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
Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two crit...Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.展开更多
Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from ...Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from low room-temperature ionic conductivity and poor mechanical strength.Composite solid electrolytes(CSEs)incorporating inorganic filler offer promise but are hindered by poor interfacial compatibility.This study addresses this critical issue through surface engineering.Mercaptopropyl trimethoxysilane(MPTMS)is used to modify garnet-type Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)particles,introducing thiol groups(-SH)onto their surface.Subsequently,thiol-functionalized LLZTO(LLZTO@MPTMS)participate in the insitu copolymerization of polyethylene glycol methyl methacrylate(PEGMEMA)and crosslinker polyethylene glycol dimethacrylate(PEGDMA),yielding a novel PEO-based CSE(PCSE).The effects of PEGMEMA molecular weight,PEGMEMA/PEGDMA ratio,and LLZTO@MPTMS content have been systematically examined to optimize the electrolyte.The resulting PCSE exhibits an ionic conductivity of 1.20×10^(-4)S·cm^(-1)at 30℃,a lithium-ion transference number of 0.36,and a wide electrochemical stability window up to 5.1 V(vs.Li^(+)/Li).Li/PCSE/Li symmetric cells demonstrate stable cycling for nearly 240 h at 0.05 mA·cm^(-2),indicating enhanced interface compatibility with lithium metal and effective dendrite suppression.Furthermore,LiFePO_(4)/PCSE/Li full cells deliver a high initial discharge capacity of 155.0 mAh·g^(-1)at 0.1 C and retain 76.0%capacity after 100 cycles,alongside excellent rate capability.These results confirm that the combined strategy of LLZTO surface modification with MPTMS and in-situ copolymerization effectively mitigates interfacial issues,presenting a promising material system for high-performance solid-state LIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region inter...Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.展开更多
Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(...Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.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
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
As the transition to renewable energy accelerates,sodium metal batteries have emerged as a viable and economical substitute for lithium-ion technology.The unstable solid electrolyte interphase on sodium metal anodes c...As the transition to renewable energy accelerates,sodium metal batteries have emerged as a viable and economical substitute for lithium-ion technology.The unstable solid electrolyte interphase on sodium metal anodes continues to provide a significant challenge to attaining long-term cycle stability and safety.Natural solid electrolyte interphase layers frequently demonstrate inadequate mechanical integrity and deficient ionic conductivity,resulting in dendritic formation,diminished Coulombic efficiency,and capacity degradation.展开更多
Solid polymer electrolytes(SPEs)offer enhanced safety for next-generation lithium-ion batteries(LIBs)but typically suffer from low lithium-ion transference numbers(t_(Li^(+))),leading to concentration polarization and...Solid polymer electrolytes(SPEs)offer enhanced safety for next-generation lithium-ion batteries(LIBs)but typically suffer from low lithium-ion transference numbers(t_(Li^(+))),leading to concentration polarization and dendritic growth.To address this,we designed a boron-containing SPE(GBOEE)leveraging the electron-deficient nature of boron to immobilize anions.Thermogravimetric analysis revealed the stability of GBOEE up to 284.9℃.The optimized GBOEE-6.7 exhibited a high t_(Li^(+))of 0.49 and an ionic conductivity of 5.75×10^(-5)S·cm^(-1)at 30℃,with a 5.15 V electrochemical window.Symmetric Li//Li cells demonstrated stable cycling for 600 h at 0.05 mA·cm^(-2)with minimal polarization(0.15 V).LiFePO_(4)//Li cells delivered a high initial discharge capacity of 153.4 mAh·g^(-1)and 99.7%capacity retention after 100 cycles at 0.1 C.These results underscore the effectiveness of boron integration in designing high-performance,dendrite-suppressing SPEs for safe lithiummetal batteries(LMBs).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
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
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
Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the...Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.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
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
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
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
