Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacl...Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacles beyond the issue of ionic conductivity.This investigation unveils a novel formulation that constructs an anion-rich solvation sheath within strong solvents,effectively addressing all three of these challenges to bolster low-temperature performance.The developed electrolyte,characterized by an enhanced concentration of contact ion pairs(CIPs)and aggregates(AGGs),facilitates the formation of an inorganic-rich interphase layer on the anode and cathode particles.This promotes de-solvation at low temperatures and stabilizes the electrode-electrolyte interphase.Full cells composed of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)and graphite,when equipped with this electrolyte,showcase remarkable cycle stability and capacity retention,with 93.3% retention after 500 cycles at room temperature(RT)and 95.5%after 120 cycles at -20℃.This study validates the utility of the anion-rich solvation sheath in strong solvents as a strategy for the development of low-temperature electrolytes.展开更多
Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium me...Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.展开更多
The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions durin...The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions during cycling.Electrolyte additive modification is considered one of the most effective and simplest methods for solving the aforementioned problems.Herein,the pyridine derivatives(PD)including 2,4-dihydroxypyridine(2,4-DHP),2,3-dihydroxypyridine(2,3-DHP),and 2-hydroxypyrdine(2-DHP),were em-ployed as novel electrolyte additives in ZnSO_(4)electrolyte.Both density functional theory calculation and experimental findings demonstrated that the incorporation of PD additives into the electrolyte effectively modulates the solvation structure of hydrated Zn ions,thereby suppressing side reactions in AZIBs.Ad-ditionally,the adsorption of PD molecules on the zinc anode surface contributed to uniform Zn deposi-tion and dendrite growth inhibition.Consequently,a 2,4-DHP-modified Zn/Zn symmetrical cell achieved an extremely long cyclic stability up to 5650 h at 1 mA cm^(-2).Furthermore,the Zn/NH_(4)V_(4)O_(10)full cell with 2,4-DHP-containing electrolyte exhibited an outstanding initial capacity of 204 mAh g^(-1),with a no-table capacity retention of 79%after 1000 cycles at 5 A g^(-1).Hence,this study expands the selection of electrolyte additives for AZIBs,and the working mechanism of PD additives provides new insights for electrolyte modification enabling highly reversible zinc anode.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
Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challe...Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.展开更多
Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience e...Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience especially for electric vehicles,the development of a fast-charging technology for LIBs has become a critical focus.In commercial LIBs,the slow kinetics of Li+intercalation into the graphite anode from the electrolyte solution is known as the main restriction for fast-charging.We summarize the recent advances in obtaining fast-charging graphite-based anodes,mainly involving modifications of the electrolyte solution and graphite anode.Specifically,strategies for increasing the ionic conductivity and regulating the Li+solvation/desolvation state in the electrolyte solution,as well as optimizing the fabrication and the intrinsic activity of graphite-based anodes are discussed in detail.This review considers practical ways to obtain fast Li+intercalation kinetics into a graphite anode from the electrolyte as well as analysing progress in the commercialization of fast-charging LIBs.展开更多
LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully ...LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully revealed.Herein,we systematically studied the evolution of solvation structures with increasing LiNO_(3) concentration in both carbonate and ether electrolytes.The results from molecular dynamics simulations unveil that the Li^(+)solvation structure is less affected in carbonate electrolytes,while in ether electrolytes,there is a significant decrease of solvent molecules in Li^(+)coordination,and a larger average size of Li^(+)solvation structure emerges as LiNO_(3) concentration increases.Notably,the formation of large ion aggregates with size of several nanometers(nano-clusters),is observed in ether-based electrolytes at conventional Li^(+)concentration(1 M)with higher NO_(3)^(-) ratio,which is further proved by infrared spectroscopy and small-angle X-ray scattering experiments.The nano-clusters with abundant anions are endowed with a narrow energy gap of molecular orbitals,contributing to the formation of an inorganic rich electrode/electrolyte interphase that enhances the reversibility of lithium stripping/plating with Coulombic efficiency up to 99.71%.The discovery of nano-clusters elucidates the underlying mechanism linking ions/solvent aggregation states of electrolytes to interfacial stability in advanced battery systems.展开更多
Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified W...Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.展开更多
Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side rea...Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).展开更多
Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerati...Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerating interfaces decay.Herein,we propose for the first time a novel strategy to enhance the interfacial stabilities by insitu dynamic reconstruction of weakly solvated Zn2þduring the desolvation processes at heterointerfaces.Theoretical calculations indicate that,due to built-in electric field effects(BEFs),the plating/stripping mechanism shifts from[Zn(H_(2)O)_(6)]_(2)þto[Zn(H_(2)O)_(5)(SO_(4))^(2-)]_(2)þwithout additional electrolyte additives,reducing the solvation ability of H_(2)O,enhancing the competitive coordination of SO_(4)^(2-),essentially eliminating the undesirable side effects of anodes.Hence,symmetric cells can operate stably for 3000 h(51.7-times increase in cycle life),and the full cells can operate stably for 5000 cycles(51.5-times increase in cycle life).This study provides valuable insights into the critical design of weakly solvated Zn^(2+) þand desolvation processes at heterointerfaces.展开更多
The electrospray thruster supplied by ionic liquid is a promising micro-propulsion thruster with small size and precise thrust, which can emit both cations and anions to achieve self-neutralization. In order to furthe...The electrospray thruster supplied by ionic liquid is a promising micro-propulsion thruster with small size and precise thrust, which can emit both cations and anions to achieve self-neutralization. In order to further investigate the effect of ion solvation energy on the evaporation of cations and anions from ionic liquid under the action of a uniform electric field, this paper establishes a transient Electrohydrodynamic (EHD) model for free ionic liquid droplets undergoing ion evaporation. The dynamic processes of droplet deformation and ion evaporation are simulated. And the study further focuses on the influence of different ion solvation energies for cations on the droplet morphology and the ion evaporation characteristics at the positively charged end and negatively charged end of the droplet. The results indicate that, when the ion solvation energy for cations is higher than that of anions, it will cause the ion evaporation at the positively charged end of the droplet to lag behind the ion evaporation at the negatively charged end. And the higher the ion solvation energy for the cations, the longer the evaporation lag time at the positively charged end of the droplet, which will lead to a higher peak of surface charge density that can be reached, resulting in a larger evaporation current and sharper droplet stretching deformation. Additionally, the peak surface charge density of the positively charged end of the droplet is linearly related to the ion solvation energy for cations, while the peak surface charge density of the negatively charged end remains almost unchanged and is not significantly affected by the ion solvation energy for cations.展开更多
Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions h...Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions have significant impacts on the performance and stability of lithium batteries.Therefore,comprehensively understanding anion chemistry in electrolytes is of crucial importance.Herein,indepth comprehension of anion chemistry and its positive effects on the interface,solvation structure of Li-ions,as well as the electrochemical performance of the batteries have been emphasized and summarized.This review aims to present a full scope of anion chemistry and furnish systematic cognition for the rational design of advanced electrolytes for better lithium batteries with high energy density,lifespan,and safety.Furthermore,insightful analysis and perspectives based on the current research are proposed.We hope that this review sheds light on new perspectives on understanding anion chemistry in electrolytes.展开更多
High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage...High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.展开更多
Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability...Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability and poor compatibility with high-nickel materials.This study introduces a novel electrolyte that combines bis(triethoxysilyl)methane(DMSP)as the sole solvent with lithium bis(fluorosulfonyl)imide(LiFSI)as the lithium salt.This formulation significantly improves the stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes and graphite anodes.The capacity retention of the NCM811 elec-trode increases from 5%to 95%after 1000 cycles at 1 C(3.0-4.5 V),while that of the graphite anode is improved from 22%to 92%after 400 cycles at 0.2 C(0.005-3.0 V).The NCM811//graphite pouch cell exhibits enhanced retention,rising from 12%to 66%at 25℃and from 3%to 65%at 60℃after 300 cycles at 0.2 C.Spectroscopic characterization and theoretical calculations reveal that the steric hindrance of the Si-O-CH_(3)groups in DMSP creates a weakly solvating structure,promoting the formation of Lit^(+)-FSI^(-)ion pairs and aggregation clusters,which enriches the electrode interphase with LiF,Li_(3)N,and Li_(2)SO_(3).Furthermore,DMSP with abundant Si-O effectively enhances the elasticity of the interphase layer,scav-enging harmful substances such as HF and suppressing gas evolution and transition metal dissolution.The simplicity of the DMSP-based electrolyte formulation,coupled with its superior performance,ensures scalability for large-scale manufacturing and practical application in the high-voltage battery.This work provides critical insights into improving interfacial chemistry and addressing compatibility issues in high-voltageNi-rich cathodes.展开更多
