High voltage is necessary for high energy lithium-ion batteries but difficult to achieve because of the highly deteriorated cyclability of the batteries.A novel strategy is developed to extend cyclability of a high vo...High voltage is necessary for high energy lithium-ion batteries but difficult to achieve because of the highly deteriorated cyclability of the batteries.A novel strategy is developed to extend cyclability of a high voltage lithium-ion battery,LiNi_(0.5)Mn_(1.5)O_(4)/Graphite(LNMO/Graphite)cell,which emphasizes a rational design of an electrolyte additive that can effectively construct protective interphases on anode and cathode and highly eliminate the effect of hydrogen fluoride(HF).5-Trifluoromethylpyridine-trime thyl lithium borate(LTFMP-TMB),is synthesized,featuring with multi-functionalities.Its anion TFMPTMB-tends to be enriched on cathode and can be preferentially oxidized yielding TMB and radical TFMP-.Both TMB and radical TFMP can combine HF and thus eliminate the detrimental effect of HF on cathode,while the TMB dragged on cathode thus takes a preferential oxidation and constructs a protective cathode interphase.On the other hand,LTFMP-TMB is preferentially reduced on anode and constructs a protective anode interphase.Consequently,a small amount of LTFMP-TMB(0.2%)in 1.0 M LiPF6in EC/DEC/EMC(3/2/5,wt%)results in a highly improved cyclability of LNMO/Graphite cell,with the capacity retention enhanced from 52%to 80%after 150 cycles at 0.5 C between 3.5 and 4.8 V.The as-developed strategy provides a model of designing electrolyte additives for improving cyclability of high voltage batteries.展开更多
Aqueous zinc-ion capacitors (ZICs) are considered as potential candidates for next generation electrochemical energy storage devices due to their high safety and low cost.However,the existing aqueous ZICs usually have...Aqueous zinc-ion capacitors (ZICs) are considered as potential candidates for next generation electrochemical energy storage devices due to their high safety and low cost.However,the existing aqueous ZICs usually have the problems of zinc dendrite growth and unsatisfactory performance at low temperature.Herein,an erythritol (Eryt) additive with inhibition of zinc dendrites and anti-freezing capability was introduced into the ZnSO4electrolyte.The experimental characterization and theoretical calculation confirm that the Eryt adsorbed on the surface of zinc anodes regulates the deposition orientation of Zn^(2+) and inhibits the formation of dendrites.It also reconstructs the solvation structure in the electrolyte to reduce water activity,enabling the electrolyte to have a lower freezing point for operation at low temperature.With the assistance of Eryt,the Zn||Zn symmetric cell exhibits a long cycle life of 2000 h,while the ZIC assembled with activated carbon (AC) cathode and zinc anode (Zn||AC) maintains a capacity retention of 98.2% after 30,000 cycles at a current density of 10 A g^(-1)(even after 10,000 cycles at-20°C,the capacity retention rate reached 94.8%.).This work provides a highly scalable,low-cost and effective strategy for the protection of the anodes of low-temperature aqueous ZICs.展开更多
Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on...Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries.In this study,methyl vinyl sulfone(MVS),a sulfone-based functional electrolyte additive,is used in an additive engineering strategy to control Lielectrolyte interactions and address the aforementioned problems.Li dendrite growth may be restricted,and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer.The electrochemical performance of an ethylene carbonate/dimethyl carbonate(EC/DMC)+1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability,maintaining a low overvoltage for over 750 h at 1 mA cm^(-2),and capacity of 1 mA h cm^(-2).Additionally,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g^(-1).This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.展开更多
Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic re...Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.展开更多
The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side reactio...The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side reactions.Herein,to stabilize both zinc anodes and water molecules,we developed a modified electrolyte by adding a trace amount of N,N-diethylformanmide(DEF)into the ZnSO_(4)electrolyte for the first time in zinc ion batteries.The effectiveness of DEF is predicted by the comparison of donor number and its preferential adsorption behavior on the zinc anode is further demonstrated by several spectroscopy characterizations,electrochemical methods,and molecular dynamics simulation.The modified electrolyte with 5%v.t.DEF content can ensure a stable cycling life longer than 3400 h of Zn‖Zn symmetric cells and an ultra-reversible Zn stripping/plating process with a high coulombic efficiency of 99.7%.The Zn‖VO_(2)full cell maintains a capacity retention of 83.5%and a 104 mA h g^(-1)mass capacity after 1000cycles.This work provides insights into the role of interfacial adsorption behavior and the donor number of additive molecules in designing low-content and effective aqueous electrolytes.展开更多
Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theor...Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theory calculation,and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts,magnesium bis(trifluoromethanesulfonyl)imide(MgTFSI_(2)),and MgCl_(2),with different additives in 1,2-dimethoxyethane(DME)solvent.We found that the formed[Mg_(3)(μ-Cl)_(4)(DME)mTFSI_(2)](m=3,5)inner-shell solvation clusters in MgTFSI_(2)-MgCl_(2)/DME electrolyte could easily decompose and form a MgO-and MgF_(2)-rich SEI.Such electron-rich inorganic species in the SEI,especially MgF_(2),turned out to be detrimental for Mg plating/stripping.To reduce the MgF_(2)and MgO contents in SEI,we introduce an electron-deficient tri(2,2,2-trifluoroethyl)borate(TFEB)additive in the electrolyte.Mg//Mg cells using the MgTFSI_(2)-MgCl_(2)/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of~150 mV.Even with the presence of 800 ppm H_(2)O,the electrolyte with TFEB additive could still preserve its good electrochemical performance.The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo6S8 and Mg//CuS full cells,showing great potential for future applications.展开更多
Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environ...Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.展开更多
B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)t...B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)to facilitate the rapid Li+migration.Nevertheless,its wide-temperature application has been limited by the instability of B-derived CEI layer at high temperature.Herein,dual electrolyte additives,consisting of lithium tetraborate(Li_(2)TB)and 2,4-difluorobiphenyl(FBP),are proposed to boost the widetemperature performances of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)cathode.Theoretical calculation and electrochemical performances analyses indicate that Li_(2)TB and FBP undergo successive decomposition to form a unique dual-layer CEI.FBP acts as a synergistic filming additive to Li_(2)TB,enhancing the hightemperature performance of NCM cathode while preserving the excellent low-temperature cycle stability and the superior rate capability conferred by Li_(2)TB additive.Therefore,the capacity retention of NCM‖Li cells using optimal FBP-Li_(2)TB dual electrolyte additives increases to 100%after 200 cycles at-10℃,99%after 200 cycles at 25℃,and 83%after 100 cycles at 55℃,respectively,much superior to that of base electrolyte(63%/69%/45%).More surprisingly,galvanostatic c ha rge/discharge experiments at different temperatures reveal that NCM‖Li cells using FBP-Li_(2)TB additives can operate at temperatures ranging from-40℃to 60℃.This synergistic interphase modification utilizing dual electrolyte additives to construct a unique dual-layer CEI adaptive to a wide temperature range,provides valuable insights to the practical applications of NCM cathodes for all-climate batteries.展开更多
The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capac...The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capacity,energy density,service life,and rate discharge performance.By raising the voltage at the charge/discharge plateau,the energy density of the battery is increased.However,this causes transition metal dissolution,irreversible phase changes of the cathode active material,and parasitic electrolyte oxidation reactions.This article presents an overview of these concerns to provide a clear explanation of the issues involved in the development of electrolytes for high-voltage lithium-ion batteries.Additionally,solidstate electrolytes enable various applications and will likely have an impact on the development of batteries with high energy densities.It is necessary to improve the high-voltage performance of electrolytes by creating solvents with high thermal stabilities and high voltage resistance and additives with superior film forming performance,multifunctional capabilities,and stable lithium salts.To offer suggestions for the future development of high-energy lithium-ion batteries,we conclude by offering our own opinions and insights on the current development of lithium-ion batteries.展开更多
The Li metal battery with ultrahigh-nickel cathode(LiNi_(x)M_(1-x)O_(2),M=Mn,Co,and x≥0.9)under high-voltage is regarded as one of the most promising approaches to fulfill the ambitious target of 400 Wh/kg.However,th...The Li metal battery with ultrahigh-nickel cathode(LiNi_(x)M_(1-x)O_(2),M=Mn,Co,and x≥0.9)under high-voltage is regarded as one of the most promising approaches to fulfill the ambitious target of 400 Wh/kg.However,the practical application is impeded by the instability of electrode/electrolyte interface and Ni-rich cathode itself.Herein we proposed an electron-defect electrolyte additive trimethyl borate(TMB)which is paired with the commercial carbonate electrolyte to construct highly conductive fluorine-and boron-rich cathode electrolyte interface(CEI)on LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)surface and solid electrolyte interphase(SEI)on lithium metal surface.The modified CEI effectively mitigates the structural transformation from layered to disordered rock-salt phase,and consequently alleviate the dissolution of transition metal ions(TMs)and its“cross-talk”effect,while the enhanced SEI enables stable lithium plating/striping and thus demonstrated good compatibility between electrolyte and lithium metal anode.As a result,the common electrolyte with 1 wt%TMB enables 4.7 V NCM90/Li cell cycle stably over 100 cycles with 70%capacity retention.This work highlights the significance of the electron-defect boron compounds for designing desirable interfacial chemistries to achieve high performance NCM90/Li battery under high voltage operation.展开更多