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the financial support from the Natural Science Foundation of Jiangsu Province(BK20231292)the Jiangsu Agricultural Science and Technology Innovation Fund(CX(24)3091)+6 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX25_1429)the National Key R&D Program of China(2024YFE0109200)the Fundamental Research Funds for the Central Universities(No.2024300440)Guangdong Basic and Applied Basic Research Foundation(2025A1515011098)the National Natural Science Foundation of China(12464032)the Natural Science Foundation of Jiangxi Province(20232BAB201032)Ji'an Science and Technology Plan Project(2024H-100301)。
文摘Zn-I_(2) batteries have emerged as promising next-generation energy storage systems owing to their inherent safety,environmental compatibility,rapid reaction kinetics,and small voltage hysteresis.Nevertheless,two critical challenges,i.e.,zinc dendrite growth and polyiodide shuttle effect,severely impede their commercial viability.To conquer these limitations,this study develops a multifunctional separator fabricated from straw-derived carboxylated nanocellulose,with its negative charge density further reinforced by anionic polyacrylamide incorporation.This modification simultaneously improves the separator’s mechanical properties,ionic conductivity,and Zn^(2+)ion transfer number.Remarkably,despite its ultrathin 20μm profile,the engineered separator demonstrates exceptional dendrite suppression and parasitic reaction inhibition,enabling Zn//Zn symmetric cells to achieve impressive cycle life(>1800 h at 2 m A cm^(-2)/2 m Ah cm^(-2))while maintaining robust performance even at ultrahigh areal capacities(25 m Ah cm^(-2)).Additionally,the separator’s anionic characteristic effectively blocks polyiodide migration through electrostatic repulsion,yielding Zn-I_(2) batteries with outstanding rate capability(120.7 m Ah g^(-1)at 5 A g^(-1))and excellent cyclability(94.2%capacity retention after 10,000 cycles).And superior cycling stability can still be achieved under zinc-deficient condition and pouch cell configuration.This work establishes a new paradigm for designing high-performance zinc-based energy storage systems through rational separator engineering.
基金supported by the 2024 Capital Construction Funds within the Provincial Budget of Jilin Provincial Development and Reform Commission[2024C018-2].
文摘Traditional lithium-ion batteries(LIBs)employing liquid electrolytes face inherent safety risks,motivating the development of solid polymer electrolytes(SPEs)like polyethylene oxide(PEO).However,pure PEO suffers from low room-temperature ionic conductivity and poor mechanical strength.Composite solid electrolytes(CSEs)incorporating inorganic filler offer promise but are hindered by poor interfacial compatibility.This study addresses this critical issue through surface engineering.Mercaptopropyl trimethoxysilane(MPTMS)is used to modify garnet-type Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)particles,introducing thiol groups(-SH)onto their surface.Subsequently,thiol-functionalized LLZTO(LLZTO@MPTMS)participate in the insitu copolymerization of polyethylene glycol methyl methacrylate(PEGMEMA)and crosslinker polyethylene glycol dimethacrylate(PEGDMA),yielding a novel PEO-based CSE(PCSE).The effects of PEGMEMA molecular weight,PEGMEMA/PEGDMA ratio,and LLZTO@MPTMS content have been systematically examined to optimize the electrolyte.The resulting PCSE exhibits an ionic conductivity of 1.20×10^(-4)S·cm^(-1)at 30℃,a lithium-ion transference number of 0.36,and a wide electrochemical stability window up to 5.1 V(vs.Li^(+)/Li).Li/PCSE/Li symmetric cells demonstrate stable cycling for nearly 240 h at 0.05 mA·cm^(-2),indicating enhanced interface compatibility with lithium metal and effective dendrite suppression.Furthermore,LiFePO_(4)/PCSE/Li full cells deliver a high initial discharge capacity of 155.0 mAh·g^(-1)at 0.1 C and retain 76.0%capacity after 100 cycles,alongside excellent rate capability.These results confirm that the combined strategy of LLZTO surface modification with MPTMS and in-situ copolymerization effectively mitigates interfacial issues,presenting a promising material system for high-performance solid-state LIBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.52125405 and U22A20108)Thailand Science Research and Innovation Fund Chulalongkorn University,National Research Council of Thailand(NRCT)and Chulalongkorn University(N42A660383).D.D.Zhang would like to thank the financial support from the Scientific Research Fund of Liaoning Provincial Education Department of China(No.JYTQN2023289)+3 种基金Liaoning Provincial Science and Technology Joint Plan(Fund)Project(No.2023-BSBA-259)and the opening project of State Key Laboratory of Metastable Materials Science and Technology,Yanshan University(No.202404).J.Cao would like to acknowledge the support from National Natural Science Foundation of China(Grant No.52402279)China Postdoctoral Science Foundation Special Funding(Grant Nos.2025T180002,2024M751753)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(No.202401).