Explorations into new electrolytes have highlighted the critical impact of solvation structure on battery performance,Classical molecular dynamics(CMD)using semi-empirical force fields has become an essential tool for...Explorations into new electrolytes have highlighted the critical impact of solvation structure on battery performance,Classical molecular dynamics(CMD)using semi-empirical force fields has become an essential tool for simulating solvation structures.However,mainstream force fields often lack accuracy in describing strong ion-solvent interactions,causing disparities between CMD simulations and experimental observations.Although some empirical methods have been employed in some of the studies to address this issue,their effectiveness has been limited.Our CMD research,supported by quantum chemical calculations and experimental data,reveals that the solvation structure is influenced not only by the charge model but also by the polarization description.Previous empirical approaches that focused solely on adjusting ion-solvent interaction strengths overlooked the importance of polarization effects.Building on this insight,we propose integrating the Drude polarization model into mainstream force fields and verify its feasibility in carbonate,ether,and nitrile electrolytes.Our experimental results demonstrate that this approach significantly enhances the accuracy of CMD-simulated solvation structures.This work is expected to provide a more reliable CMD method for electrolyte design,shielding researchers from the pitfalls of erroneous simulation outcomes.展开更多
Developing rechargeable aqueous Zn batteries for large-scale energy storage is impeded by inadequate reversibility and stability of the Zn anode,primarily caused by parasitic reactions and heterogeneous deposition.Thi...Developing rechargeable aqueous Zn batteries for large-scale energy storage is impeded by inadequate reversibility and stability of the Zn anode,primarily caused by parasitic reactions and heterogeneous deposition.This study proposes an economical electrolyte strategy to address these Zn-related issues.The addition of a supporting salt enhances the thermodynamic stability of water,reduces the number of highly reactive water molecules,and modulates the interfacial electrostatic interaction.This approach effectively suppresses hydrogen evolution reaction and uncontrolled deposition.Remarkably,the rationally proportioned electrolyte allows a high average Coulombic efficiency of 99.93%for 1000 cycles in a Zn‖Cu battery and a prolonged lifespan exceeding 4800 h in Zn‖Zn cells.The knock-on effect is that Zn‖MnO_(2)pouch cells deliver stable cycling performance,demonstrating the viability of this approach for practical applications.展开更多
The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution...The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.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
Rechargeable batteries are essential energy storage devices that power portable devices and electrical vehicles throughout the wo rld.In general,it is thought that the electrochemical performance of recha rgeable batt...Rechargeable batteries are essential energy storage devices that power portable devices and electrical vehicles throughout the wo rld.In general,it is thought that the electrochemical performance of recha rgeable batteries is mostly determined by the electrodes within them and that the electrolyte plays a relatively passive role.However,ion transport and storage can be greatly influenced by the electrolyte solution structure,specifically,ion solvation within the bulk and ion desolvation across the electrode/electrolyte interfaces.Herein,we studied the role of the electrolyte as an active component of electrochemical energy storage devices.We found that with an appropriate electrolyte formulation,ion storage in disordered carbonaceous anode materials can occur spontaneously without externally supplied electrical energy.Reduced graphene oxide(RGO)in an ether-based electrolyte demonstrates'spontaneous'ion storage behaviors of adsorbing and inserting the solvated ions utilizing facilitated permeability and wettability of RGO,which results in Coulombic efficiency of~145%due to additional charging capacity of~180 mAh g^(-1)during electrochemical processes.The unexpected spontaneous ion storage behavior was extensively investigated using a combination of electrochemical analyses and diagnostics,advanced characterizations,and computational simulation.We believe the spontaneous ion storage behavior offers a new way to further improve the energy efficiency of practical rechargeable batteries.展开更多
Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered ...Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered by low ionic conductivity and the growth of lithium dendrites.To achieve ordered transport of Li^(+)ions in quasi-solid electrolytes(QSEs),improve ionic conductivity,and homogenize Li^(+)fluxes on the surface of the lithium metal anode(LMA),we propose a novel method.This method involves constructing"ion relay stations"in QSEs by introducing cyano-functionalized boron nitride nanosheets into pentaerythritol tetraacrylate(PETEA)-based polymer electrolytes.The functionalized boron nitride nanosheets promote the dissociation of lithium salts through ion-dipole interactions,optimizing the solvated structure to facilitate the orderly transport of Li+ions,resulting in an ionic conductivity of2.5×10^(-3)S cm^(-1)at 30℃.Notably,this strategy regulates the Li^(+)distribution on the surface of the LMA,effectively inhibiting the growth of lithium dendrites,Li‖Li symmetrical cells using this type of electrolyte maintain stability for over 2000 h at 2 mA cm^(-2)and 2 mAh cm^(-2).Additionally,with a high LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)loading of 8.5 mg cm^(-2),the cells exhibit excellent cycling performance,retaining a high capacity after 400 cycles.This innovative QSE design strategy represents a significant advancement towards the development of high-performance QSLMBs.展开更多
基金the National Natural Science Foundation of China(No.22279070[L.Wang]and U21A20170[X.He])the Ministry of Science and Technology of China(No.2019YFA0705703[L.Wang])。
文摘Lithium-ion batteries(LIBs)face significant limitations in low-temperature environments,with the slow interfacial de-solvation process and the hindered Li+transport through the interphase layer emerging as key obstacles beyond the issue of ionic conductivity.This investigation unveils a novel formulation that constructs an anion-rich solvation sheath within strong solvents,effectively addressing all three of these challenges to bolster low-temperature performance.The developed electrolyte,characterized by an enhanced concentration of contact ion pairs(CIPs)and aggregates(AGGs),facilitates the formation of an inorganic-rich interphase layer on the anode and cathode particles.This promotes de-solvation at low temperatures and stabilizes the electrode-electrolyte interphase.Full cells composed of LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622)and graphite,when equipped with this electrolyte,showcase remarkable cycle stability and capacity retention,with 93.3% retention after 500 cycles at room temperature(RT)and 95.5%after 120 cycles at -20℃.This study validates the utility of the anion-rich solvation sheath in strong solvents as a strategy for the development of low-temperature electrolytes.
基金supported by the National Natural Science Foundation of China(52372249)support by the Program of Shanghai Academic Research Leader(21XD1424400)。
文摘Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.
基金supported by the Key Science and Technol-ogy Program of Henan Province(No.232102241020)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)+1 种基金the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001)the Natural Science Foundation of Henan Province(242300420021).
文摘The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions during cycling.Electrolyte additive modification is considered one of the most effective and simplest methods for solving the aforementioned problems.Herein,the pyridine derivatives(PD)including 2,4-dihydroxypyridine(2,4-DHP),2,3-dihydroxypyridine(2,3-DHP),and 2-hydroxypyrdine(2-DHP),were em-ployed as novel electrolyte additives in ZnSO_(4)electrolyte.Both density functional theory calculation and experimental findings demonstrated that the incorporation of PD additives into the electrolyte effectively modulates the solvation structure of hydrated Zn ions,thereby suppressing side reactions in AZIBs.Ad-ditionally,the adsorption of PD molecules on the zinc anode surface contributed to uniform Zn deposi-tion and dendrite growth inhibition.Consequently,a 2,4-DHP-modified Zn/Zn symmetrical cell achieved an extremely long cyclic stability up to 5650 h at 1 mA cm^(-2).Furthermore,the Zn/NH_(4)V_(4)O_(10)full cell with 2,4-DHP-containing electrolyte exhibited an outstanding initial capacity of 204 mAh g^(-1),with a no-table capacity retention of 79%after 1000 cycles at 5 A g^(-1).Hence,this study expands the selection of electrolyte additives for AZIBs,and the working mechanism of PD additives provides new insights for electrolyte modification enabling highly reversible zinc anode.
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supported by the Natural Science Foundation of Henan Province(No.242300420021)the Major Science and Technology Projects of Henan Province(No.221100230200)+4 种基金the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Key Science and Technology Program of Henan Province(No.232102241020)the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province(No.S202310464012)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001).
文摘Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.