Electrolytic aqueous zinc-manganese(Zn–Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn–Mn batteries is the sluggish...Electrolytic aqueous zinc-manganese(Zn–Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn–Mn batteries is the sluggish deposition reaction kinetics of manganese oxide during the charge process and short cycle life. We show that, incorporating ZnO electrolyte additive can form a neutral and highly viscous gel-like electrolyte and render a new form of electrolytic Zn–Mn batteries with significantly improved charging capabilities. Specifically, the ZnO gel-like electrolyte activates the zinc sulfate hydroxide hydrate assisted Mn^(2+) deposition reaction and induces phase and structure change of the deposited manganese oxide(Zn_(2)Mn_(3)O_8·H_(2)O nanorods array), resulting in a significant enhancement of the charge capability and discharge efficiency. The charge capacity increases to 2.5 mAh cm^(-2) after 1 h constant-voltage charging at 2.0 V vs. Zn/Zn^(2+), and the capacity can retain for up to 2000 cycles with negligible attenuation. This research lays the foundation for the advancement of electrolytic Zn–Mn batteries with enhanced charging capability.展开更多
Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious sid...Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.展开更多
Lithium-metal battery based on Ni-rich cathode provides high energy density but presents poor cyclic stability due to the unstable electrode/electrolyte interfaces on both cathode and anode.In this work,we report a ne...Lithium-metal battery based on Ni-rich cathode provides high energy density but presents poor cyclic stability due to the unstable electrode/electrolyte interfaces on both cathode and anode.In this work,we report a new strategy to address this issue.It is found that the cyclic stability of Ni-rich/Li battery can be significantly improved by using succinic anhydride(SA) as an electrolyte additive.Specifically,the capacity retention of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/Li cell is improved from 14% to 83% after 200cycles at 1 C between 3.0 and 4.35 V by applying 5% SA.The underlying mechanism of SA contribution is understood by comparing the effects of malic anhydride(MA) and citraconic anhydride(CA), both of which share a similar molecular structure to SA but show different effects.On anode side,SA can but MA and CA cannot form a protective solid electrolyte interphase(SEI) on Li anode.On cathode side,three anhydrides can suppress the formation of hydrogen fluoride from electrolyte oxidation decomposition,but SA behaves best.Typically,MA shows adverse effects on the interface stability of Li anode and NCM811 cathode,which originates from its high acidity.Though the acidity of MA can be mitigated by substituting a methyl for one H atom at its C=C bond,the substituent CA cannot compete with SA in cyclic stability improvement of the cell,because the SEI resulting from CA is not as robust as that from SA,which is related to the binding energy of the SEI components.This understanding reveals the importance of the electrolyte acidity on the Ni-rich cathode and the robustness of the SEI on Li anode,which is helpful for rationally designing new electrolyte additives to further improve the cyclic stability of high-energydensity Ni-rich/Li batteries.展开更多
The feasibility for natural graphite(NG)to replace artificial graphite(AG)in organic electrolytes with different additives are investigated.Although the strong film-forming additives contributes to form robust solid e...The feasibility for natural graphite(NG)to replace artificial graphite(AG)in organic electrolytes with different additives are investigated.Although the strong film-forming additives contributes to form robust solid electrolyte interphase(SEI)film on graphite particle surface,great differences in gas evolution,lithium inventory loss and other side reactions are observed.Lithium bis(oxalato)borate(Li BOB)and fluoroethylene carbonate(FEC)are found more effective and the combination shows to be more promising.In the optimized electrolyte,natural graphite anode exhibits excellent long-term cycling capability.After 800 cycles at high temperature,the capacity retention is comparable to that using artificial graphite.The mechanisms for the capacity-fading of the full cells with AG and NG anode are investigated by ICP,SEM and polarization studies.The results shows that NG electrode consumes more active lithium due to the rough surface and larger volume expansion.The rapid capacity-fading in the initial 100 cycles is related to the instability of the SEI film aroused from large volume expansion.The systematic analysis is inspiriting for the development of high performance lithium ion batteries with reduced cost.展开更多
Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic com...Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic composite interfacial layer rich in benzene ring groups,polyisocyanates,and LiF was obtained on SiO_(x)anode by the introduction of 4-fluorophenyl isocyanate(FPI)and fluoroethylene carbonate(FEC)co-additives in electrolyte.The SiO_(x)anode material shows a capacity retention of 69.2%after 100 cycles at a current density of 1 A g^(-1)and rate capacity of 523 m A h g^(-1)at the current density of 3A g^(-1),while the SiO_(x)anode cycling in reference electrolyte has almost no capacity.展开更多
This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_...This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.展开更多
Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be...Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be solved for extended storage and cycle life.Here,we proposed that an electrolyte additive with an intermediate chelation strength of zinc ion—strong enough to exclude water molecules from the zinc metal-electrolyte interface and not too strong to cause a significant energy barrier for zinc ion dissociation—can benefit the electrochemical stability by suppressing hydrogen evolution reaction,overpotential growth,and den-drite formation.Penta-sodium diethylene-triaminepentaacetic acid salt was selected for such a purpose.It has a suitable chelating ability in aqueous solutions to adjust solvation sheath and can be readily polarized under electrical loading conditions to further improve the passivation.Zn||Zn symmetric cells can be stably operated over 3500 h at 1 mA cm^(-2).Zn||NH4V4O10 full cells with the additive show great cycling stability with 84.6%capacity retention after 500 cycles at 1 A g^(-1).Since the additive not only reduces H2 evolution and corrosion but also modifies Zn2+diffusion and deposition,highlyreversible Zn electrodes can be achieved as verified by the experimental results.Our work offers a practical approach to the logical design of reliable electrolytes for high-performance aqueous batteries.展开更多
Considerable research efforts have been dedicated to investigating the side reactions and the growth of Zn dendritic in aqueous zinc-ion batteries(AZIBs).The incorporation of organic solvents as additives in electroly...Considerable research efforts have been dedicated to investigating the side reactions and the growth of Zn dendritic in aqueous zinc-ion batteries(AZIBs).The incorporation of organic solvents as additives in electrolytes has yielded highly promising results.Nevertheless,their pervasive use has been hindered by concerns regarding their toxicity,flammability,and economic viability.Herein,we propose the utilization of γ-valerolactone(γ-V),a novel eco-friendly solvent,as an alternative for conventional organic additives to improve the performance of Zn anode.Experimental investigations and theoretical analyses have verified that γ-V additives can diminish the Zn^(2+)-desolvation energy and enhance Zn^(2+) transport kinetics.The adsorbed γ-V molecules modulate the nucleation and diffusion of Zn^(2+),facilitating Zn growth along the(002) crystal plane,thus inhibiting dendrite formation and side reactions.Consequently,the modified electrolyte with 3% γ-V exhibit highly reversible cycling for 2800 h at1 mA cm^(-2) and 1 mA h cm^(-2) in Zn//Zn symmetric cell.The Zn//KVOH coin cells deliver a capacity retention of 74.7% after 1000 cycles at 5 A g^(-1).The Zn//KVOH pouch cells maintain a capacity retention of78.7% over 90 cycles at 3 A g^(-1).Notably,the γ-V additives also effectively alleviate the self-discharge phenomenon.This work provides valuable insights on the development of aqueous zinc-ion batteries with superior safety through the modulation of electrolytes using eco-friendly additives.展开更多
Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrit...Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.展开更多
Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode ...Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.展开更多
基金supported by the National Natural Science Foundation of China(22179041)。
文摘High voltage is necessary for high energy lithium-ion batteries but difficult to achieve because of the highly deteriorated cyclability of the batteries.A novel strategy is developed to extend cyclability of a high voltage lithium-ion battery,LiNi_(0.5)Mn_(1.5)O_(4)/Graphite(LNMO/Graphite)cell,which emphasizes a rational design of an electrolyte additive that can effectively construct protective interphases on anode and cathode and highly eliminate the effect of hydrogen fluoride(HF).5-Trifluoromethylpyridine-trime thyl lithium borate(LTFMP-TMB),is synthesized,featuring with multi-functionalities.Its anion TFMPTMB-tends to be enriched on cathode and can be preferentially oxidized yielding TMB and radical TFMP-.Both TMB and radical TFMP can combine HF and thus eliminate the detrimental effect of HF on cathode,while the TMB dragged on cathode thus takes a preferential oxidation and constructs a protective cathode interphase.On the other hand,LTFMP-TMB is preferentially reduced on anode and constructs a protective anode interphase.Consequently,a small amount of LTFMP-TMB(0.2%)in 1.0 M LiPF6in EC/DEC/EMC(3/2/5,wt%)results in a highly improved cyclability of LNMO/Graphite cell,with the capacity retention enhanced from 52%to 80%after 150 cycles at 0.5 C between 3.5 and 4.8 V.The as-developed strategy provides a model of designing electrolyte additives for improving cyclability of high voltage batteries.
基金the financial supports of the National Natural Science Foundation of China(22109045,21875065)the China Postdoctoral Science Foundation Funded Project(2021M701191).
文摘Aqueous zinc-ion capacitors (ZICs) are considered as potential candidates for next generation electrochemical energy storage devices due to their high safety and low cost.However,the existing aqueous ZICs usually have the problems of zinc dendrite growth and unsatisfactory performance at low temperature.Herein,an erythritol (Eryt) additive with inhibition of zinc dendrites and anti-freezing capability was introduced into the ZnSO4electrolyte.The experimental characterization and theoretical calculation confirm that the Eryt adsorbed on the surface of zinc anodes regulates the deposition orientation of Zn^(2+) and inhibits the formation of dendrites.It also reconstructs the solvation structure in the electrolyte to reduce water activity,enabling the electrolyte to have a lower freezing point for operation at low temperature.With the assistance of Eryt,the Zn||Zn symmetric cell exhibits a long cycle life of 2000 h,while the ZIC assembled with activated carbon (AC) cathode and zinc anode (Zn||AC) maintains a capacity retention of 98.2% after 30,000 cycles at a current density of 10 A g^(-1)(even after 10,000 cycles at-20°C,the capacity retention rate reached 94.8%.).This work provides a highly scalable,low-cost and effective strategy for the protection of the anodes of low-temperature aqueous ZICs.
