The unavoidable dendrite growth and shuttle effect have long been stranglehold challenges limiting the safety and practicality of lithium-sulfur batteries.Herein,we propose a dual-action strategy to address the lithiu...The unavoidable dendrite growth and shuttle effect have long been stranglehold challenges limiting the safety and practicality of lithium-sulfur batteries.Herein,we propose a dual-action strategy to address the lithium dendrite issue in stages by constructing a multifunctional surface-negatively-charged nanodiamond layer with high ductility and robust puncture resistance on polypropylene (PP) separator.The uniformly loaded compact negative layer can not only significantly enhance electron transmission efficiency and promote uniform lithium deposition,but also reduce the formation of dendrite during early deposition stage.Most importantly,under the strong puncture stress encountered during the deterioration of lithium dendrite growth under limiting current,the high ductility and robust puncture resistance(145.88 MPa) of as-obtained nanodiamond layer can effectively prevent short circuits caused by unavoidable lithium dendrite.The Li||Li symmetrical cells assembled with nanodiamond layer modified PP demonstrated a stable cycle of over 1000 h at 2 mA cm^(-2)with a polarization voltage of only 29.3 mV.Additionally,the negative charged layer serves as a physical barrier blocking lithium polysulfide ions,effectively mitigating capacity attenuation.The improved cells achieved a capacity decay of only 0.042%per cycle after 700 cycles at 3 C,demonstrating effective suppression of dendrite growth and capacity attenuation,showing promising prospect.展开更多
The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design c...The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.展开更多
Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capac...Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capacitance of carbon cathode materials and the dendrite growth on Zn anode have set fatal drawbacks to their energy density and cycle stability.Herein,we demonstrate that,in 1 M Zn(CF_(3)SO_(3))_(2)/DMF(N,N-dimethylformamide)electrolyte,confining oxygen in carbon cathode materials via high-energy ball milling can synergistically introduce additional pseudocapacitance on the cathode side while suppressing the dendrite growth on Zn anode side,which jointly lead to high energy density(94 Wh kg^(−1)at 448 W kg^(−1))and long cycle stability of ZICs.The hydroxyl group in carbon cathode can be transformed to C–O–Zn together with the release of protons during the initial discharge,which in turn stimulates the defluorination of CF_(3)SO_(3)^(-)anions and formation of ZnF_(2)on both cathode and anode.The ZnF2 formed on the surface of the Zn anode suppresses the dendrite growth by regulating the Zn^(2+)deposition/stripping in a reticular structure,resulting in the excellent cycle stability.This work provides a facile strategy to rationally design and construct high energy and stable ZICs through engineering the oxygen-bearing functional groups in carbon cathode materials.展开更多
The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Here...The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Herein,we report a cucumber-like lithiophilic composite skeleton(CLCS)fabricated through a facile oxidationimmersion-reduction method.The stepwise Li deposition and stripping,determined using in situ Raman spectra during the galvanostatic Li charging/discharging process,promote the formation of a dendrite-free Li metal anode.Furthermore,numerous pyridinic N,pyrrolic N,and CuxN sites with excellent lithiophilicity work synergistically to distribute Li ions and suppress the formation of Li dendrites.Owing to these advantages,cells based on CLCS exhibit a high Coulombic efficiency of 97.3%for 700 cycles and an improved lifespan of 2000 h for symmetric cells.The full cells assembled with LiFePO_(4)(LFP),SeS_(2) cathodes and CLCS@Li anodes demonstrate high capacities of 110.1 mAh g^(−1) after 600 cycles at 0.2 A g^(−1) in CLCS@Li|LFP and 491.8 mAh g^(−1) after 500 cycles at 1 A g^(−1) in CLCS@Li|SeS2.The unique design of CLCS may accelerate the application of Li metal anodes in commercial Li metal batteries.展开更多
Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigatio...Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.展开更多
A highly stable zinc metal anode modified with a fluorinated graphite nanosheets(FGNSs)coating was designed.The porous structure of the coating layer effectively hinders lateral mass transfer of Zn ions and suppresses...A highly stable zinc metal anode modified with a fluorinated graphite nanosheets(FGNSs)coating was designed.The porous structure of the coating layer effectively hinders lateral mass transfer of Zn ions and suppresses dendrite growth.Moreover,the high electronegativity exhibited by fluorine atoms creates an almost superhydrophobic solid-liquid interface,thereby reducing the interaction between solvent water and the zinc substrate.Consequently,this leads to a significant inhibition of hydrogen evolution corrosion and other side reactions.The modified anode demonstrates exceptional cycling stability,as symmetric cells exhibit sustained cycling for over 1400 h at a current density of 5 mA/cm^(2).Moreover,the full cells with NH_(4)V_(4)O_(10)cathode exhibit an impressive capacity retention rate of 92.2%after undergoing 1000 cycles.展开更多
The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cos...The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cost,non-toxic maltitol as the electrolyte additive.The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane,and thus hinder the immediate contact between Zn metal and H_(2)O.Meanwhile,strong interaction between maltitol and H_(2)O molecules can restrain the activity of H_(2)O.Besides,the"IHP adsorption effect"along with the low LUMO energy level of maltitol-CF_(3)SO_(3)^(-)can promote the in-situ formation of an organic-inorganic complex solid electrolyte interface(SEI)layer.As a result,the hydrogen/oxygen evolution side reaction,corrosion,and dendrites issues are effectively suppressed,thereby leading to highly reversible and dendrite-free Zn plating/stripping.The Zn‖I_(2)battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability,showing a capacity retention of 75%over 20000 charge-discharge cycles at a large current density of 5 A g^(-1).In addition,the capacity of the device has almost no obvious decay over20000 cycles even at-30℃.This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.展开更多
