower nucleation overpotential and uniform lithium deposition.When coupled with Li-rich manganese-based(LRM)cathode of Li1.2Mn0.54Ni0.13Co0.13O2,the anode-free full cell exhibits significantly improved cycle stability over 100 cycles and capacity retention of 63.3%and 57%after 80 and 100 cycles,respectively.We believe that PDS-Li can be used to ensure stable cycling performance and high-energy-density in AFLMBs.
基金supported by the CAS Project of Young Scientists in Basic Research(YSBR-058)the National Natural Science Foundation of China(22279135)+2 种基金the Outstanding Youth Foundation of Liaoning Province(2023JH3/10200019)the Dalian Science and Technology Innovation Fund(2023JJ11CG004)the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy(YIICE E411010316)。
文摘Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay in AF-SSLBs,either determined by dead Li or solid electrolyte interface(SEI),limits the proposal of effective strategies to prolong cycling life.To clarify the underlying mechanism,herein,the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance(ss-NMR)technology in a typical LiPF6-based polymer electrolyte.The results show that the initial capacity loss is attributed to the formation of SEI,while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm^(−2)cycle−1.To reduce the active Li loss,the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior,which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds,respectively.As a result,the initial Coulombic efficiency(ICE)and stable CE increase by 15.1%and 15.3%in Li-Cu cells,which guides the rational design of high-performance AF-SSLBs.
基金supported by the Creative Research Initiative Program(2015R1A3A2028975)funded by the National Research Foundation of Korea(NRF)+2 种基金supported by LG energy solution-KAIST Frontier Research Laboratory(2022)the National Research Foundation of Korea(NRF)grants(MSIT,NRF-2021M3H4A1A03047333)supported(funded)by the Semiconductor-Secondary Battery Interfacing Platform Technology Development Project of NNFC
文摘Lithium metal batteries(LMBs)and anode-free LMBs(AFLMBs)present a solution to the need for batteries with a significantly superior theoretical energy density.However,their adoption is hindered by low Coulombic efficiency(CE)and rapid capacity fading,primarily due to the formation of unstable solid electrolyte interphase(SEI)layer and Li dendrite growth as a result of uneven Li plating.Here,we report on the use of a stoichiometric Ti_(3)C_(2)T_(x)(S-Ti_(3)C_(2)T_(x))MXene coating on the copper current collector to enhance the cyclic stability of an anode-free lithium metal battery.The S-Ti_(3)C_(2)T_(x)coating provides abundant nucleation sites,thereby lowering the overpotential for Li nucleation,and promoting uniform Li plating.Additionally,the fluorine(-F)termination of S-Ti_(3)C_(2)T_(x)participates in the SEI formation,producing a LiF-rich SEI layer,vital for stabilizing the SEI and improving cycle life.Batteries equipped with S-Ti_(3)C_(2)T_(x)@Cu current collectors displayed reduced Li consumption during stable SEI formation,resulting in a significant decrease in capacity loss.AFLMBs with S-Ti_(3)C_(2)T_(x)@Cu current collectors achieved a high initial capacity density of 4.2 mAh cm^(-2),70.9%capacity retention after 50 cycles,and an average CE of 98.19%in 100 cycles.This innovative application of MXenes in the energy field offers a promising strategy to enhance the performance of AFLMBs and could potentially accelerate their commercial adoption.
基金Korea Institute of Energy Technology Evaluation and Planning,Grant/Award Number:20214000000520Ministry of Trade,Industry and Energy,Grant/Award Number:20009985。
文摘Anode-free all-solid-state batteries(AF-ASSBs)have received significant attention as a next-generation battery system due to their high energy density and safety.However,this system still faces challenges,such as poor Coulombic efficiency and short-circuiting caused by Li dendrite growth.In this study,the AF-ASSBs are demonstrated with reliable and robust electrochemical properties by employing Cu-Sn nanotube(NT)thin layer(~1μm)on the Cu current collector for regulating Li electrodeposition.Li_(x)Sn phases with high Li-ion diffusivity in the lithiated Cu-Sn NT layer enable facile Li diffusion along with its one-dimensional hollow geometry.The unique structure,in which Li electrodeposition takes place between the Cu-Sn NT layer and the current collector by the Coble creep mechanism,improves cell durability by preventing solid electrolyte(SE)decomposition and Li dendrite growth.Furthermore,the large surface area of the Cu-Sn NT layer ensures close contact with the SE layer,leading to a reduced lithiation overpotential compared to that of a flat Cu-Sn layer.The Cu-Sn NT layer also maintains its structural integrity owing to its high mechanical properties and porous nature,which could further alleviate the mechanical stress.The LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM)|SE|Cu-Sn NT@Cu cell with a practical capacity of 2.9 mAh cm^(−2) exhibits 83.8%cycle retention after 150 cycles and an average Coulombic efficiency of 99.85%at room temperature.It also demonstrates a critical current density 4.5 times higher compared to the NCM|SE|Cu cell.