基金supported by the Korea Institute for Advancement of Technology (KIAT) grant funded by the Korea Government (MOTIE) (P0017012, Human Resource Development Program for Industrial Innovation)the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (RS2024-00411892)。
文摘Anode materials for rechargeable electric car batteries are obtained from Li-metal owing to their extremely high specific capacity and low redox potential.Unfortunately,safety concerns related to dendrite formation on the anode surface caused by the uneven distribution of Li-ions during the discharge process interfere with the use of Li-metal in industrial batteries.In this study,methyl vinyl sulfone(MVS),a sulfone-based functional electrolyte additive,is used in an additive engineering strategy to control Lielectrolyte interactions and address the aforementioned problems.Li dendrite growth may be restricted,and transition metal degradation on the surface of the cathode can be reduced by the MVS-derived functional electrolyte additive interfacial layer.The electrochemical performance of an ethylene carbonate/dimethyl carbonate(EC/DMC)+1 wt% MVS Li-metal anode of a Li||Li symmetric cell exhibits remarkable cycle stability,maintaining a low overvoltage for over 750 h at 1 mA cm^(-2),and capacity of 1 mA h cm^(-2).Additionally,LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811) full cells with the MVS additive exhibit enhanced electrochemical stability for 250 cycles at a current density of 100 mA g^(-1).This study provides an innovative approach for stabilizing the metal-electrolyte interfacial layer that may be used for practical applications in metal-based rechargeable batteries.
基金financially National Natural Science Foundation of China (22309165)Excellent Youth Foundation of Henan Province (242300421126)+6 种基金Talent Development Funding Project of Shanghai (2021030)Joint Fund of Science and Technology R&D Plan of Henan Province (232301420053)Postdoctoral Science Foundation of China (2023M743170)Key Research Projects of Higher Education Institutions of Henan Province (24A530010, and 23A530002)Key Laboratory of Adv. Mater. of Ministry of Education (Adv Mat2023-17)State Key Laboratory of Inorganic Synthesis & Preparative Chemistry Jilin University (2024-34)Frontier Exploration Projects of Longmen Laboratory of Henan (LMQYTSKT021)。
文摘Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.
基金supported by the National Natural Science Foundation of China[51874110 and 51604089]the Natural Science Foundation of Heilongjiang Province[YQ2021B004]+1 种基金the Open Project of the State Key Laboratory of Urban Water Resource and Environment[QA202138]the Fundamental Research Funds for the Central Universities[HIT.DZJJ.2023055]。
文摘The aqueous zinc ion batteries(AZIBs)are thought as promising competitors for electrochemical energy storage,though their wide application is curbed by the uncontrollable dendrite growth and gas evolution side reactions.Herein,to stabilize both zinc anodes and water molecules,we developed a modified electrolyte by adding a trace amount of N,N-diethylformanmide(DEF)into the ZnSO_(4)electrolyte for the first time in zinc ion batteries.The effectiveness of DEF is predicted by the comparison of donor number and its preferential adsorption behavior on the zinc anode is further demonstrated by several spectroscopy characterizations,electrochemical methods,and molecular dynamics simulation.The modified electrolyte with 5%v.t.DEF content can ensure a stable cycling life longer than 3400 h of Zn‖Zn symmetric cells and an ultra-reversible Zn stripping/plating process with a high coulombic efficiency of 99.7%.The Zn‖VO_(2)full cell maintains a capacity retention of 83.5%and a 104 mA h g^(-1)mass capacity after 1000cycles.This work provides insights into the role of interfacial adsorption behavior and the donor number of additive molecules in designing low-content and effective aqueous electrolytes.
基金supported by the National Natural Science Foundation of China(22150710516,U1832218).
文摘Rechargeable magnesium metal batteries need an electrolyte that forms a stable and ionically conductive solid electrolyte interphase(SEI)on the anodes.Here,we used molecular dynamic simulation,density functional theory calculation,and X-ray photoelectron spectroscopy analysis to investigate the solvation structures and SEI compositions in electrolytes consisting of dual-salts,magnesium bis(trifluoromethanesulfonyl)imide(MgTFSI_(2)),and MgCl_(2),with different additives in 1,2-dimethoxyethane(DME)solvent.We found that the formed[Mg_(3)(μ-Cl)_(4)(DME)mTFSI_(2)](m=3,5)inner-shell solvation clusters in MgTFSI_(2)-MgCl_(2)/DME electrolyte could easily decompose and form a MgO-and MgF_(2)-rich SEI.Such electron-rich inorganic species in the SEI,especially MgF_(2),turned out to be detrimental for Mg plating/stripping.To reduce the MgF_(2)and MgO contents in SEI,we introduce an electron-deficient tri(2,2,2-trifluoroethyl)borate(TFEB)additive in the electrolyte.Mg//Mg cells using the MgTFSI_(2)-MgCl_(2)/DME-TFEB electrolyte could cycle stably for over 400 h with a small polarization voltage of~150 mV.Even with the presence of 800 ppm H_(2)O,the electrolyte with TFEB additive could still preserve its good electrochemical performance.The optimized electrolyte also enabled stable cycling and high-rate capability for Mg//Mo6S8 and Mg//CuS full cells,showing great potential for future applications.