With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large...With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies.However,the notorious Zn dendrites and low Coulombic effi-ciency(CE)limit further development of AZIBs,due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes.In this review,critical issues and advances are summarized in electrolyte engineering strategies.These strategies are focused on active water molecules during electrochemical process,including high-concentration electrolytes,ionic liquids,gel-polymer elec-trolytes and functional additives.With suppressed active water molecules,the solvation and de-solvation behavior of Zn^(2+)can be regulated,thereby modulating the electrochemical performance of Zn anode.Finally,the inherent problems of these strategies are discussed,and some promising directions are pro-vided on electrolytes engineering for high performance Zn anode in AZIBs.展开更多
Zinc-ion hybrid capacitors(ZHCs),integrating the high power density of supercapacitors and high energy density of batteries,are an emerging and sustainable electrochemical energy storage device.However,the poor rate p...Zinc-ion hybrid capacitors(ZHCs),integrating the high power density of supercapacitors and high energy density of batteries,are an emerging and sustainable electrochemical energy storage device.However,the poor rate performance,low utilization of active sites and unsatisfactory cycling life of capacitive-type cathode are still current technical challenges,while the uneven deposition of zinc anode generates a large number of dendrites,which can easily penetrate the separator to cause device failure,greatly limiting the commercialization prospects of ZHCs.Here,this review systematically elaborates on the current research progress of cathode materials for ZHCs,including preparation methods and structural design of porous carbon and heteroatom-doped porous carbon,deeply analyzing and discussing the energy storage mechanism and electrochemical behavior.Moreover,this review analyzes the causes and inhibition mechanisms of zinc dendrites,including electrolyte modification,induced uniform deposition of zinc and zinc anode modification,systematically elaborating on the three directions of current modification strategies for zinc anode.Finally,the current challenges and future development of cathode materials and dendrite suppression were prospected,developing a high-performance ZHCs.展开更多
As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfi...As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfides with Sn-O dual doping,which is a powerful solution to comprehensively improve the performance of a material.The combination of O and Sn-aliovalent doping not only enables an improved ionic conductivity but more importantly realizes an intensively enhanced interfacial compatibility between argyrodite and Li metal and Li dendrite suppression capability.The assembled battery with Sn-O dual-doped electrolyte and Li anode demonstrates high capacity and decent cycling stability.Dual doping is thus believed to be an effective way to develop high performance sulfide solid electrolytes.展开更多
The solid polymer electrolyte(SPE) is one of the most promising candidates for building solid lithium batteries with high energy density and safety due to its advantages of flexibility and light-weight.However,the con...The solid polymer electrolyte(SPE) is one of the most promising candidates for building solid lithium batteries with high energy density and safety due to its advantages of flexibility and light-weight.However,the conventional monolayered electrolytes usually exhibit unstable contacts with either high-voltage cathodes or Li-metal anodes during cell operation.Herein,heterogeneous dual-layered electrolyte membranes(HDEMs) consisting of the specific functional polymer matrixes united with the designed solid ceramic fillers are constructed to address the crucial issues of interfacial instability.The electrolyte layers composed of the high-conductivity and oxidation-resistance polyacrylonitrile(PAN) combined with Li_(0.33)La_(0.557)TiO_(3) nanofibers are in contact with the high-voltage cathodes,achieving the compatible interface between the cathodes and the electrolytes.Meanwhile,the electrolyte layers composed of the highstability and dendrite-resistance polyethylene oxide(PEO) with Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12) nanoparticles are in contact with the Li-metal anodes,aiming to suppress the dendrite growth,as well as avoid the passivation between the PAN and the Li-metal.Consequently,the solid LiNi_(0.6)Co_(0.2)Mn_(0.2)O2‖Li full cells based on the designed HDEMs show the good rate and cycling performance,i.e.the discharge capacity of 170.1 mAh g^(-1) with a capacity retention of 78.2% after 100 cycles at 0.1 C and 30℃.The results provide an effective strategy to construct the heterogeneous electrolyte membranes with double-side stable electrode/-electrolyte interfaces for the high-voltage and dendrite-free solid lithium batteries.展开更多
Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and...Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and side reactions.This study introduces a polyanionic strategy to address these formidable issues by developing a hydrogel electrolyte(PACXHE)with carboxyl groups.Notably,the carboxyl groups within the hydrogel structure establish favorable channels to promote the transport of Zn^(2+)ions.They also expedite the desolvation of hydrated Zn^(2+)ions,leading to enhanced deposition kinetics.Additionally,these functional groups confine interfacial planar diffusion and promote preferential deposition along the(002)plane of Zn,enabling a smooth surface texture of the Zn anode.This multifaceted regulation successfully achieves the suppression of Zn dendrites and side reactions,thereby enhancing the electrochemical reversibility and service life during plating/stripping cycles.Therefore,such an electrolyte demonstrates a high average Coulombic efficiency of 97.7%for 500 cycles in the Zn‖Cu cell and exceptional cyclability with a duration of 480 h at 1 mA cm^(-2)/1 mA h cm^(-2)in the Zn‖Zn cell.Beyond that,the Zn-ion hybrid micro-capacitor employing PACXHE exhibits satisfactory cycling stability,energy density,and practicality for energy storage in flexible,intelligent electronics.The present polyanionic-based hydrogel strategy and the development of PACXHE represent significant advancements in the design of hydrogel electrolytes,paving the way for a more sustainable and efficient future in the energy storage field.展开更多