文摘Lithium-ion batteries(LIBs)are an electrochemical energy storage technology that has been widely used for portable electrical devices,electric vehicles,and grid storage,etc.To satisfy the demand for user convenience especially for electric vehicles,the development of a fast-charging technology for LIBs has become a critical focus.In commercial LIBs,the slow kinetics of Li+intercalation into the graphite anode from the electrolyte solution is known as the main restriction for fast-charging.We summarize the recent advances in obtaining fast-charging graphite-based anodes,mainly involving modifications of the electrolyte solution and graphite anode.Specifically,strategies for increasing the ionic conductivity and regulating the Li+solvation/desolvation state in the electrolyte solution,as well as optimizing the fabrication and the intrinsic activity of graphite-based anodes are discussed in detail.This review considers practical ways to obtain fast Li+intercalation kinetics into a graphite anode from the electrolyte as well as analysing progress in the commercialization of fast-charging LIBs.
基金supported by the National Natural Science Foundation of China(No.22372083,52201259)the National Key R&D Program of China(2021YFB2500300)+2 种基金the Fundamental Research Funds for the Central Universities:Nankai University(63241607)the Natural Science Foundation of Tianjin(No.22JCZDJC00380)the Young Elite Scientist Sponsorship Program by CAST.
文摘LiNO_(3) is known to significantly enhance the reversibility of lithium metal batteries;however,the modification of solvation structures in various solvents and its further impact on the interface have not been fully revealed.Herein,we systematically studied the evolution of solvation structures with increasing LiNO_(3) concentration in both carbonate and ether electrolytes.The results from molecular dynamics simulations unveil that the Li^(+)solvation structure is less affected in carbonate electrolytes,while in ether electrolytes,there is a significant decrease of solvent molecules in Li^(+)coordination,and a larger average size of Li^(+)solvation structure emerges as LiNO_(3) concentration increases.Notably,the formation of large ion aggregates with size of several nanometers(nano-clusters),is observed in ether-based electrolytes at conventional Li^(+)concentration(1 M)with higher NO_(3)^(-) ratio,which is further proved by infrared spectroscopy and small-angle X-ray scattering experiments.The nano-clusters with abundant anions are endowed with a narrow energy gap of molecular orbitals,contributing to the formation of an inorganic rich electrode/electrolyte interphase that enhances the reversibility of lithium stripping/plating with Coulombic efficiency up to 99.71%.The discovery of nano-clusters elucidates the underlying mechanism linking ions/solvent aggregation states of electrolytes to interfacial stability in advanced battery systems.
基金supported by Hengyang City,Hunan Province Science and Technology Innovation Project(No.202250045319)the National Natural Science Foundation of China(Nos.11375084,21808125)the Scientific Research Planning Project of Jilin Provincial Education Department(No.JJKH20241249KJ)。
文摘Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
基金funded by the National Natural Science Foundation of China(22478632)Key Scientific and Technological Project of Henan Province(242102321032).
文摘Continuous-flow upgrading of pentaerythritol synthesis technology via base-catalyzed aldol and Cannizzaro reactions of formaldehyde and acetaldehyde faces the challenge of effectively controlling the critical side reaction of hydroxymethyl acetaldehyde(HA)to the acrolein intermediate.Here,we first identified the forms of industrial formaldehyde as methane diol that easily converts to the alkaline formaldehyde under alkaline(NaOH)environment.The carbonyl group of alkaline formaldehyde induces deprotonation of acetaldehyde instead of the recognized base-hydroxyl group-induced deprotonation,and it needs to overcome only 18.31 kcal·mol^(-1)(1 kcal=4.186 kJ)energy barrier to form key intermediates of HA.The sodium solvation cage formed by NaOH hexa-coordinated formaldehyde effectively inhibits the alkalinity,thus contributing to a high energy barrier(46.21 kcal·mol^(-1))to unwanted acrolein formation.In addition,the solvation cage gradually opens to increase the alkalinity with the consumption of formaldehyde,thus facilitating the subsequent Cannizzaro reaction(to overcome 11.77 kcal·mol^(-1)).In comparison,strong alkalinity promotes the formation of acrolein(36.65 kcal·mol^(-1))to initiate the acetal side reaction,while weak alkalinity reduces the possibility of the Cannizzaro reaction(to overcome 20.44 kcal·mol^(-1)).This theoretically reveals the importance of the segmented feeding of weak and strong bases to successively control the aldol reaction and Cannizzaro reaction,and the combination of Na_(2)CO_(3) or HCOONa with NaOH improves the pentaerythritol yield by 7%to 13%compared to that of NaOH alone(70%yield)within 1 min at a throughput of 155.7 ml·min^(-1).