基金the China Scholarship Council(CSC)for funding(no.201806310116)。
文摘Mg-air batteries have attracted tremendous attention as a potential next-generation power source for portable electronics and e-transportation due to their remarkable high theoretical volumetric energy density,environmental sustainability,and cost-effectiveness.However,the fast hydrogen evolution reaction(HER)in NaCl-based aqueous electrolytes impairs the performance of Mg-air batteries and leads to poor specific capacity,low energy density,and low utilization.Thus,the conventionally used NaCl solute was proposed to be replaced by NaNO_(3)and acetic acid additive as a corrosion inhibitor,therefore an electrolyte engineering for long-life time Mg-air batteries is reported.The resulting Mg-air batteries based on this optimized electrolyte demonstrate an improved discharge voltage reaching~1.8 V for initial 5 h at a current density of 0.5 mA/cm^(2) and significantly prolonged cells'operational lifetime to over 360 h,in contrast to only~17 h observed in NaCl electrolyte.X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry were employed to analyse the composition of surface film and scanning electron microscopy combined with transmission electron microscopy to clarify the morphology changes of the surface layer as a function of acetic acid addition.The thorough studies of chemical composition and morphology of corrosion products have allowed us to elucidate the working mechanism of Mg anode in this optimized electrolyte for Mg-air batteries.
基金supported by the National Natural Science Foundation of China(No.21972049)。
文摘B-containing electrolyte additives are widely used to enhance the cycle performance at low temperature and the rate capability of lithium-ion batteries by constructing an efficient cathode electrolyte interphase(CEI)to facilitate the rapid Li+migration.Nevertheless,its wide-temperature application has been limited by the instability of B-derived CEI layer at high temperature.Herein,dual electrolyte additives,consisting of lithium tetraborate(Li_(2)TB)and 2,4-difluorobiphenyl(FBP),are proposed to boost the widetemperature performances of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)cathode.Theoretical calculation and electrochemical performances analyses indicate that Li_(2)TB and FBP undergo successive decomposition to form a unique dual-layer CEI.FBP acts as a synergistic filming additive to Li_(2)TB,enhancing the hightemperature performance of NCM cathode while preserving the excellent low-temperature cycle stability and the superior rate capability conferred by Li_(2)TB additive.Therefore,the capacity retention of NCM‖Li cells using optimal FBP-Li_(2)TB dual electrolyte additives increases to 100%after 200 cycles at-10℃,99%after 200 cycles at 25℃,and 83%after 100 cycles at 55℃,respectively,much superior to that of base electrolyte(63%/69%/45%).More surprisingly,galvanostatic c ha rge/discharge experiments at different temperatures reveal that NCM‖Li cells using FBP-Li_(2)TB additives can operate at temperatures ranging from-40℃to 60℃.This synergistic interphase modification utilizing dual electrolyte additives to construct a unique dual-layer CEI adaptive to a wide temperature range,provides valuable insights to the practical applications of NCM cathodes for all-climate batteries.
基金supported by the Shandong Provincial Natural Science Foundation,China(No.ZR2019MEM014)。
文摘The electrolyte directly contacts the essential parts of a lithium-ion battery,and as a result,the electrochemical properties of the electrolyte have a significant impact on the voltage platform,charge discharge capacity,energy density,service life,and rate discharge performance.By raising the voltage at the charge/discharge plateau,the energy density of the battery is increased.However,this causes transition metal dissolution,irreversible phase changes of the cathode active material,and parasitic electrolyte oxidation reactions.This article presents an overview of these concerns to provide a clear explanation of the issues involved in the development of electrolytes for high-voltage lithium-ion batteries.Additionally,solidstate electrolytes enable various applications and will likely have an impact on the development of batteries with high energy densities.It is necessary to improve the high-voltage performance of electrolytes by creating solvents with high thermal stabilities and high voltage resistance and additives with superior film forming performance,multifunctional capabilities,and stable lithium salts.To offer suggestions for the future development of high-energy lithium-ion batteries,we conclude by offering our own opinions and insights on the current development of lithium-ion batteries.
基金financially supported by the National Key Research and Development Program of China(2022YFE0206300)the National Natural Science Foundation of China(U21A2081,22075074,22209047)+1 种基金the Natural Science Foundation of Hunan Province(2022JJ40140)the Hunan Provincial Department of Education Outstanding Youth Project(22B0864,23B0037)。
文摘The Li metal battery with ultrahigh-nickel cathode(LiNi_(x)M_(1-x)O_(2),M=Mn,Co,and x≥0.9)under high-voltage is regarded as one of the most promising approaches to fulfill the ambitious target of 400 Wh/kg.However,the practical application is impeded by the instability of electrode/electrolyte interface and Ni-rich cathode itself.Herein we proposed an electron-defect electrolyte additive trimethyl borate(TMB)which is paired with the commercial carbonate electrolyte to construct highly conductive fluorine-and boron-rich cathode electrolyte interface(CEI)on LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)surface and solid electrolyte interphase(SEI)on lithium metal surface.The modified CEI effectively mitigates the structural transformation from layered to disordered rock-salt phase,and consequently alleviate the dissolution of transition metal ions(TMs)and its“cross-talk”effect,while the enhanced SEI enables stable lithium plating/striping and thus demonstrated good compatibility between electrolyte and lithium metal anode.As a result,the common electrolyte with 1 wt%TMB enables 4.7 V NCM90/Li cell cycle stably over 100 cycles with 70%capacity retention.This work highlights the significance of the electron-defect boron compounds for designing desirable interfacial chemistries to achieve high performance NCM90/Li battery under high voltage operation.