Li metal anode holds great promise to realize high-energy battery systems.However,the safety issue and limited lifetime caused by the uncontrollable growth of Li dendrites hinder its commercial application.Herein,an i...Li metal anode holds great promise to realize high-energy battery systems.However,the safety issue and limited lifetime caused by the uncontrollable growth of Li dendrites hinder its commercial application.Herein,an interlayer-bridged 3D lithiophilic rGO-Ag-S-CNT composite is proposed to guide uniform and stable Li plating/stripping.The 3D lithiophilic rGO-Ag-S-CNT host is fabricated by incorporating Ag-modified reduced graphene oxide(rGO)with S-doped carbon nanotube(CNT),where the rGO and CNT are closely connected via robust Ag-S covalent bond.This strong Ag-S bond could enhance the structural stability and electrical connection between rGO and CNT,significantly improving the electrochemical kinetics and uniformity of current distribution.Moreover,density functional theory calculation indicates that the introduction of Ag-S bond could further boost the binding energy between Ag and Li,which promotes homogeneous Li nucleation and growth.Consequently,the rGO-Ag-S-CNT-based anode achieves a lower overpotential(7.3 mV at 0.5 mA cm^(−2)),higher Coulombic efficiency(98.1%at 0.5 mA cm^(−2)),and superior long cycling performance(over 500 cycles at 2 mA cm−2)as compared with the rGO-Ag-CNT-and rGO-CNT-based anodes.This work provides a universal avenue and guidance to build a robust Li metal host via constructing a strong covalent bond,effectively suppressing the Li dendrites growth to prompt the development of Li metal battery.展开更多
When I read the paper“Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries”from Prof.Jianmin Ma’s group,which was published in Science Bulletin(doi.org/10.1016/j.scib.2020.09.018...When I read the paper“Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries”from Prof.Jianmin Ma’s group,which was published in Science Bulletin(doi.org/10.1016/j.scib.2020.09.018),I felt excited as presented a multi-factor principle for applying potassium perfluorinated sulfonates to suppress the dendrite growth and protect the cathode from the viewpoint of electrolyte additives.The effects of these additives are revealed through experimental results,molecular dynamics simulations and first-principle calculations.Specifically,it involves the influence of additives on Li^(+)solvation structure,solid electrolyte interphase(SEI),Li growth and nucleation.Following the guidance of the multi-factor principle,every part of the additive molecule should be utilized to regulate electrolytes.This multifactor principle for electrolyte additive molecule design(EAMD)offers a unique insight on understanding the electrochemical behavior of iontype electrolyte additives on both the Li metal anode and high-voltage cathode.In these regards,I would be delighted to write a highlight for this innovative work and,hopefully,it may raise more interest in the areas of electrolyte additives.展开更多
Building lithium fluoride(LiF)-rich solid electrolyte interphases(SEIs)by the decomposition of fluorinated salts has been widely adopted to be effective to suppress lithium dendrite growth,thus prolonging the lifespan...Building lithium fluoride(LiF)-rich solid electrolyte interphases(SEIs)by the decomposition of fluorinated salts has been widely adopted to be effective to suppress lithium dendrite growth,thus prolonging the lifespan of fast-charging lithium metal batteries(LMBs).Nevertheless,the slow dissociation of LiF salts reduces both their utilization and the formation of inorganic SEI.Herein,cellulose acetate(CA)was incorporated into the electrolyte to create an inorganic-rich SEI through ester groups,where the lithiophilic oxygen atoms in the ester group(C═O)enhanced lithium-ion diffusion and anion dissociation rates.Therefore,rapid ion diffusion and dendrite-free anodes were achieved in the ester-based electrolyte with CA(named as CA-E).As a result,the lithium symmetric batteries with the CA-E electrolyte exhibited stable cycling performance for 5,000 h at a current density/capacity of 3 mA cm^(-2)/1 mAh cm^(-2),while a short-circuiting was observed after~450 h for the bare electrolyte.Benefiting from the rational design,lithium iron phosphate batteries with the CA-E electrolyte showed an excellent C-rate performance with a capacity of 100.7 mAh g^(−1) at the rate of 10 C.Moreover,a specific capacity of 110.3 mAh g^(−1) was maintained after 300 cycles at the rate of 6 C with a Coulombic efficiency of 99.87%.This work proposes a new approach to dendrite inhibitors for fast-charging LMBs.展开更多
Rechargeable aqueous zinc batteries(RAZBs)offer a promising solution for large-scale energy storage due to the abundance,low cost,and safety of Zn.However,practical applications are hindered by Zn anode instability,de...Rechargeable aqueous zinc batteries(RAZBs)offer a promising solution for large-scale energy storage due to the abundance,low cost,and safety of Zn.However,practical applications are hindered by Zn anode instability,dendrite growth,and hydrogen evolution reactions(HER).Chaotropic Zn(ClO_(4))2 electrolytes are favorable for low-temperature operations but exacerbate these issues due to their high acidity,leading to severe Zn corrosion and layered double hydroxide formation.We propose a biomimetic strategy using methylguanidoacetic acid(creatine)as a low-cost,eco-friendly additive to address these challenges.Creatine acts as a proton pocket to finely tune the pH of acidic Zn(ClO_(4))2 electrolytes for suppressing HER and stabilizing the Zn anode.Furthermore,the formed creatinine cations adsorb on the Zn surface,promoting highly controlled Zn deposition with a preferred(002)orientation.This approach significantly enhances battery cycling performance,with Zn||Zn cells demonstrating extended cycling stability at both low and high current densities.Zn||Cu cells exhibited improved Coulombic efficiency over thousands of cycles,indicating highly reversible Zn plating/stripping.Notably,stable cell operations were realized at the temperature as low as−35℃ without electrolyte freezing.Our findings highlight the potential of biomimetic proton regulation and interfacial modulation for improving the stability and reversibility of Zn plating/stripping in RAZBs.展开更多
Aqueous zinc battery has been regarded as one of the most promising energy storage systems due to its low cost and environmental benignity.However,the safety concern on Zn anodes caused by uncontrolled Zn dendrite gro...Aqueous zinc battery has been regarded as one of the most promising energy storage systems due to its low cost and environmental benignity.However,the safety concern on Zn anodes caused by uncontrolled Zn dendrite growth in aqueous electrolyte hinders their application.Herein,sucrose with multi-hydroxyl groups has been introduced into aqueous electrolyte to modify Zn^(2+)solvation environment and create a protection layer on Zn anode,thus effectively retarding the growth of zinc dendrites.Atomistic simulations and experiments confirm that sucrose molecules can enter into the solvation sheath of Zn^(2+),and the as-formed unique solvation structure enhances the mobility of Zn^(2+).Such fast Zn^(2+)kinetics in sucrose-modified electrolyte can successfully suppress the dendrite growth.With this sucrose-modified aqueous electrolyte,Zn/Zn symmetric cells present more stable cycle performance than those using pure aqueous electrolyte;Zn/C cells also deliver an impressive higher energy density of 129.7 Wh·kg^(−1)and improved stability,suggesting a great potential application of sucrose-modified electrolytes for future Zn batteries.展开更多
