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
Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) ...Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.展开更多
Currently,although some progress has been made in infancy-stage rocking-chair aqueous zinc-ion batteries(AZIBs),more discussions have focused only on the different electrochemical performances displayed by different m...Currently,although some progress has been made in infancy-stage rocking-chair aqueous zinc-ion batteries(AZIBs),more discussions have focused only on the different electrochemical performances displayed by different material types rather than the intrinsic ion transport migration electrochemistry.Herein,we for the first time delve into the mechanism of tailoring the solvation sheath and desolvation processes at the electrode/electrolyte interfaces to enhance the structural stabilities in the deep discharge states.In this work,the TiO_(2)front interfaces are induced on electrochemically active but unstable TiSe_(2)host materials to construct unique TiO_(2)/TiSe_(2)-C heterointerfaces.According to X-ray absorption near edge structure(XANES),differential electrochemical mass spectrometry(DEMS),and electrochemical quartz crystal microbalance(EQCM),the intercalated species are transformed from[Zn(H_(2)O)_(6)]^(2+)to[Zn(H_(2)O)_(2)]^(2+)due to the built-in electric fields(BEFs)effects,further accelerating the ion transfer kinetics.Furthermore,owing to the absence of high-energy desolvation solvents released from desolvation processes,hydrogen evolution reaction(HER)energy barriers,Ti-Se bond strength,and structural stabilities are significantly improved,and the initial CE and HER overpotentials of the TiO_(2)/TiSe_(2)-C heterointerfaces increased from 13.76%to 84.7%,and from 1.04 to 1.30 V,respectively,and the H2 precipitation current density even at-1.3 V decreased by 73.2%.This work provides valuable insights into the complex interface electrochemical mechanism of tailoring the solvation sheath and desolvation processes toward rocking-chair zinc-ion batteries.展开更多
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
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
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
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
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
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
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
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
The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an ...The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.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
Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfat...Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfate)(Zn(NH_(2)SO_(3))_(2))with a monovalent anion,NH_(2)SO_(3)^(-),was synthesized and dissolved in different ratios of dimethyl sulfoxide(DMSO)and H_(2)O as electrolytes for Zn-ion batteries(ZIBs).From the perspective of game theory,the influences of DMSO and H_(2)O on the solvation structure and electrochemical performance of the Zn(NH_(2)SO_(3))_(2)based electrolytes has been meticulously discussed.Computations and spectra analysis indicate that DMSO molecules are reluctant to penetrate the primary solvation structure of Zn^(2+)ions.Indeed,increasing DMSO in electrolytes can induce a transition from solvent-separated ion pairs(SSIP)to contact ion pairs(CIP),resulting in an enrichment of anions in the primary solvation structure.This alteration can significantly suppress parasitic reactions,enhance nucleation density,and refine the deposition morphology during the Zn plating process,leading to superior cyclic stability and high coulombic efficiency(CE)of Zn//Cu and Zn//Zn cells.However,the enrichment of anions in the primary solvation structure also inhibits the activity of Zn^(2+)ions,amplifies the polarization effect,and engenders a sluggish ionization dynamics,resulting in the low energy conversion efficiency of the battery.These findings underscore the influence of the anion ratio within the primary solvation structure on electrochemical properties of electrolytes for ZIBs,which may be a pivotal determinant in the Zn deposition process.展开更多
Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a s...Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.展开更多
Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.How...Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.However,uneven Na deposition and slow charge transfer kinetics still significantly impair their low temperature and rate performance.Herein,we report a non-solvating trifluoromethoxy benzene(PhOCF_(3))that modulates dipole–dipole interactions in the solvation structure.This modulation effectively reduces the affinity between Na+and solvents,promoting an anion-rich solvation sheath formation and significantly enhancing room temperature electrochemical performance in SMBs.Furthermore,temperature-dependent spectroscopic characterizations and molecular dynamics simulations reveal that these dipole–dipole interactions thermodynamically exclude solvent molecules from inner Na^(+)solvation sphere at low temperatures,which endows the electrolyte with exceptional temperature adaptability,leading to remarkable improvement in low temperature SMB performance.Consequently,Na||Vanadium phosphate sodium(NVP)cells with the optimized electrolyte achieve 10,000 cycles at 10 C with capacity retention of 90.2%at 25℃and over 650 cycles at 0.5 C with a capacity of 92.1 mA h g^(−1)at−40℃.This work probed the temperature-responsive property of Na+solvation structure and designed the temperature-adaptive electrolyte by regulating solvation structure via dipole–dipole interactions,offering a valuable guidance for low temperature electrolytes design for SMBs.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