基金financially supported by the National Natural Science Foundation of China(51977097).
文摘Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerating interfaces decay.Herein,we propose for the first time a novel strategy to enhance the interfacial stabilities by insitu dynamic reconstruction of weakly solvated Zn2þduring the desolvation processes at heterointerfaces.Theoretical calculations indicate that,due to built-in electric field effects(BEFs),the plating/stripping mechanism shifts from[Zn(H_(2)O)_(6)]_(2)þto[Zn(H_(2)O)_(5)(SO_(4))^(2-)]_(2)þwithout additional electrolyte additives,reducing the solvation ability of H_(2)O,enhancing the competitive coordination of SO_(4)^(2-),essentially eliminating the undesirable side effects of anodes.Hence,symmetric cells can operate stably for 3000 h(51.7-times increase in cycle life),and the full cells can operate stably for 5000 cycles(51.5-times increase in cycle life).This study provides valuable insights into the critical design of weakly solvated Zn^(2+) þand desolvation processes at heterointerfaces.
基金supported by the National Key R&D Program of China(No.2020YFC2201100)the National Natural Science Foundation of China(Nos.12175032,12102082,12275044,12402327,12405290 and 12211530449)+4 种基金the Joint Program of the Science and Technology Program of Liaoning,China(No.2023JH2/101700285)the Fundamental Research Funds for the Central Universities of China(Nos.DUT22RC(3)078,DUT23RC(3)040 and DUT24ZD106)the S&T Program of Hebei,China(No.246Z2301G)the S&T Innovation Program of Hebei,China(Nos.SJMYF2022X18 and SJMYF2022X06)the Beijing Engineering Research Center of Efficient and Green Aerospace Propulsion Technology and Advanced Space Propulsion Laboratory of BICE,China(No.LabASP-2023-07).
文摘The electrospray thruster supplied by ionic liquid is a promising micro-propulsion thruster with small size and precise thrust, which can emit both cations and anions to achieve self-neutralization. In order to further investigate the effect of ion solvation energy on the evaporation of cations and anions from ionic liquid under the action of a uniform electric field, this paper establishes a transient Electrohydrodynamic (EHD) model for free ionic liquid droplets undergoing ion evaporation. The dynamic processes of droplet deformation and ion evaporation are simulated. And the study further focuses on the influence of different ion solvation energies for cations on the droplet morphology and the ion evaporation characteristics at the positively charged end and negatively charged end of the droplet. The results indicate that, when the ion solvation energy for cations is higher than that of anions, it will cause the ion evaporation at the positively charged end of the droplet to lag behind the ion evaporation at the negatively charged end. And the higher the ion solvation energy for the cations, the longer the evaporation lag time at the positively charged end of the droplet, which will lead to a higher peak of surface charge density that can be reached, resulting in a larger evaporation current and sharper droplet stretching deformation. Additionally, the peak surface charge density of the positively charged end of the droplet is linearly related to the ion solvation energy for cations, while the peak surface charge density of the negatively charged end remains almost unchanged and is not significantly affected by the ion solvation energy for cations.
基金supported by National Key Research and Development Program of China(2022YFB2402200)the China Postdoctoral Science Foundation(grant nos.2023T160591)the Joint Fund of the Technical R&D Program of Henan Province(grant nos.232301420044).
文摘Electrolytes are crucial components in electrochemical energy storage devices,sparking considerable research interest.However,the significance of anions in the electrolytes is often underestimated.In fact,the anions have significant impacts on the performance and stability of lithium batteries.Therefore,comprehensively understanding anion chemistry in electrolytes is of crucial importance.Herein,indepth comprehension of anion chemistry and its positive effects on the interface,solvation structure of Li-ions,as well as the electrochemical performance of the batteries have been emphasized and summarized.This review aims to present a full scope of anion chemistry and furnish systematic cognition for the rational design of advanced electrolytes for better lithium batteries with high energy density,lifespan,and safety.Furthermore,insightful analysis and perspectives based on the current research are proposed.We hope that this review sheds light on new perspectives on understanding anion chemistry in electrolytes.
基金supported by the National Key Research and Development Program of China(2022YFB3803400)。
文摘High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.