Aqueous zinc(Zn)ion batteries(AZIBs)are regarded as one of the promising candidates for next-generation electrochemical energy storage systems due to their low cost,high safety,and environmental friendliness.However,t...Aqueous zinc(Zn)ion batteries(AZIBs)are regarded as one of the promising candidates for next-generation electrochemical energy storage systems due to their low cost,high safety,and environmental friendliness.However,the commercialization of AZIBs has been severely restricted by the growth of dendrite at the Zn metal anode.Tailoring the planar-structured Zn anodes into threedimensional(3D)structures has proven to be an effective way to modulate the plating/stripping behavior of Zn anodes,resulting in the suppression of dendrite formation.This review provides an up-to-date review of 3D structured Zn metal anodes,including working principles,design,current status,and future prospects.We aim to give the readers a comprehensive understanding of 3D-structured Zn anodes and their effective usage to enhance AZIB performance.展开更多
Lithium metal batteries(LMBs)based on metallic Li exhibit high energy density to be competent for advanced energy storage applications.However,the unstable solid electrolyte interphase(SEI)layer due to continuous deco...Lithium metal batteries(LMBs)based on metallic Li exhibit high energy density to be competent for advanced energy storage applications.However,the unstable solid electrolyte interphase(SEI)layer due to continuous decomposition of electrolytes,and the attendant problem of Li dendrite growth frustrate their commercialization process.Herein,a hybrid SEI comprising abundant LiF,lithiophilic Li-Ge alloy,and Ge nanoparticles is constructed via a simple brush coating method.This fluorinated interface layer with embedded Ge-containing components isolates the Li anode from the corrosive electrolyte and facilitates homogenous Li nucleation as well as uniform growth.Consequently,the modified Li anode exhibits remarkable stability without notorious Li dendrites,delivering stable cycling lives of more than 1000 h for symmetric Li||Li cells and over 600 cycles for Li||Cu cells at 1 mA·cm^(−2).Moreover,the reinforced Li anodes endow multiple full-cell architectures with dramatically improved cyclability under different test conditions.This work provides rational guidance to design an artificial hybrid SEI layer and would stimulate more ideas to solve the dendrite issue and promote the further development of advanced LMBs.展开更多
Rechargeable aqueous zinc(Zn)ion batteries(AZIBs)using low-cost and safe Zn metal anodes are considered promising candidates for future grid-scale energy storage systems,but the Zn dendrite problem severely hinders th...Rechargeable aqueous zinc(Zn)ion batteries(AZIBs)using low-cost and safe Zn metal anodes are considered promising candidates for future grid-scale energy storage systems,but the Zn dendrite problem severely hinders the further prospects of AZIBs.Regulating Zn depositing behaviors toward horizontal alignment is highly effective and thus has received huge attention.However,such a strategy is usually based on previous substrate engineering,which requires complex preparation or expensive equipment.Therefore,it is essential to develop a novel solution that can realize horizontally aligned Zn flake deposition via easy operation and low cost.Herein,we report an ultrathin and robust Kevlar membrane as the interlayer to mechanically suppress Zn dendrite growth.Compared to the randomly distributed flaky dendrites in the control group,the deposited Zn sheets would grow into parallel alignment with the existence of such interlayer.As the dendrites are effectively suppressed,Zn||Cu asymmetric,Zn||Zn symmetric,and Zn||MnO_(2)full batteries using Kevlar interlayer deliver significantly improved cycling stabilities.Furthermore,the Zn||MnO_(2)pouch cell using a Kevlar interlayer delivers stable cycling performance and shows stable operation during multi-angle folding.We believe this work provides a new possibility for regulating Zn deposition from a crystallographic perspective.展开更多
基金National Natural Science Foundation of China (Grant 52372083, 52173255)Opening Project of the Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials (JSKC24025)+1 种基金Special Funds for the Trans-formation of Scientific and Technological Achievements in Jiangsu Province(BA2023003)Collaborative Innovation Center for Advanced Micro/nanomaterials and Equipment (Co-constructed by Jiangsu Province and Ministry of Education)。
文摘The unavoidable dendrite growth and shuttle effect have long been stranglehold challenges limiting the safety and practicality of lithium-sulfur batteries.Herein,we propose a dual-action strategy to address the lithium dendrite issue in stages by constructing a multifunctional surface-negatively-charged nanodiamond layer with high ductility and robust puncture resistance on polypropylene (PP) separator.The uniformly loaded compact negative layer can not only significantly enhance electron transmission efficiency and promote uniform lithium deposition,but also reduce the formation of dendrite during early deposition stage.Most importantly,under the strong puncture stress encountered during the deterioration of lithium dendrite growth under limiting current,the high ductility and robust puncture resistance(145.88 MPa) of as-obtained nanodiamond layer can effectively prevent short circuits caused by unavoidable lithium dendrite.The Li||Li symmetrical cells assembled with nanodiamond layer modified PP demonstrated a stable cycle of over 1000 h at 2 mA cm^(-2)with a polarization voltage of only 29.3 mV.Additionally,the negative charged layer serves as a physical barrier blocking lithium polysulfide ions,effectively mitigating capacity attenuation.The improved cells achieved a capacity decay of only 0.042%per cycle after 700 cycles at 3 C,demonstrating effective suppression of dendrite growth and capacity attenuation,showing promising prospect.
基金supported by the National Natural Science Foundation of China(Nos.22208221,22178221)the Natural Science Foundation of Guangdong Province(Nos.2024A1515011078,2024A1515011507)+1 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20220818095805012,JCYJ20230808105109019)the Start-up Research Funding of Shenzhen University(No.868-000001032522).
文摘The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.
基金financially supported by the Natural Science Foundation of Xiamen,China(No.3502Z202373070).
