Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and th...Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.展开更多
Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures....Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.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 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
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
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
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
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
Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with ...Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.展开更多
The practical application of energy-dense lithium(Li)metal batteries is severely hindered by the lack of suitable electrolytes.Weakening solvent coordination to enhance Li+kinetics has become a critical principle in e...The practical application of energy-dense lithium(Li)metal batteries is severely hindered by the lack of suitable electrolytes.Weakening solvent coordination to enhance Li+kinetics has become a critical principle in electrolyte design.Here,we propose an electrolyte design strategy that weakens Li^(+)-solvent coordination through the synergistic drag effects of dual diluents.Specifically,the-CF_(2)H group in ethyl 1,1,2,2-tetrafluoroethyl ether(ETE)forms hydrogen bonds with the oxygen atom in 1,2-dimethoxyethane(DME),while the electron-donating-N=and C_(2)H_(5)O-groups in ethoxy(pentafluoro)cyclotriphosphazene(PFPN)coordinate synergistically with Li^(+).The combined effects of hydrogen bonding between ETE and DME,along with the coordination of PFPN with Li^(+),weaken the Li^(+)-DME interaction and promote anion-enriched solvation structure,thereby facilitating Li^(+)desolvation process and forming an inorganic-rich solid-electrolyte interphase.In a Li metal battery with a 30μm ultrathin Li anode and high-loading LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)cathode(23.5 mg cm^(-2)),80% of capacity was achieved after 430 cycles at 4.3 V and 84% after 310 cycles at 4.5 V.Furthermore,a 331 mAh pouch cell achieved 148 cycles with 94.9% of capacity retention.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 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
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
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
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
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
Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensur...Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensuring the performance of SICs in low-temperature environments is crucial for applications in high-altitude cold regions,where the desolvation process of Na+and the transport process in the solid electrolyte interphase(SEI)are determinant.In this paper,we proposed a multi-ether modulation strategy to construct a solvation sheath with multi-ether participation by modulating the coordination of Na+and solvents.This unique solvation sheath not only reduces the desolvation energy barrier of Na+,but more importantly forms a Na_(2)O-rich inorganic SEI and enhances the ionic dynamics of Na+.Benefiting from the excellent solvation structure design,SICs prepared with this electrolyte can achieve energy density of up to 178 Wh·kg^(-1) and ultra-high power density of 42390 W·kg^(-1) at room temperature.Notably,this SIC delivers record-high energy densities of 149 Wh·kg^(-1) and 119 Wh·kg^(-1) as well as power densities of up to 25200 W·kg^(-1) and 24591 W·kg^(-1) at−20℃ and−40℃,respectively.This work provides new ideas for the development of high-performance SICs for low-temperature operating environments.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
The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batt...The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batteries(SIBs).In this study,an anionic chemistry strategy is proposed to strengthen Na^(+)-anion coordination in the solvation sheath,and subsequently reduce the coordination numbers of EC solvents with the addition of NaClO_(4)into NaPF_(6)/EC/DEC electrolytes.Theoretical and experimental results confirm that the competitive coordination capabilities of Na^(+)-ClO_(4)^(-),with high binding energy,induce a wide electrochemical window up to 4.8 V,highly reversible Na^(+)plating/stripping,and fast desolvation kinetics at the electrode/electrolyte interface,thereby hindering the continuous electrolyte decomposition.The optimized electrolyte PEDCF-0.20 demonstrates weakened Na^(+)-EC coordination,increased interaction of Na^(+)-anion in solvation,facilitating the formation of an inorganic-rich interface layer.Consequently,a 2.1 A h cylindrical full cell of hard carbon//NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)delivers an impressive capacity retention of 93.7% after 300 cycles at an extended charging cutoff voltage of 4.1 V.This work provides a new insight into regulating the competitive coordination of anions to guarantee the remarkable cycling stability of high-voltage SIBs.展开更多
Furious dendritic growth and destructive parasitic reactions(hydrogen evolution reaction,corrosion,and passivation)severely degraded the development of aqueous Zn-ion batteries(AZIBs)in the field of grid and stationar...Furious dendritic growth and destructive parasitic reactions(hydrogen evolution reaction,corrosion,and passivation)severely degraded the development of aqueous Zn-ion batteries(AZIBs)in the field of grid and stationary energy storage.Herein,trace amount of tetracycline hydrochloride(TC-HCl)additive(only 0.5 mM)is employed as a mediator to steer a stable Zn anode-electrolyte interface.Informed by theoretical calculations and experiment analysis,TC molecule with zincophilic groups can remodel the solvation sheath and disrupt H-bonds network due to its high electronegative O atoms,which effectively expedites the desolvation process and reduces the electrochemical activity of solvent water.Additionally,the TC molecules are preferentially adsorbed on the Zn electrode than active water molecules,which are beneficial for steering uniform nucleation and restricting the erosion of electrode.Benefitting from these synergistic effects,the Zn//Zn symmetric cell containing TC-HCl additive exhibits an ultra-long cycle life of exceeding 2200 h at 1.0 mA cm^(-2)and 1.0 mAh cm^(-2).Accordingly,the practical Zn//α-MnO_(2)full cell using the modified electrolyte also demonstrates the enhanced performance.This study provides valuable insights into the widespread use of trace electrolyte additives and facilitates the industrialization of AZIBs with long lifespans.展开更多
基金supported by the National Key Research and Development Programs(2021YFB2400400)Major Science and Technology Innovation Project of Hunan Province(2020GK10102020GK1014-4)+7 种基金National Natural Science Foundation of China(32201162)the 70th general grant of China Postdoctoral Science Foundation(2021M702947)Natural Science Foundation of Henan(232300420404)Key Scientific and Technological Project of Henan Province(232102320290,232102311156)Key Research Project Plan for Higher Education Institutions in Henan Province(24A150009,23B430011)Doctor Foundation of Henan University of Engineering(D2022002)the Science and Technology Innovation Program of Hunan Province(2023RC3154)the scientific research projects of Education Department of Hunan Province(23A0188)。
文摘Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metallic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of electrochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and interface characteristics are presented.Following the influences of different strategies involving designing advanced electrode structu re,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engineering to regulate zinc ion solvated sheath structure and transport behavior are summarized and discussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.