基金supported by the National Natural Science Foundation of China(Grant No.52372281)the Fundamental Research Funds for the Central Universities(Grant No.2232024G-07)+1 种基金the Key Laboratory of Advanced Fiber Materials(Grant No.KF2517)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning.
文摘Anode-free Li metal batteries(AFLMBs)impose stringent demands on active Li utilization due to the absence of exogenous Li.Moreover,the poor cycling reversibility of Li metal and significant active Li loss have hindered the development of AFLMBs.Herein,for the first time,we establish the correlation between the electrochemical structural connectivity of Li deposits and the loss pathways of active Li.Li nucleation behavior is optimized via the self-driven formation of hydroxyl-modified lithiophilic Cu nanoparticles from CuOHF.Dense columnar Li stacks with stable bulk-phase electronic pathways and interfacial kinetic structures are achieved through a high-density spatial multidimensional nucleation mechanism,which restricts the quasi-linear accumulation of irreversible Li to only 0.003 mg per cycle.Meanwhile,the regulated Li growth process exhibits homogeneous and rapid interfacial mass transfer with extremely low concentration polarization.The anode-free LiFePO_(4) pouch cell retains 61.4%of its initial reversible capacity after 100 cycles.Insights into active Li utilization derived from this work will accelerate the development of high-performance AFLMBs.
基金supported by the National Science Fund for Distinguished Young Scholars(Grant 52225201)the National Natural Science Foundation of China(Grants 52072085,52271207,52372213,and 52402241)+2 种基金the National Key Research and Development Program of China(Grant 2023YFE0201000)the Postdoctoral Fellowship Program of CPSF(Grants 2023M740899,GZC20233435)the Heilongjiang Touyan Innovation Team Program.
文摘Anode-free sodium-ion batteries(AFSIBs)achieve energy storage by completely eliminating traditional anode active materials and relying solely on the reversible plating and stripping of sodium from the anode source onto the current collector surface.This approach fundamentally addresses the limitations of energy density and safety inherent in conventional sodium batteries,positioning it as a promising candidate for high-energy“super-lithium”electrochemical storage technology.However,this innovative design also places unprecedentedly stringent demands on the current collector,making it a critical component in determining cell performance.This review systematically outlines the prevailing methodologies and research progress on modifying collectors for AFSIBs,with a focus on material sodophilicity engineering and structural modulation.By comprehensively reviewing the process of different sodium-friendly material modifications,interfacial functional modulation,porous structure configuration,and gradient engineering on the cell performance,the essential elements for enhancing the electrochemical performance of the current collector are outlined.Building on this,the paper discusses the challenges and opportunities in this field and suggests new research directions for developing high-performance AFSIBs.
基金the funding support from the National Natural Science Foundation of China(grant nos.92372122 and 52471242)the Fundamental Research Funds for the Central Universities(grant nos.KY2060000269,WK2060000040,KY2060000150,and GG2060127001)+3 种基金the Joint Laboratory for University of Science and Technology of China(USTC),Yanchang Petroleum(grant no.2022ZKD-03)the Shandong Province Natural Science Foundation(grant no.ZR2024ZD01)support from the China Postdoctoral Science Foundation(grant no.2023M730562)the Jiangsu Funding Program for Excellent Postdoctoral Talent(grant no.2023ZB187).