文摘Zinc-ion capacitors(ZICs)are promising energy storage devices due to their balance between the energy and power densities inherited from Zn-ion batteries and supercapacitors,respectively.However,the low specific capacitance of carbon cathode materials and the dendrite growth on Zn anode have set fatal drawbacks to their energy density and cycle stability.Herein,we demonstrate that,in 1 M Zn(CF_(3)SO_(3))_(2)/DMF(N,N-dimethylformamide)electrolyte,confining oxygen in carbon cathode materials via high-energy ball milling can synergistically introduce additional pseudocapacitance on the cathode side while suppressing the dendrite growth on Zn anode side,which jointly lead to high energy density(94 Wh kg^(−1)at 448 W kg^(−1))and long cycle stability of ZICs.The hydroxyl group in carbon cathode can be transformed to C–O–Zn together with the release of protons during the initial discharge,which in turn stimulates the defluorination of CF_(3)SO_(3)^(-)anions and formation of ZnF_(2)on both cathode and anode.The ZnF2 formed on the surface of the Zn anode suppresses the dendrite growth by regulating the Zn^(2+)deposition/stripping in a reticular structure,resulting in the excellent cycle stability.This work provides a facile strategy to rationally design and construct high energy and stable ZICs through engineering the oxygen-bearing functional groups in carbon cathode materials.
基金This work is well supported by National Natural Science Foundation of China(52073170,21975154)Shanghai Municipal Education Commission(Innovation Program(2019-01-07-00-09-E00021)Innovative Research Team of High-level Local Universities in Shanghai.The authors also acknowledge Lab for Microstructure,Instrumental Analysis&Research Center,Shanghai University,for their help on materials characterization.Moreover,the authors thank High Performance Computing Center of Shanghai University,and Shanghai Engineering Research Center of Intelligent Computing System(No.19DZ2252600)for the assistance of computing resources and technical support.
文摘The uncontrolled formation of lithium(Li)dendrites and the unnecessary consumption of electrolyte during the Li plating/stripping process have been major obstacles in developing safe and stable Li metal batteries.Herein,we report a cucumber-like lithiophilic composite skeleton(CLCS)fabricated through a facile oxidationimmersion-reduction method.The stepwise Li deposition and stripping,determined using in situ Raman spectra during the galvanostatic Li charging/discharging process,promote the formation of a dendrite-free Li metal anode.Furthermore,numerous pyridinic N,pyrrolic N,and CuxN sites with excellent lithiophilicity work synergistically to distribute Li ions and suppress the formation of Li dendrites.Owing to these advantages,cells based on CLCS exhibit a high Coulombic efficiency of 97.3%for 700 cycles and an improved lifespan of 2000 h for symmetric cells.The full cells assembled with LiFePO_(4)(LFP),SeS_(2) cathodes and CLCS@Li anodes demonstrate high capacities of 110.1 mAh g^(−1) after 600 cycles at 0.2 A g^(−1) in CLCS@Li|LFP and 491.8 mAh g^(−1) after 500 cycles at 1 A g^(−1) in CLCS@Li|SeS2.The unique design of CLCS may accelerate the application of Li metal anodes in commercial Li metal batteries.
基金supported by the National Natural Science Foundation of China(52272258 and 52411530056)the Beijing Nova Program(20220484214)+1 种基金Key R&D and Transformation Projects in Qinghai Province(2023-HZ-801)the financial support from the China Scholarship Council(No.202006210070)。
文摘Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.
基金supported by Young Elite Scientists Sponsorship Program by CAST,China(No.2023QNRC001)the Science and Technology Innovation Program of Hunan Province,China(No.2022RC1078)+1 种基金the Natural Science Foundation of Hunan Province,China(No.2023JJ10060)the Scientific Research Fund of Hunan Provincial Education Department,China(No.23A0003)。
文摘A highly stable zinc metal anode modified with a fluorinated graphite nanosheets(FGNSs)coating was designed.The porous structure of the coating layer effectively hinders lateral mass transfer of Zn ions and suppresses dendrite growth.Moreover,the high electronegativity exhibited by fluorine atoms creates an almost superhydrophobic solid-liquid interface,thereby reducing the interaction between solvent water and the zinc substrate.Consequently,this leads to a significant inhibition of hydrogen evolution corrosion and other side reactions.The modified anode demonstrates exceptional cycling stability,as symmetric cells exhibit sustained cycling for over 1400 h at a current density of 5 mA/cm^(2).Moreover,the full cells with NH_(4)V_(4)O_(10)cathode exhibit an impressive capacity retention rate of 92.2%after undergoing 1000 cycles.
基金supported by the National Natural Science Foundation of China(52261160384)the Shenzhen Science and Technology Innovation Commission(RCYX20221008092934093)+1 种基金the Shenzhen Science and Technology Program(KJZD20230923114107014)the support from Testing Technology Center of Materials and Devices,Tsinghua Shenzhen International Graduate School。
文摘The development of aqueous Zn batteries is limited by parasitic water reactions,corrosion,and dendrite growth.To address these challenges,an inner Helmholtz plane(IHP)regulation method is proposed by employing low-cost,non-toxic maltitol as the electrolyte additive.The preferential adsorption behavior of maltitol can expel the water from the inner Helmholtz plane,and thus hinder the immediate contact between Zn metal and H_(2)O.Meanwhile,strong interaction between maltitol and H_(2)O molecules can restrain the activity of H_(2)O.Besides,the"IHP adsorption effect"along with the low LUMO energy level of maltitol-CF_(3)SO_(3)^(-)can promote the in-situ formation of an organic-inorganic complex solid electrolyte interface(SEI)layer.As a result,the hydrogen/oxygen evolution side reaction,corrosion,and dendrites issues are effectively suppressed,thereby leading to highly reversible and dendrite-free Zn plating/stripping.The Zn‖I_(2)battery with hybrid electrolytes also demonstrates high electrochemical performance and ultralong cycling stability,showing a capacity retention of 75%over 20000 charge-discharge cycles at a large current density of 5 A g^(-1).In addition,the capacity of the device has almost no obvious decay over20000 cycles even at-30℃.This work offers a successful electrolyte regulation strategy via the IHP adsorption effect to design electrolytes for high-performance rechargeable Zn-ion batteries.
基金supported by the Science Fund for Natural Science Foundation of Hunan Province(No.2023JJ20064)the National Natural Science Foundation of China(No.52377222)Natural Science Foundation of Hunan Province(No.2023JJ50012).