基金supported by the National Natural Science Foundation of China (Grant No. 22179041)the Guangzhou Science and Technology Plan Project (Grant No. 2024A04J4354)the Guangdong Basic and Applied Basic Research Foundation (Grant No. 2024A1515010034)
文摘Enhancing the energy density of lithium-ion batteries through high-voltage cathodes holds great pro-mise.However,traditional carbonate-based electrolytes face significant challenges due to limited oxida-tive stability and poor compatibility with high-nickel materials.This study introduces a novel electrolyte that combines bis(triethoxysilyl)methane(DMSP)as the sole solvent with lithium bis(fluorosulfonyl)imide(LiFSI)as the lithium salt.This formulation significantly improves the stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes and graphite anodes.The capacity retention of the NCM811 elec-trode increases from 5%to 95%after 1000 cycles at 1 C(3.0-4.5 V),while that of the graphite anode is improved from 22%to 92%after 400 cycles at 0.2 C(0.005-3.0 V).The NCM811//graphite pouch cell exhibits enhanced retention,rising from 12%to 66%at 25℃and from 3%to 65%at 60℃after 300 cycles at 0.2 C.Spectroscopic characterization and theoretical calculations reveal that the steric hindrance of the Si-O-CH_(3)groups in DMSP creates a weakly solvating structure,promoting the formation of Lit^(+)-FSI^(-)ion pairs and aggregation clusters,which enriches the electrode interphase with LiF,Li_(3)N,and Li_(2)SO_(3).Furthermore,DMSP with abundant Si-O effectively enhances the elasticity of the interphase layer,scav-enging harmful substances such as HF and suppressing gas evolution and transition metal dissolution.The simplicity of the DMSP-based electrolyte formulation,coupled with its superior performance,ensures scalability for large-scale manufacturing and practical application in the high-voltage battery.This work provides critical insights into improving interfacial chemistry and addressing compatibility issues in high-voltageNi-rich cathodes.
基金supported by the Science and Technology Project of State Grid Corporation of China(5419-202199552A-0-5-ZN).
文摘Explorations into new electrolytes have highlighted the critical impact of solvation structure on battery performance,Classical molecular dynamics(CMD)using semi-empirical force fields has become an essential tool for simulating solvation structures.However,mainstream force fields often lack accuracy in describing strong ion-solvent interactions,causing disparities between CMD simulations and experimental observations.Although some empirical methods have been employed in some of the studies to address this issue,their effectiveness has been limited.Our CMD research,supported by quantum chemical calculations and experimental data,reveals that the solvation structure is influenced not only by the charge model but also by the polarization description.Previous empirical approaches that focused solely on adjusting ion-solvent interaction strengths overlooked the importance of polarization effects.Building on this insight,we propose integrating the Drude polarization model into mainstream force fields and verify its feasibility in carbonate,ether,and nitrile electrolytes.Our experimental results demonstrate that this approach significantly enhances the accuracy of CMD-simulated solvation structures.This work is expected to provide a more reliable CMD method for electrolyte design,shielding researchers from the pitfalls of erroneous simulation outcomes.
基金financially supported by the National Natural Science Foundation of China(No.52371114 and No.51971118).
文摘Developing rechargeable aqueous Zn batteries for large-scale energy storage is impeded by inadequate reversibility and stability of the Zn anode,primarily caused by parasitic reactions and heterogeneous deposition.This study proposes an economical electrolyte strategy to address these Zn-related issues.The addition of a supporting salt enhances the thermodynamic stability of water,reduces the number of highly reactive water molecules,and modulates the interfacial electrostatic interaction.This approach effectively suppresses hydrogen evolution reaction and uncontrolled deposition.Remarkably,the rationally proportioned electrolyte allows a high average Coulombic efficiency of 99.93%for 1000 cycles in a Zn‖Cu battery and a prolonged lifespan exceeding 4800 h in Zn‖Zn cells.The knock-on effect is that Zn‖MnO_(2)pouch cells deliver stable cycling performance,demonstrating the viability of this approach for practical applications.