基金supported by the National Natural Science Foundation of China (grant No.52072322)the Department of Science and Technology of Sichuan Province (CN) (grant no.23GJHZ0147,23ZDYF0262,2022YFG0294)Research and Innovation Fund for Graduate Students of Southwest Petroleum University (No.:2022KYCX111)。
文摘Safety remains a persistent challenge for high-energy-density lithium metal batteries(LMBs).The development of safe and non-flammable electrolytes is especially important in harsh conditions such as high temperatures.Herein,a flame-retardant,low-cost and thermally stable long chain phosphate ester based(tributyl phosphate,TBP)electrolyte is reported,which can effectively enhance the cycling stability of highly loaded high-nickel LMBs with high safety through co-solvation strategy.The interfacial compatibility between TBP and electrode is effectively improved using a short-chain ether(glycol dimethyl ether,DME),and a specially competitive solvation structure is further constructed using lithium borate difluorooxalate(LiDFOB)to form the stable and inorganic-rich electrode interphases.Benefiting from the presence of the cathode electrolyte interphase(CEI)and solid electrolyte interphase(SEI)enriched with LiF and Li_(x)PO_(y)F_(z),the electrolyte demonstrates excellent cycling stability assembled using a 50μm lithium foil anode in combination with a high loading NMC811(15.4 mg cm^(-2))cathode,with 88%capacity retention after 120 cycles.Furthermore,the electrolyte exhibits excellent high-temperature characteristics when used in a 1-Ah pouch cell(N/P=0.26),and higher thermal runaway temperature(238℃)in the ARC(accelerating rate calorimeter)demonstrating high safety.This novel electrolyte adopts long-chain phosphate as the main solvent for the first time,and would provide a new idea for the development of extremely high safety and high-temperature electrolytes.
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(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 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 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financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Fujian Province(2023J05047)+1 种基金the Natural Science Foundation of Xiamen,China(3502Z202372036)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations.
文摘Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.
基金supported by the Fund of University of South China(201RGC013 and 200XQD052)the Youth Science Fund Project of Hunan Provincial Natural Science Foundation(2224SZ048)。
文摘The practical application of energy-dense lithium(Li)metal batteries is severely hindered by the lack of suitable electrolytes.Weakening solvent coordination to enhance Li+kinetics has become a critical principle in electrolyte design.Here,we propose an electrolyte design strategy that weakens Li^(+)-solvent coordination through the synergistic drag effects of dual diluents.Specifically,the-CF_(2)H group in ethyl 1,1,2,2-tetrafluoroethyl ether(ETE)forms hydrogen bonds with the oxygen atom in 1,2-dimethoxyethane(DME),while the electron-donating-N=and C_(2)H_(5)O-groups in ethoxy(pentafluoro)cyclotriphosphazene(PFPN)coordinate synergistically with Li^(+).The combined effects of hydrogen bonding between ETE and DME,along with the coordination of PFPN with Li^(+),weaken the Li^(+)-DME interaction and promote anion-enriched solvation structure,thereby facilitating Li^(+)desolvation process and forming an inorganic-rich solid-electrolyte interphase.In a Li metal battery with a 30μm ultrathin Li anode and high-loading LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2)cathode(23.5 mg cm^(-2)),80% of capacity was achieved after 430 cycles at 4.3 V and 84% after 310 cycles at 4.5 V.Furthermore,a 331 mAh pouch cell achieved 148 cycles with 94.9% of capacity retention.