文摘Aqueous zinc-ion batteries(AZIBs)offer promising safety and affordability,but suffer from dendritic Zn growth and parasitic side reactions at the electrode-electrolyte interface.Herein,we construct a dual-region interfacial modulation framework by molecularly reconfiguring the Helmholtz double layer via trace methyl methacrylate(MMA).Exploiting its amphiphilic and functionally asymmetric architecture,MMA enables a coordinated interfacial reconstruction that disrupts Zn^(2+)solvation in the outer Helmholtz plane,builds a chemisorbed coordination layer in the inner plane,and modulates local interfacial chemistry with spatial precision.This dualregion regulation collectively suppresses water reactivity,facilitates Zn^(2+)desolvation,and drives crystallo-graphically preferred deposition along the(101)plane,promoting lateral growth and mitigating dendrite for-mation.As a result,symmetric Zn||Zn cells exhibit over 4200 h of stable cycling at 1 mA cm^(-2) and maintain 1100 h of operation at 2 mA cm^(-2),even at 0℃.Zn||Ti half-cells achieve a Coulombic efficiency of 99.83%,while Zn||NH_(4)V_(4)O_(10) full cells deliver 93.92%capacity retention after 400 cycles at 2 A g^(-1),and preserve 85.3%after 300 cycles at 0℃.This work demonstrates a scalable,mechanism-driven electrolyte design paradigm for dendrite-free and high-performance aqueous Zn metal batteries.
基金supported by the National Natural Science Foundation of China(22269020,42167068,U23A20582)the Gansu Province Higher Education Industry Support Plan Project(2023CYZC-17,2023CYZC-68)+1 种基金the Key Project of Natural Science Foundation of Gansu Province(25JRRA004)2024 Major Cultivation Project for University Research and Innovation Platforms(2024CXPT-10).
文摘Aqueous Zn-ion storage offers high capacity and safety,but practical use is hindered by dendrite formation,side reactions,and hydrogen evolution,affecting stability and efficiency.Herein,tetramethylol acetylenediurea(TA)is proposed as an effective electrolyte additive that modulates the Zn^(2+)deposition environment via coordination competition.The polar functional groups of TA restructure the solvation sheath,while its molecular dipoles generate localized electric fields that accelerate Zn^(2+)migration and promote directional(002)-oriented deposition.These effects collectively suppress side reactions and enhance Zn plating/stripping reversibility.The four hydroxyl(–OH)and conjugated ketone groups(C=O)in the TA molecule have strong coordination ability(Lewis basicity)and can form a stable[Zn(TA)(H_(2)O)_(n)]^(2+)with Zn^(2+),reducing the number of free water molecules and the proportion of active water in the solvation sheath.The TA molecules are adsorbed onto the Zn anode surface,leading to the redistribution of the local spatial electric field and homogenization of ion flux dynamics.Its conjugated planar structure can induce Zn^(2+)to preferentially deposit along the(002)crystal plane.Zn//Zn symmetric cell using TA-containing ZnSO4 electrolyte exhibits stable cycling for more than 2240 h at 1 mA cm^(−2),1 mAh cm^(−2).The Zn//activated carbon(AC)full-cell can stably cycle 30,000 cycles at 5 A g^(−1)with a capacity retention rate of 90%.This study provides important insights into electrolyte engineering strategies for stabilizing Zn anodes,highlighting the potential of molecular design additives in next-generation Zn^(2+)energy storage systems.