基金supported by the National Natural Science Foundation of China(No.11047164)the National Key Laboratory of Infrared Detection Technologies(No.IRDT-23-S01)the Shanghai Explorer Program(No.24TS1403400)。
文摘The high safety of aqueous magnesium ion batteries(AMIBs)contrasts with their limited electrochemical performance.To overcome electrolyte-induced parasitic reactions,it is essential to understand the dynamic evolution of concentration-dependent metal ion solvation structures(MISSs).This study systematically reveals the solvation structure evolution of MgCl_(2) aqueous solutions across a full concentration range(0-30 M)and its impact on electrochemical properties using molecular dynamics simulations and density functional theory calculations.Results indicate that six characteristic solvation configurations exist,exhibiting a dynamic,concentration-dependent inter-evolution defined as the solvation structure evolutionary processes(SSEP).The four-phase glass transition mechanism in solvation structure evolution is revealed by analyzing the percentage of each type of solvation structure in different concentrations.The study shows that conductivity is directly related to the dynamic transitions of dominant solvation structures,with a shift in the Mg^(2+) coordination mode—from octahedral through pentahedral intermediates to tetrahedral—revealing a concentration-dependent ion transport mechanism.At low concentrations,free-state stochastic diffusion predominates,reaching a maximum conductivity before transitioning to relay transport within a restricted network at high concentrations.Key contributions include:a general strategy for electrolyte design based on the solvation structure evolution process,which quantitatively correlates structural occupancy with migration properties,and the“Concentration Window”regulation model that balances high conductivity with reduced side reactions.These findings clarify the structural origins of anomalous conductivity in highly concentrated electrolytes and establish a mapping between microstructural evolution and macroscopic performance,providing a theoretical basis for engineering high-security electrolytes of AMIBs.
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 faculty research fund of Sejong Universityfunding from the National Research Foundation of Korea(NRF)under grant number NRF-2022R1F1A1071444+2 种基金funding from NRF under grant numbers NRF-2022R1A2B5B03001781Funding provided by the Department of Energy Office of Energy EfficiencyRenewable Energy Vehicles Technology Office。
文摘Rechargeable batteries are essential energy storage devices that power portable devices and electrical vehicles throughout the wo rld.In general,it is thought that the electrochemical performance of recha rgeable batteries is mostly determined by the electrodes within them and that the electrolyte plays a relatively passive role.However,ion transport and storage can be greatly influenced by the electrolyte solution structure,specifically,ion solvation within the bulk and ion desolvation across the electrode/electrolyte interfaces.Herein,we studied the role of the electrolyte as an active component of electrochemical energy storage devices.We found that with an appropriate electrolyte formulation,ion storage in disordered carbonaceous anode materials can occur spontaneously without externally supplied electrical energy.Reduced graphene oxide(RGO)in an ether-based electrolyte demonstrates'spontaneous'ion storage behaviors of adsorbing and inserting the solvated ions utilizing facilitated permeability and wettability of RGO,which results in Coulombic efficiency of~145%due to additional charging capacity of~180 mAh g^(-1)during electrochemical processes.The unexpected spontaneous ion storage behavior was extensively investigated using a combination of electrochemical analyses and diagnostics,advanced characterizations,and computational simulation.We believe the spontaneous ion storage behavior offers a new way to further improve the energy efficiency of practical rechargeable batteries.
基金supported by the Natural Science Foundation of China(52488201)。
文摘Quasi-solid-state lithium-metal batteries(QSLMBs)are promising candidates for next-generation battery systems due to their high energy density and enhanced safety.However,their practical application has been hindered by low ionic conductivity and the growth of lithium dendrites.To achieve ordered transport of Li^(+)ions in quasi-solid electrolytes(QSEs),improve ionic conductivity,and homogenize Li^(+)fluxes on the surface of the lithium metal anode(LMA),we propose a novel method.This method involves constructing"ion relay stations"in QSEs by introducing cyano-functionalized boron nitride nanosheets into pentaerythritol tetraacrylate(PETEA)-based polymer electrolytes.The functionalized boron nitride nanosheets promote the dissociation of lithium salts through ion-dipole interactions,optimizing the solvated structure to facilitate the orderly transport of Li+ions,resulting in an ionic conductivity of2.5×10^(-3)S cm^(-1)at 30℃.Notably,this strategy regulates the Li^(+)distribution on the surface of the LMA,effectively inhibiting the growth of lithium dendrites,Li‖Li symmetrical cells using this type of electrolyte maintain stability for over 2000 h at 2 mA cm^(-2)and 2 mAh cm^(-2).Additionally,with a high LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)loading of 8.5 mg cm^(-2),the cells exhibit excellent cycling performance,retaining a high capacity after 400 cycles.This innovative QSE design strategy represents a significant advancement towards the development of high-performance QSLMBs.