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 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 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(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support from National Outstanding Youth Science Fund(52222314)Near Space Technology and Industry Guidance Fund Project(LKJJ-2023010-01)+3 种基金CNPC Innovation Found(2021DQ02-1001)Dalian Outstanding Youth Science and Technology Talent Project(2023RJ006)Dalian Science and Technology Innovation Project(2022JJ12GX022)Xinghai Talent Cultivation Plan(X20200303).
文摘Sodium-ion hybrid capacitors(SICs),which combine the high energy density of batteries with the high power density and long cycle life of capacitors,are considered promising next-generation energy storage devices.Ensuring the performance of SICs in low-temperature environments is crucial for applications in high-altitude cold regions,where the desolvation process of Na+and the transport process in the solid electrolyte interphase(SEI)are determinant.In this paper,we proposed a multi-ether modulation strategy to construct a solvation sheath with multi-ether participation by modulating the coordination of Na+and solvents.This unique solvation sheath not only reduces the desolvation energy barrier of Na+,but more importantly forms a Na_(2)O-rich inorganic SEI and enhances the ionic dynamics of Na+.Benefiting from the excellent solvation structure design,SICs prepared with this electrolyte can achieve energy density of up to 178 Wh·kg^(-1) and ultra-high power density of 42390 W·kg^(-1) at room temperature.Notably,this SIC delivers record-high energy densities of 149 Wh·kg^(-1) and 119 Wh·kg^(-1) as well as power densities of up to 25200 W·kg^(-1) and 24591 W·kg^(-1) at−20℃ and−40℃,respectively.This work provides new ideas for the development of high-performance SICs for low-temperature operating environments.
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.
基金financially supported by the National Natural Science Foundation of China(52202228,52402298)Science Research Project of Hebei Education Department(BJK2022011)+3 种基金Central Funds Guiding the Local Science and Technology Development of Hebei Province(236Z4404G)Beijing Tianjin Hebei Basic Research Cooperation Special Project(E2024202273)Science and Technology Correspondent Project of Tianjin(24YDTPJC00240)supported by the U.S.Department of Energy’s Office of Science,Office of Basic Energy Science,Materials Sciences and Engineering Division。
文摘The poor electrode/electrolyte interface compatibility and inferior electrolyte oxidative tolerance in commercial ethylene carbonate(EC)-based electrolytes have hindered the development of high-voltage sodium-ion batteries(SIBs).In this study,an anionic chemistry strategy is proposed to strengthen Na^(+)-anion coordination in the solvation sheath,and subsequently reduce the coordination numbers of EC solvents with the addition of NaClO_(4)into NaPF_(6)/EC/DEC electrolytes.Theoretical and experimental results confirm that the competitive coordination capabilities of Na^(+)-ClO_(4)^(-),with high binding energy,induce a wide electrochemical window up to 4.8 V,highly reversible Na^(+)plating/stripping,and fast desolvation kinetics at the electrode/electrolyte interface,thereby hindering the continuous electrolyte decomposition.The optimized electrolyte PEDCF-0.20 demonstrates weakened Na^(+)-EC coordination,increased interaction of Na^(+)-anion in solvation,facilitating the formation of an inorganic-rich interface layer.Consequently,a 2.1 A h cylindrical full cell of hard carbon//NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)delivers an impressive capacity retention of 93.7% after 300 cycles at an extended charging cutoff voltage of 4.1 V.This work provides a new insight into regulating the competitive coordination of anions to guarantee the remarkable cycling stability of high-voltage SIBs.
基金supported by the National Natural Science Foundation of China(51702081)。
文摘Furious dendritic growth and destructive parasitic reactions(hydrogen evolution reaction,corrosion,and passivation)severely degraded the development of aqueous Zn-ion batteries(AZIBs)in the field of grid and stationary energy storage.Herein,trace amount of tetracycline hydrochloride(TC-HCl)additive(only 0.5 mM)is employed as a mediator to steer a stable Zn anode-electrolyte interface.Informed by theoretical calculations and experiment analysis,TC molecule with zincophilic groups can remodel the solvation sheath and disrupt H-bonds network due to its high electronegative O atoms,which effectively expedites the desolvation process and reduces the electrochemical activity of solvent water.Additionally,the TC molecules are preferentially adsorbed on the Zn electrode than active water molecules,which are beneficial for steering uniform nucleation and restricting the erosion of electrode.Benefitting from these synergistic effects,the Zn//Zn symmetric cell containing TC-HCl additive exhibits an ultra-long cycle life of exceeding 2200 h at 1.0 mA cm^(-2)and 1.0 mAh cm^(-2).Accordingly,the practical Zn//α-MnO_(2)full cell using the modified electrolyte also demonstrates the enhanced performance.This study provides valuable insights into the widespread use of trace electrolyte additives and facilitates the industrialization of AZIBs with long lifespans.