文摘With the low cost,excellent safety and high theoretical specific capacity,aqueous zinc-ion batteries(AZ-IBs)are considered as a potential rival for lithium-ion batteries to promote the sustainable development of large-scale energy storage technologies.However,the notorious Zn dendrites and low Coulombic effi-ciency(CE)limit further development of AZIBs,due to the unstable electrochemical deposition/stripping behavior of Zn anode in aqueous zinc ion electrolytes.In this review,critical issues and advances are summarized in electrolyte engineering strategies.These strategies are focused on active water molecules during electrochemical process,including high-concentration electrolytes,ionic liquids,gel-polymer elec-trolytes and functional additives.With suppressed active water molecules,the solvation and de-solvation behavior of Zn^(2+)can be regulated,thereby modulating the electrochemical performance of Zn anode.Finally,the inherent problems of these strategies are discussed,and some promising directions are pro-vided on electrolytes engineering for high performance Zn anode in AZIBs.
基金financially supported by the National Natural Science Foundation of China(No.52372228)Sichuan Science and Technology Program(No.2018RZ0074)。
文摘Zinc-ion hybrid capacitors(ZHCs),integrating the high power density of supercapacitors and high energy density of batteries,are an emerging and sustainable electrochemical energy storage device.However,the poor rate performance,low utilization of active sites and unsatisfactory cycling life of capacitive-type cathode are still current technical challenges,while the uneven deposition of zinc anode generates a large number of dendrites,which can easily penetrate the separator to cause device failure,greatly limiting the commercialization prospects of ZHCs.Here,this review systematically elaborates on the current research progress of cathode materials for ZHCs,including preparation methods and structural design of porous carbon and heteroatom-doped porous carbon,deeply analyzing and discussing the energy storage mechanism and electrochemical behavior.Moreover,this review analyzes the causes and inhibition mechanisms of zinc dendrites,including electrolyte modification,induced uniform deposition of zinc and zinc anode modification,systematically elaborating on the three directions of current modification strategies for zinc anode.Finally,the current challenges and future development of cathode materials and dendrite suppression were prospected,developing a high-performance ZHCs.
基金supported by the National Key R&D Program of China(No.2018YFB0104300)the Natural Science Foundation of Hebei Province(No.E2018203301)。
文摘As a type of candidate for all-solid-state Li batteries,argyrodite solid electrolytes possess high ionic conductivity,but poor compatibility against Li metal.Here,we report novel Li_(6) PS_(5) I-based argyrodite sulfides with Sn-O dual doping,which is a powerful solution to comprehensively improve the performance of a material.The combination of O and Sn-aliovalent doping not only enables an improved ionic conductivity but more importantly realizes an intensively enhanced interfacial compatibility between argyrodite and Li metal and Li dendrite suppression capability.The assembled battery with Sn-O dual-doped electrolyte and Li anode demonstrates high capacity and decent cycling stability.Dual doping is thus believed to be an effective way to develop high performance sulfide solid electrolytes.
基金supported by the National Key R&D Program of China (Grant No. 2018YFB0104300)the National Natural Science Foundation of China (Grant No. U1932205, 51771222, 22005163 and 52002197)the ‘‘Taishan Scholars Program”, and the Project of Qingdao Leading Talents in Entrepreneurship and Innovation。
文摘The solid polymer electrolyte(SPE) is one of the most promising candidates for building solid lithium batteries with high energy density and safety due to its advantages of flexibility and light-weight.However,the conventional monolayered electrolytes usually exhibit unstable contacts with either high-voltage cathodes or Li-metal anodes during cell operation.Herein,heterogeneous dual-layered electrolyte membranes(HDEMs) consisting of the specific functional polymer matrixes united with the designed solid ceramic fillers are constructed to address the crucial issues of interfacial instability.The electrolyte layers composed of the high-conductivity and oxidation-resistance polyacrylonitrile(PAN) combined with Li_(0.33)La_(0.557)TiO_(3) nanofibers are in contact with the high-voltage cathodes,achieving the compatible interface between the cathodes and the electrolytes.Meanwhile,the electrolyte layers composed of the highstability and dendrite-resistance polyethylene oxide(PEO) with Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12) nanoparticles are in contact with the Li-metal anodes,aiming to suppress the dendrite growth,as well as avoid the passivation between the PAN and the Li-metal.Consequently,the solid LiNi_(0.6)Co_(0.2)Mn_(0.2)O2‖Li full cells based on the designed HDEMs show the good rate and cycling performance,i.e.the discharge capacity of 170.1 mAh g^(-1) with a capacity retention of 78.2% after 100 cycles at 0.1 C and 30℃.The results provide an effective strategy to construct the heterogeneous electrolyte membranes with double-side stable electrode/-electrolyte interfaces for the high-voltage and dendrite-free solid lithium batteries.
基金funded by the National Natural Science Foundation of China(U2003216)the National Key Research and Development Program of China(2022YFB4101600)+1 种基金the Shanghai Cooperation Organisation Project(2022E01020)the Scientific Research Program of the Higher Education Institution of Xinjiang(XJEDU2022P004)。
文摘Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and side reactions.This study introduces a polyanionic strategy to address these formidable issues by developing a hydrogel electrolyte(PACXHE)with carboxyl groups.Notably,the carboxyl groups within the hydrogel structure establish favorable channels to promote the transport of Zn^(2+)ions.They also expedite the desolvation of hydrated Zn^(2+)ions,leading to enhanced deposition kinetics.Additionally,these functional groups confine interfacial planar diffusion and promote preferential deposition along the(002)plane of Zn,enabling a smooth surface texture of the Zn anode.This multifaceted regulation successfully achieves the suppression of Zn dendrites and side reactions,thereby enhancing the electrochemical reversibility and service life during plating/stripping cycles.Therefore,such an electrolyte demonstrates a high average Coulombic efficiency of 97.7%for 500 cycles in the Zn‖Cu cell and exceptional cyclability with a duration of 480 h at 1 mA cm^(-2)/1 mA h cm^(-2)in the Zn‖Zn cell.Beyond that,the Zn-ion hybrid micro-capacitor employing PACXHE exhibits satisfactory cycling stability,energy density,and practicality for energy storage in flexible,intelligent electronics.The present polyanionic-based hydrogel strategy and the development of PACXHE represent significant advancements in the design of hydrogel electrolytes,paving the way for a more sustainable and efficient future in the energy storage field.