The exceptional electrochemical performance of zinc anodes is frequently impeded by inadequate deposition kinetics and interfacial chemistry.Herein,we introduce the stereoisomerism to inform the balanced selection of ...The exceptional electrochemical performance of zinc anodes is frequently impeded by inadequate deposition kinetics and interfacial chemistry.Herein,we introduce the stereoisomerism to inform the balanced selection of electrolyte additives,taking into account their solvation and adsorption properties,to achieve the optimal deposition behaviors and electrochemical performance.The three-point coplanar adsorption configuration,in comparison to two-point adsorption,effectively mitigates the interference of water molecules and establishes a coplanar templating effect.This approach fosters a uniform distribution of charges,encourages the preferential orientation growth of(002)planes for uniform zinc deposition.Moreover,an appropriate level of solvation ability can modulate the solvation structure without substantially increasing the de-solvation energy barrier,thereby facilitating faster deposition kinetics than what is observed in cases of strong solvation.As a result,Zn//Zn cell can achieve an excellent performance of more than 3470 h at 2 mA cm^(-2)and 1 mAh cm^(-2),and Zn//AC full cell can work for 50000 cycles at 3 A g^(-1).Additionally,under practical conditions(N/P=4.37),the assembled Zn//I2 full cell demonstrates stable lifespan for 710 cycles at 1 A g^(-1).This work showcases the interplay between adsorption configuration of stereoisomeric additives on the cycling.展开更多
The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate elect...The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.展开更多
Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,ramp...Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.展开更多
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funded by National Natural Science Foundation of China (22379072, 92372111, 22179070)the Startup Foundation for Introducing Talent of NUIST (2022r038)+1 种基金the Jiangsu Specially Appointed Professor Program, the Natural Science Foundation of Jiangsu Province (BK20220073)the Fundamental Research Funds for the Central Universities (RF1028623157)。
文摘Designing anion-dominated weak solvation structures is often achieved by elevating the concentration of Li salts.However,this is accompanied by the increase in the cost.Herein,a medium concentration electrolyte (1 M) with weak solvation structures is established by the multi-anion strategy.Multiple anions in the electrolyte strengthen the anion-solvent interactions through stronger ion–dipole interactions.This reduces the quantity of free solvent and improves the reduction resistance of solvents.In addition,the Li ion–solvent interaction is weakened,facilitating the anions to enter the solvation sheaths of Li ions.This multi-anion-dominated weak solvation structures boost Li ion diffusion in the electrolyte,accelerate the desolvation process of Li ions,and induce inorganic-rich solid electrolyte interphase and uniform Li deposition.An average Coulombic efficiency of 99.1%for repeated Li plating/stripping can be achieved.Li||LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cells with a high cathode loading of 3.0 m A h cm^(-2) can maintain a capacity retention as high as 95% after 150 cycles.This finding provides novel standpoints to modulate the interaction of solvation structures and extend the lifespan of high-energy–density Li metal batteries.
基金supported by the National Natural Science Foundation of China(51977097).
文摘Currently,although some progress has been made in infancy-stage rocking-chair aqueous zinc-ion batteries(AZIBs),more discussions have focused only on the different electrochemical performances displayed by different material types rather than the intrinsic ion transport migration electrochemistry.Herein,we for the first time delve into the mechanism of tailoring the solvation sheath and desolvation processes at the electrode/electrolyte interfaces to enhance the structural stabilities in the deep discharge states.In this work,the TiO_(2)front interfaces are induced on electrochemically active but unstable TiSe_(2)host materials to construct unique TiO_(2)/TiSe_(2)-C heterointerfaces.According to X-ray absorption near edge structure(XANES),differential electrochemical mass spectrometry(DEMS),and electrochemical quartz crystal microbalance(EQCM),the intercalated species are transformed from[Zn(H_(2)O)_(6)]^(2+)to[Zn(H_(2)O)_(2)]^(2+)due to the built-in electric fields(BEFs)effects,further accelerating the ion transfer kinetics.Furthermore,owing to the absence of high-energy desolvation solvents released from desolvation processes,hydrogen evolution reaction(HER)energy barriers,Ti-Se bond strength,and structural stabilities are significantly improved,and the initial CE and HER overpotentials of the TiO_(2)/TiSe_(2)-C heterointerfaces increased from 13.76%to 84.7%,and from 1.04 to 1.30 V,respectively,and the H2 precipitation current density even at-1.3 V decreased by 73.2%.This work provides valuable insights into the complex interface electrochemical mechanism of tailoring the solvation sheath and desolvation processes toward rocking-chair zinc-ion batteries.