文摘The emerging Li//H_(2)battery is a promising candidate for energy storage systems to meet the demand for the worldwide transition to clean and sustainable energy.To leverage the H_(2)electrode’s advantages and decrease costs,a high areal capacity anode-free Li anode is ideal.Here we propose using a pseudocapacitive Cu(PC-Cu)substrate to accommodate the high areal capacity anode-free Li//H_(2)battery(AFLHB).The PC-Cu substrate exhibits intense electrochemical adsorption and intrinsic strong chemisorption to Li,which leads to aggregation of the Li salts so as to induce enrichment of interfacial lithiophilicity.This aids uniform Li nucleation,anion concentration,and robust SEI formation.The AFLHB displays stable cycling at a high areal capacity of 5 mAh cm^(-2)with an average coulombic efficiency of 98.80%for over 350 h.Notably,the PC-Cu substrate enables superdense Li deposition with only 7%thickness exceeding the theoretical value.Moreover,the modified substrate enables a reversible Li stripping/plating at an ultralarge areal capacity of 20 mAh cm^(-2).This work presents an interfacial lithiophilicity enrichment strategy to stabilize the cycling performance of high areal capacity AFLHB and advances this novel battery system one step closer to practical application.
基金support from the National Natural Science Foundation of China(52471242,92372122,21825302,22303094)the Fundamental Research Funds for the Central Universities(WK2060000040,KY2060000150,GG2060127001).
文摘Aqueous Zn batteries(AZBs)suffer from poor Zn anode reversibility.To address this issue,excess Zn foil is often utilized to prolong the cycle life,but it reduces the actual battery energy density.In this work,we use methylurea molecules to in situ form a solid electrolyte interphase(SEI)layer on the Zn anode,achieving reversible Zn plating/stripping with a maximal Coulombic efficiency(CE)of 99.99%and extending the anode's lifespan to 4500 cycles.Leveraging this highly reversible chemistry,we fabricate and test various anode-free Zn batteries.An anode-free Zn-AC cell exhibits stable cycling for exceeding 5000 cycles,an anode-free Zn-I_(2) battery with high specific capacities achieves a stable cycle life of 1000 cycles,and an anode-free Zn-Br_(2) battery with a high areal capacity of 4 mAh cm^(-2) demonstrates a stable cycle life of 450 cycles.Characterization of the SEI using TEM and DFT calculations reveal the formation mechanisms of the ZnCO_(3)-and ZnS-rich amorphous SEI layer.These results indicate that the design of desirable SEI compositions could pave the way for developing low-cost,high-performance anode-free AZBs.
基金financially supported by the National Natural Science Foundation of China(No.22279164)the Hunan Provincial Science and Technology Plan Projects of China(No.2022RC3050 and No.2017TP1001)the cooperation project from Guangdong DFP New Material Group Co.Ltd.
文摘Anode-free sodium batteries(AFSBs)have attracted increasing attention for their high energy density.However,they suffer from rapid capacity decline resulting from sodium dendrite growth at the sodium/host interface and irreversible side reactions at the electrolyte/sodium interface.Herein,a GaInSn-coated Cu foil(G-Cu),prepared by a simple brush coating method,was applied as the sodiophilic current collector to regulate sodium nucleation behavior.In addition,a nonexpendable functional electrolyte additive,hexamethyldisiloxane(HMDSO),was introduced,which could be absorbed on the sodium surface and serve as a protective layer against corrosion side reactions at the electrolyte/sodium interface.It is interesting to note that this additive barely participated in forming the solid electrolyte interphase.The synergetic effects of sodiophilic interface design and electrolyte regulation enable reversible sodium plating and stripping.Ultimately,the AFSB assembled using G-Cu and HMDSO electrolyte with a highly loaded Na_(3)V_(2)(PO_(4))_(3) cathode(≈12.5 mg cm^(−2))delivers a discharge capacity of 84.5 mAh g^(−1) after 200 cycles with a high capacity retention of 87.6%,significantly extending its operation lifespan.
文摘The zinc(Zn)batteries have challenges include uncontrollable dendritic growth,unreasonable negative to positive ratio and limited areal capacity.This highlight presents the latest development to resolve the uncontrollable Zn dendrite formation at high areal capacities of 200 mAh·cm^(-2) through a two-dimensional metal/metal-Zn alloy heterostructured interface.The anode-free Zn batteries with an attractive and practical pouch cell energy density of 62 Wh·kg^(-1) enlighten an arena towards their commercialization.