基金This work is supported by Singapore Ministry of Education academic research grant Tier 2 (MOE2019-T2-1-181).
文摘Li metal anode holds great promise to realize high-energy battery systems.However,the safety issue and limited lifetime caused by the uncontrollable growth of Li dendrites hinder its commercial application.Herein,an interlayer-bridged 3D lithiophilic rGO-Ag-S-CNT composite is proposed to guide uniform and stable Li plating/stripping.The 3D lithiophilic rGO-Ag-S-CNT host is fabricated by incorporating Ag-modified reduced graphene oxide(rGO)with S-doped carbon nanotube(CNT),where the rGO and CNT are closely connected via robust Ag-S covalent bond.This strong Ag-S bond could enhance the structural stability and electrical connection between rGO and CNT,significantly improving the electrochemical kinetics and uniformity of current distribution.Moreover,density functional theory calculation indicates that the introduction of Ag-S bond could further boost the binding energy between Ag and Li,which promotes homogeneous Li nucleation and growth.Consequently,the rGO-Ag-S-CNT-based anode achieves a lower overpotential(7.3 mV at 0.5 mA cm^(−2)),higher Coulombic efficiency(98.1%at 0.5 mA cm^(−2)),and superior long cycling performance(over 500 cycles at 2 mA cm−2)as compared with the rGO-Ag-CNT-and rGO-CNT-based anodes.This work provides a universal avenue and guidance to build a robust Li metal host via constructing a strong covalent bond,effectively suppressing the Li dendrites growth to prompt the development of Li metal battery.
基金financial support from the Natural Sciences and Engineering Research Council of Canada(NSERC)Institut National de la Recherche Scientifique(INRS)
文摘When I read the paper“Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries”from Prof.Jianmin Ma’s group,which was published in Science Bulletin(doi.org/10.1016/j.scib.2020.09.018),I felt excited as presented a multi-factor principle for applying potassium perfluorinated sulfonates to suppress the dendrite growth and protect the cathode from the viewpoint of electrolyte additives.The effects of these additives are revealed through experimental results,molecular dynamics simulations and first-principle calculations.Specifically,it involves the influence of additives on Li^(+)solvation structure,solid electrolyte interphase(SEI),Li growth and nucleation.Following the guidance of the multi-factor principle,every part of the additive molecule should be utilized to regulate electrolytes.This multifactor principle for electrolyte additive molecule design(EAMD)offers a unique insight on understanding the electrochemical behavior of iontype electrolyte additives on both the Li metal anode and high-voltage cathode.In these regards,I would be delighted to write a highlight for this innovative work and,hopefully,it may raise more interest in the areas of electrolyte additives.
基金supported by the National Natural Science Foundation of China(no.22208039)China Association for Science and Technology Youth Talent Sup(214024000090)+1 种基金Dalian Science and Technology Talent Innovation Support Plan(2022RQ036)Basic Scientific Program of Education Department of Liaoning Province(LJKMZ20220878).
文摘Building lithium fluoride(LiF)-rich solid electrolyte interphases(SEIs)by the decomposition of fluorinated salts has been widely adopted to be effective to suppress lithium dendrite growth,thus prolonging the lifespan of fast-charging lithium metal batteries(LMBs).Nevertheless,the slow dissociation of LiF salts reduces both their utilization and the formation of inorganic SEI.Herein,cellulose acetate(CA)was incorporated into the electrolyte to create an inorganic-rich SEI through ester groups,where the lithiophilic oxygen atoms in the ester group(C═O)enhanced lithium-ion diffusion and anion dissociation rates.Therefore,rapid ion diffusion and dendrite-free anodes were achieved in the ester-based electrolyte with CA(named as CA-E).As a result,the lithium symmetric batteries with the CA-E electrolyte exhibited stable cycling performance for 5,000 h at a current density/capacity of 3 mA cm^(-2)/1 mAh cm^(-2),while a short-circuiting was observed after~450 h for the bare electrolyte.Benefiting from the rational design,lithium iron phosphate batteries with the CA-E electrolyte showed an excellent C-rate performance with a capacity of 100.7 mAh g^(−1) at the rate of 10 C.Moreover,a specific capacity of 110.3 mAh g^(−1) was maintained after 300 cycles at the rate of 6 C with a Coulombic efficiency of 99.87%.This work proposes a new approach to dendrite inhibitors for fast-charging LMBs.
基金supported by the National Key R&D Program of China(2021YFA1201800)the Fundamental Research Funds for the Central Universities(WK3430000007).
文摘Rechargeable aqueous zinc batteries(RAZBs)offer a promising solution for large-scale energy storage due to the abundance,low cost,and safety of Zn.However,practical applications are hindered by Zn anode instability,dendrite growth,and hydrogen evolution reactions(HER).Chaotropic Zn(ClO_(4))2 electrolytes are favorable for low-temperature operations but exacerbate these issues due to their high acidity,leading to severe Zn corrosion and layered double hydroxide formation.We propose a biomimetic strategy using methylguanidoacetic acid(creatine)as a low-cost,eco-friendly additive to address these challenges.Creatine acts as a proton pocket to finely tune the pH of acidic Zn(ClO_(4))2 electrolytes for suppressing HER and stabilizing the Zn anode.Furthermore,the formed creatinine cations adsorb on the Zn surface,promoting highly controlled Zn deposition with a preferred(002)orientation.This approach significantly enhances battery cycling performance,with Zn||Zn cells demonstrating extended cycling stability at both low and high current densities.Zn||Cu cells exhibited improved Coulombic efficiency over thousands of cycles,indicating highly reversible Zn plating/stripping.Notably,stable cell operations were realized at the temperature as low as−35℃ without electrolyte freezing.Our findings highlight the potential of biomimetic proton regulation and interfacial modulation for improving the stability and reversibility of Zn plating/stripping in RAZBs.