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 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 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.
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 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 National Natural Science Foundation of China(52272258 and 52411530056)the Beijing Nova Program(20220484214)+1 种基金Key R&D and Transformation Projects in Qinghai Province(2023-HZ-801)the financial support from the China Scholarship Council(No.202006210070)。
文摘Aqueous zinc-ion batteries encounter impediments on their trajectory towards commercialization,primarily due to challenges such as dendritic growth,hydrogen evolution reaction.Throughout recent decades of investigation,electrolyte modulation by using function additives is widely considered as a facile and efficient way to prolong the Zn anode lifespan.Herein,N-(2-hydroxypropyl)ethylenediamine is employed as an additive to attach onto the Zn surface with a substantial adsorption energy with(002)facet.The as-formed in-situ solid-electrolyte interphase layer effectively mitigates hydrogen evolution reaction by constructing a lean-water internal Helmholtz layer.Additionally,N-(2-hydroxypropyl)ethylenediamine establishes a coordination complex with Zn^(2+),thereby modulating the solvation structure and enhancing the mobility of Zn^(2+).As expected,the Zn-symmetrical cell with N-(2-hydroxypropyl)ethylenediamine additive demonstrated successful cycling exceeding 1500 h under 1 mA cm^(-2) for0.5 mAh cm^(-2).Furthermore,the Zn//δ-MnO_(2) battery maintains a capacity of approximately 130 mAh g^(-1) after 800 cycles at 1 A g^(-1),with a Coulombic efficiency surpassing 98%.This work presents a streamlined approach for realizing aqueous zinc-ion batteries with extended service life.
基金supported by the National Key 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Recruitment Program of Global Experts(China)the Hundred-Talent Project of Fujian+1 种基金Fuzhou UniversityFuda Zijin Hydrogen Energy Technology Co.,Ltd for the financial support。
文摘The electrochemical instability of traditional ether-based electrolytes poses a challenge for their use in high-voltage lithium metal batteries.Herein,a synergetic optimization strategy was proposed by introducing an additive with a strong electron-withdrawing group and significant steric hindrance-isosorbide dinitrate(ISDN),reconstructing the solvation structure and solid electrolyte interphase(SEI),enabling highly stable and efficient lithium metal batteries.We found that ISDN can strengthen the interaction between Li^(+)and the anions of lithium salts and weaken the interaction between Li^(+)and the solvent in the solvation structure.It promotes the formation of a LiF-rich and LiN_(x)O_(y)-rich SEI layer,enhancing the uniformity and compactness of Li deposition and inhibiting solvent decomposition,which effectively expands the electrochemical window to 4.8 V.The optimized Li‖Li cells offer stable cycling over 1000 h with an overpotential of only 57.7 mV at 1 mA cm^(-2).Significantly,Li‖3.7 mA h LiFePO_(4)cells retain 108.3%of initial capacity after 546 cycles at a rate of 3 C.Under high-loading conditions(Li‖4.9 mA h LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)full cells)and a cutoff voltage of 4.5 V,the ISDN-containing electrolyte enables stable cycling for 140 cycles.This study leverages steric hindrance and electron-withdrawing effect to synergistically reconstruct the Li^(+)solvation structure and promote stable SEI formation,establishing a novel electrolyte paradigm for high-energy lithium metal batteries.
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 National Natural Science Foundation of China(51972187 and 22279068)the Natural Science Foundation of Shandong Province(ZR2023ME182)the Fundation of Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials(Anhui University of Technology)(GFST2024KF03)。
文摘Monovalent anions,with relatively low charge density,exhibit weak bond energy with Zn^(2+)ions,which facilitates the solubility of Zn salts and the regulation of solvation structures.In this study,zinc bis(aminosulfate)(Zn(NH_(2)SO_(3))_(2))with a monovalent anion,NH_(2)SO_(3)^(-),was synthesized and dissolved in different ratios of dimethyl sulfoxide(DMSO)and H_(2)O as electrolytes for Zn-ion batteries(ZIBs).From the perspective of game theory,the influences of DMSO and H_(2)O on the solvation structure and electrochemical performance of the Zn(NH_(2)SO_(3))_(2)based electrolytes has been meticulously discussed.Computations and spectra analysis indicate that DMSO molecules are reluctant to penetrate the primary solvation structure of Zn^(2+)ions.Indeed,increasing DMSO in electrolytes can induce a transition from solvent-separated ion pairs(SSIP)to contact ion pairs(CIP),resulting in an enrichment of anions in the primary solvation structure.This alteration can significantly suppress parasitic reactions,enhance nucleation density,and refine the deposition morphology during the Zn plating process,leading to superior cyclic stability and high coulombic efficiency(CE)of Zn//Cu and Zn//Zn cells.However,the enrichment of anions in the primary solvation structure also inhibits the activity of Zn^(2+)ions,amplifies the polarization effect,and engenders a sluggish ionization dynamics,resulting in the low energy conversion efficiency of the battery.These findings underscore the influence of the anion ratio within the primary solvation structure on electrochemical properties of electrolytes for ZIBs,which may be a pivotal determinant in the Zn deposition process.