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(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financially supported by the National Natural Science Foundation of China(Nos.52271211,52203043,and 52072120)the Science and Technology Innovation Program of Hunan Province(No.2023RC3185),Chinathe HORIZONMarie Skøodowska-Curie Actions-2021-PF(No.101065098),European Union.
文摘As the transition to renewable energy accelerates,sodium metal batteries have emerged as a viable and economical substitute for lithium-ion technology.The unstable solid electrolyte interphase on sodium metal anodes continues to provide a significant challenge to attaining long-term cycle stability and safety.Natural solid electrolyte interphase layers frequently demonstrate inadequate mechanical integrity and deficient ionic conductivity,resulting in dendritic formation,diminished Coulombic efficiency,and capacity degradation.
基金supported by the 2024 Capital Construction Funds within the Provincial Budget of Jilin Provincial Development and Reform Commission[2024C018-2].
文摘Solid polymer electrolytes(SPEs)offer enhanced safety for next-generation lithium-ion batteries(LIBs)but typically suffer from low lithium-ion transference numbers(t_(Li^(+))),leading to concentration polarization and dendritic growth.To address this,we designed a boron-containing SPE(GBOEE)leveraging the electron-deficient nature of boron to immobilize anions.Thermogravimetric analysis revealed the stability of GBOEE up to 284.9℃.The optimized GBOEE-6.7 exhibited a high t_(Li^(+))of 0.49 and an ionic conductivity of 5.75×10^(-5)S·cm^(-1)at 30℃,with a 5.15 V electrochemical window.Symmetric Li//Li cells demonstrated stable cycling for 600 h at 0.05 mA·cm^(-2)with minimal polarization(0.15 V).LiFePO_(4)//Li cells delivered a high initial discharge capacity of 153.4 mAh·g^(-1)and 99.7%capacity retention after 100 cycles at 0.1 C.These results underscore the effectiveness of boron integration in designing high-performance,dendrite-suppressing SPEs for safe lithiummetal batteries(LMBs).
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 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(No.22179093 and 21905202)。
文摘Aqueous zinc-ion batteries(AZIBs)are considered promising for safe,low-cost,and sustainable energy storage.However,their practical deployment is critically hindered by dendrite formation and parasitic reactions at the Zn anode-electrolyte interface.To address this challenge,we present a self-assembly strategy to construct vertically aligned organic-inorganic hybrid nanosheet arrays composed of polyethyleneimine-zinc hydroxide sulfate(PEI-ZHS)via a simple coating-immersion method.The protonation of polyethyleneimine in ZnSO_(4) electrolyte provides localized alkaline conditions for controlled nucleation and growth of ZHS nanosheets at the anode interfa ce.This vertically aligned na noarchitectu re allows for fast Zn^(2+)transport and even nucleation by providing abundant oriented ion-conductive microchannels and accelerating desolvation.Benefiting from these characteristics,the PEI-ZHS layer effectively mitigates side reactions and dendrite growth.As a result,the modified zinc anodes achieve excellent cycling lifespans of 5200 and 1200 h at 1 mA cm^(-2)/1 mAh cm^(-2) and 5 mA cm^(-2)/5 mAh cm^(-2),respectively,in symmetric cells.The Zn‖I_(2) full cell also shows great reversibility,retaining 93.02%of initial capacity after 4000 cycles at 1 A g^(-1).This work introduces a thermodynamically guided and scalable interfacial engineering approach that advances the stability and performance of Zn metal anodes in AZIBs.
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.