基金support from the National Natural Science Foundation of China(Nos.22075313 and 21975281)the National Key Research and Development Program of China(No.2020YFB1312902)+3 种基金the Science and Technology Project of Jiangxi Province(No.20192BCD40017)Outstanding Youth Fund of Jiangxi Province(No.20192BCB23028)Jiangxi Double Thousand Talent Program(No.JXSQ2019101072)Science Technology Major Project of Nanchang(No.2020BI47)is acknowledged.
文摘Aqueous zinc battery has been regarded as one of the most promising energy storage systems due to its low cost and environmental benignity.However,the safety concern on Zn anodes caused by uncontrolled Zn dendrite growth in aqueous electrolyte hinders their application.Herein,sucrose with multi-hydroxyl groups has been introduced into aqueous electrolyte to modify Zn^(2+)solvation environment and create a protection layer on Zn anode,thus effectively retarding the growth of zinc dendrites.Atomistic simulations and experiments confirm that sucrose molecules can enter into the solvation sheath of Zn^(2+),and the as-formed unique solvation structure enhances the mobility of Zn^(2+).Such fast Zn^(2+)kinetics in sucrose-modified electrolyte can successfully suppress the dendrite growth.With this sucrose-modified aqueous electrolyte,Zn/Zn symmetric cells present more stable cycle performance than those using pure aqueous electrolyte;Zn/C cells also deliver an impressive higher energy density of 129.7 Wh·kg^(−1)and improved stability,suggesting a great potential application of sucrose-modified electrolytes for future Zn batteries.
基金Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts and Telecommunications,Grant/Award Numbers:GDX2022010010,GZR2022010017National Natural Science Foundation of China,Grant/Award Numbers:52102265,91963119+4 种基金Postdoctoral Research Foundation of China,Grant/Award Number:2020M681681Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications,Grant/Award Numbers:NY220069,NY220085,NY223054Priority Academic Program Development of Jiangsu Higher Education Institutions,Grant/Award Number:YX030003Natural Science Foundation of Jiangsu Province,Grant/Award Number.BK20210604King Abdullah University of Science and Technology。
文摘Aqueous zinc(Zn)ion batteries(AZIBs)are regarded as one of the promising candidates for next-generation electrochemical energy storage systems due to their low cost,high safety,and environmental friendliness.However,the commercialization of AZIBs has been severely restricted by the growth of dendrite at the Zn metal anode.Tailoring the planar-structured Zn anodes into threedimensional(3D)structures has proven to be an effective way to modulate the plating/stripping behavior of Zn anodes,resulting in the suppression of dendrite formation.This review provides an up-to-date review of 3D structured Zn metal anodes,including working principles,design,current status,and future prospects.We aim to give the readers a comprehensive understanding of 3D-structured Zn anodes and their effective usage to enhance AZIB performance.
基金the National Natural Science Foundation of China(Nos.51904344 and 52172264)the Natural Science Foundation of Hunan Province of China(Nos.2021JJ10060 and 2022GK2033).
文摘Lithium metal batteries(LMBs)based on metallic Li exhibit high energy density to be competent for advanced energy storage applications.However,the unstable solid electrolyte interphase(SEI)layer due to continuous decomposition of electrolytes,and the attendant problem of Li dendrite growth frustrate their commercialization process.Herein,a hybrid SEI comprising abundant LiF,lithiophilic Li-Ge alloy,and Ge nanoparticles is constructed via a simple brush coating method.This fluorinated interface layer with embedded Ge-containing components isolates the Li anode from the corrosive electrolyte and facilitates homogenous Li nucleation as well as uniform growth.Consequently,the modified Li anode exhibits remarkable stability without notorious Li dendrites,delivering stable cycling lives of more than 1000 h for symmetric Li||Li cells and over 600 cycles for Li||Cu cells at 1 mA·cm^(−2).Moreover,the reinforced Li anodes endow multiple full-cell architectures with dramatically improved cyclability under different test conditions.This work provides rational guidance to design an artificial hybrid SEI layer and would stimulate more ideas to solve the dendrite issue and promote the further development of advanced LMBs.
基金supported by King Abdullah University of Science and Technology(KAUST),the Project of State Key Laboratory of Organic Electronics and Information Displays,Nanjing University of Posts and Telecommunications(Nos.GZR2022010017 and GDX2022010010)the National Natural Science Foundation of China(NSFC,No.91963119 and 52102265)+4 种基金China Postdoctoral Science Foundation(No.2020M681681)Jiangsu Provincial NSF(No.BK20210604)Research Startup Fund from Nanjing University of Posts and Telecommunications(NJUPT,Nos.NY220069 and NY220085)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD,No.YX030003)Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM).
文摘Rechargeable aqueous zinc(Zn)ion batteries(AZIBs)using low-cost and safe Zn metal anodes are considered promising candidates for future grid-scale energy storage systems,but the Zn dendrite problem severely hinders the further prospects of AZIBs.Regulating Zn depositing behaviors toward horizontal alignment is highly effective and thus has received huge attention.However,such a strategy is usually based on previous substrate engineering,which requires complex preparation or expensive equipment.Therefore,it is essential to develop a novel solution that can realize horizontally aligned Zn flake deposition via easy operation and low cost.Herein,we report an ultrathin and robust Kevlar membrane as the interlayer to mechanically suppress Zn dendrite growth.Compared to the randomly distributed flaky dendrites in the control group,the deposited Zn sheets would grow into parallel alignment with the existence of such interlayer.As the dendrites are effectively suppressed,Zn||Cu asymmetric,Zn||Zn symmetric,and Zn||MnO_(2)full batteries using Kevlar interlayer deliver significantly improved cycling stabilities.Furthermore,the Zn||MnO_(2)pouch cell using a Kevlar interlayer delivers stable cycling performance and shows stable operation during multi-angle folding.We believe this work provides a new possibility for regulating Zn deposition from a crystallographic perspective.