基金supported by the Natural Science Foundation of China(22379073,52373275)the Natural Science Foundation of Tianjin,China(18JCZDJC31400)the Ministry of Education Innovation Team(IRT13022).
文摘Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.
基金the financial support of National Key Research and Development Program of China(2021YFB2400300)National Natural Science Foundation of China(21875198,21875195)+1 种基金the Fundamental Research Funds for the Central Universities(20720190040)the Key Project of Science and Technology of Xiamen(3502Z20201013)。
文摘Sodium metal batteries(SMBs)are expected to become an alternative solution for energy storage and power systems in the future due to their abundant resources,substantial energy–density,and all-climate performance.However,uneven Na deposition and slow charge transfer kinetics still significantly impair their low temperature and rate performance.Herein,we report a non-solvating trifluoromethoxy benzene(PhOCF_(3))that modulates dipole–dipole interactions in the solvation structure.This modulation effectively reduces the affinity between Na+and solvents,promoting an anion-rich solvation sheath formation and significantly enhancing room temperature electrochemical performance in SMBs.Furthermore,temperature-dependent spectroscopic characterizations and molecular dynamics simulations reveal that these dipole–dipole interactions thermodynamically exclude solvent molecules from inner Na^(+)solvation sphere at low temperatures,which endows the electrolyte with exceptional temperature adaptability,leading to remarkable improvement in low temperature SMB performance.Consequently,Na||Vanadium phosphate sodium(NVP)cells with the optimized electrolyte achieve 10,000 cycles at 10 C with capacity retention of 90.2%at 25℃and over 650 cycles at 0.5 C with a capacity of 92.1 mA h g^(−1)at−40℃.This work probed the temperature-responsive property of Na+solvation structure and designed the temperature-adaptive electrolyte by regulating solvation structure via dipole–dipole interactions,offering a valuable guidance for low temperature electrolytes design for SMBs.
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 Natural Science Foundation of Hunan Province(No.2023JJ20064)the National Natural Science Foundation of China(No.52377222).
文摘The exceptional electrochemical performance of zinc anodes is frequently impeded by inadequate deposition kinetics and interfacial chemistry.Herein,we introduce the stereoisomerism to inform the balanced selection of electrolyte additives,taking into account their solvation and adsorption properties,to achieve the optimal deposition behaviors and electrochemical performance.The three-point coplanar adsorption configuration,in comparison to two-point adsorption,effectively mitigates the interference of water molecules and establishes a coplanar templating effect.This approach fosters a uniform distribution of charges,encourages the preferential orientation growth of(002)planes for uniform zinc deposition.Moreover,an appropriate level of solvation ability can modulate the solvation structure without substantially increasing the de-solvation energy barrier,thereby facilitating faster deposition kinetics than what is observed in cases of strong solvation.As a result,Zn//Zn cell can achieve an excellent performance of more than 3470 h at 2 mA cm^(-2)and 1 mAh cm^(-2),and Zn//AC full cell can work for 50000 cycles at 3 A g^(-1).Additionally,under practical conditions(N/P=4.37),the assembled Zn//I2 full cell demonstrates stable lifespan for 710 cycles at 1 A g^(-1).This work showcases the interplay between adsorption configuration of stereoisomeric additives on the cycling.
基金supported by the Lithium Resources and Lithium Materials Key Laboratory of Sichuan Province(LRMKF202405)the National Natural Science Foundation of China(52402226)+3 种基金the Natural Science Foundation of Sichuan Province(2024NSFSC1016)the Scientific Research Startup Foundation of Chengdu University of Technology(10912-KYQD2023-10240)the opening funding from Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology)(KFM202507,Ministry of Education)the funding provided by the Alexander von Humboldt Foundation。
文摘The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.
基金supported by the National Natural Science Foundation of China(22479022)the Natural Science Foundation of Liaoning Province(2020-MS-021)。
文摘Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.