基金financially supported by National Natural Science Foundation of China (22209133, 22272131, 21972111, 22211540712)Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX1411)+1 种基金Chongqing Engineering Research Center for Micro-Nano Biomedical Materials and DevicesChongqing Key Laboratory for Advanced Materials and Technologies。
文摘Electrolytic aqueous zinc-manganese(Zn–Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn–Mn batteries is the sluggish deposition reaction kinetics of manganese oxide during the charge process and short cycle life. We show that, incorporating ZnO electrolyte additive can form a neutral and highly viscous gel-like electrolyte and render a new form of electrolytic Zn–Mn batteries with significantly improved charging capabilities. Specifically, the ZnO gel-like electrolyte activates the zinc sulfate hydroxide hydrate assisted Mn^(2+) deposition reaction and induces phase and structure change of the deposited manganese oxide(Zn_(2)Mn_(3)O_8·H_(2)O nanorods array), resulting in a significant enhancement of the charge capability and discharge efficiency. The charge capacity increases to 2.5 mAh cm^(-2) after 1 h constant-voltage charging at 2.0 V vs. Zn/Zn^(2+), and the capacity can retain for up to 2000 cycles with negligible attenuation. This research lays the foundation for the advancement of electrolytic Zn–Mn batteries with enhanced charging capability.
基金financial support from the Natural Science Foundation of Shandong Province(ZR2021ZD05)the Outstanding Talents in Shandong University。
文摘Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.
基金supported by the National Natural Science Foundation of China(Grant No.21872058)。
文摘Lithium-metal battery based on Ni-rich cathode provides high energy density but presents poor cyclic stability due to the unstable electrode/electrolyte interfaces on both cathode and anode.In this work,we report a new strategy to address this issue.It is found that the cyclic stability of Ni-rich/Li battery can be significantly improved by using succinic anhydride(SA) as an electrolyte additive.Specifically,the capacity retention of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/Li cell is improved from 14% to 83% after 200cycles at 1 C between 3.0 and 4.35 V by applying 5% SA.The underlying mechanism of SA contribution is understood by comparing the effects of malic anhydride(MA) and citraconic anhydride(CA), both of which share a similar molecular structure to SA but show different effects.On anode side,SA can but MA and CA cannot form a protective solid electrolyte interphase(SEI) on Li anode.On cathode side,three anhydrides can suppress the formation of hydrogen fluoride from electrolyte oxidation decomposition,but SA behaves best.Typically,MA shows adverse effects on the interface stability of Li anode and NCM811 cathode,which originates from its high acidity.Though the acidity of MA can be mitigated by substituting a methyl for one H atom at its C=C bond,the substituent CA cannot compete with SA in cyclic stability improvement of the cell,because the SEI resulting from CA is not as robust as that from SA,which is related to the binding energy of the SEI components.This understanding reveals the importance of the electrolyte acidity on the Ni-rich cathode and the robustness of the SEI on Li anode,which is helpful for rationally designing new electrolyte additives to further improve the cyclic stability of high-energydensity Ni-rich/Li batteries.
基金financially supported by the National Key Research and Development Program of China(2016YFB0100400)the National Natural Science Foundation of China(21875154,22179090)。
文摘The feasibility for natural graphite(NG)to replace artificial graphite(AG)in organic electrolytes with different additives are investigated.Although the strong film-forming additives contributes to form robust solid electrolyte interphase(SEI)film on graphite particle surface,great differences in gas evolution,lithium inventory loss and other side reactions are observed.Lithium bis(oxalato)borate(Li BOB)and fluoroethylene carbonate(FEC)are found more effective and the combination shows to be more promising.In the optimized electrolyte,natural graphite anode exhibits excellent long-term cycling capability.After 800 cycles at high temperature,the capacity retention is comparable to that using artificial graphite.The mechanisms for the capacity-fading of the full cells with AG and NG anode are investigated by ICP,SEM and polarization studies.The results shows that NG electrode consumes more active lithium due to the rough surface and larger volume expansion.The rapid capacity-fading in the initial 100 cycles is related to the instability of the SEI film aroused from large volume expansion.The systematic analysis is inspiriting for the development of high performance lithium ion batteries with reduced cost.
基金financially supporting from the Key-Area Research and Development Program of Guangdong Province(2020B090919005)the Fundamental Research Funds for the Central Universities(HIT.OCEF.2021008)+2 种基金the Key Research and Development Program of Heilongjiang Province(GA21A102)the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0958)the National Natural Science Foundation of China(51772068)。
文摘Macro-and micro-interface instability of SiO_(x)anode caused by its dramatic volume variation during cycling will result in low Coulombic efficiency and rapid capacity degradation.In this work,an organic-inorganic composite interfacial layer rich in benzene ring groups,polyisocyanates,and LiF was obtained on SiO_(x)anode by the introduction of 4-fluorophenyl isocyanate(FPI)and fluoroethylene carbonate(FEC)co-additives in electrolyte.The SiO_(x)anode material shows a capacity retention of 69.2%after 100 cycles at a current density of 1 A g^(-1)and rate capacity of 523 m A h g^(-1)at the current density of 3A g^(-1),while the SiO_(x)anode cycling in reference electrolyte has almost no capacity.
基金financially supported by the Scientific and Technological Plan Projects of Guangzhou City(202103040001)。
文摘This work develops 2-Phenyl-1H-imidazole-1-sulfonate(PHIS)as a multi-functional electrolyte additive for H2O/HF scavenging and film formation to improve the high temperature performance of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)/graphite batteries.After 450 cycles at room temperature(25℃),the discharge capacity retentions of batteries with blank and PHIS-containing electrolyte are 56.03%and 94.92%respectively.After 230 cycles at high temperatures(45℃),their values are 75.30%and 88.38%respectively.The enhanced electrochemical performance of the batteries with PHIS-containing electrolyte is supported by the spectroscopic characterization and theoretical calculations.It is demonstrated that this PHIS electrolyte additive can facilitate the construction of the electrode interface films,remove the H2O/HF in the electrolyte,and improve the electrochemical performance of the batteries.This work not only develops a sulfonate-based electrolyte but also can stimulate new ideas of functional additives to improve the battery performance.
基金This work is financially supported by National Natural Science Foundation of China(NSFC-No.52173257 and 52372064).
文摘Aqueous zinc-ion batteries are promising due to inherent safety,low cost,low toxicity,and high volumetric capacity.However,issues of dendrites and side reactions between zinc metal anode and the electrolyte need to be solved for extended storage and cycle life.Here,we proposed that an electrolyte additive with an intermediate chelation strength of zinc ion—strong enough to exclude water molecules from the zinc metal-electrolyte interface and not too strong to cause a significant energy barrier for zinc ion dissociation—can benefit the electrochemical stability by suppressing hydrogen evolution reaction,overpotential growth,and den-drite formation.Penta-sodium diethylene-triaminepentaacetic acid salt was selected for such a purpose.It has a suitable chelating ability in aqueous solutions to adjust solvation sheath and can be readily polarized under electrical loading conditions to further improve the passivation.Zn||Zn symmetric cells can be stably operated over 3500 h at 1 mA cm^(-2).Zn||NH4V4O10 full cells with the additive show great cycling stability with 84.6%capacity retention after 500 cycles at 1 A g^(-1).Since the additive not only reduces H2 evolution and corrosion but also modifies Zn2+diffusion and deposition,highlyreversible Zn electrodes can be achieved as verified by the experimental results.Our work offers a practical approach to the logical design of reliable electrolytes for high-performance aqueous batteries.
基金National Natural Science Foundation of China (Grant No. 52103302, and No. 52070124)Shandong Provincial Natural Science Foundation (ZR2021QB182)+1 种基金Start-up Foundation for Senior Talents of Jiangsu University (21JDG041)China Postdoctoral Science Foundation (2023M731357)。
文摘Considerable research efforts have been dedicated to investigating the side reactions and the growth of Zn dendritic in aqueous zinc-ion batteries(AZIBs).The incorporation of organic solvents as additives in electrolytes has yielded highly promising results.Nevertheless,their pervasive use has been hindered by concerns regarding their toxicity,flammability,and economic viability.Herein,we propose the utilization of γ-valerolactone(γ-V),a novel eco-friendly solvent,as an alternative for conventional organic additives to improve the performance of Zn anode.Experimental investigations and theoretical analyses have verified that γ-V additives can diminish the Zn^(2+)-desolvation energy and enhance Zn^(2+) transport kinetics.The adsorbed γ-V molecules modulate the nucleation and diffusion of Zn^(2+),facilitating Zn growth along the(002) crystal plane,thus inhibiting dendrite formation and side reactions.Consequently,the modified electrolyte with 3% γ-V exhibit highly reversible cycling for 2800 h at1 mA cm^(-2) and 1 mA h cm^(-2) in Zn//Zn symmetric cell.The Zn//KVOH coin cells deliver a capacity retention of 74.7% after 1000 cycles at 5 A g^(-1).The Zn//KVOH pouch cells maintain a capacity retention of78.7% over 90 cycles at 3 A g^(-1).Notably,the γ-V additives also effectively alleviate the self-discharge phenomenon.This work provides valuable insights on the development of aqueous zinc-ion batteries with superior safety through the modulation of electrolytes using eco-friendly additives.
基金financially supported by the National Natural Science Foundation of China (No. 52377222)the Natural Science Foundation of Hunan Province, China (Nos. 2023JJ20064, 2023JJ40759)。
文摘Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(No.22075115)Natural Science Foundation of Jiangsu Province(No.BK20211352)+2 种基金Joint Funds of the National Natural Science Foundation of China(No.U2141201)Natural Science Foundation(No.22KJA430005)of Jiangsu Education Committee of ChinaPostgraduate Research and Practice Innovation Program of Jiangsu Normal University(No.2021XKT0296).
文摘Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.