With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candida...With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.展开更多
Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerati...Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerating interfaces decay.Herein,we propose for the first time a novel strategy to enhance the interfacial stabilities by insitu dynamic reconstruction of weakly solvated Zn2þduring the desolvation processes at heterointerfaces.Theoretical calculations indicate that,due to built-in electric field effects(BEFs),the plating/stripping mechanism shifts from[Zn(H_(2)O)_(6)]_(2)þto[Zn(H_(2)O)_(5)(SO_(4))^(2-)]_(2)þwithout additional electrolyte additives,reducing the solvation ability of H_(2)O,enhancing the competitive coordination of SO_(4)^(2-),essentially eliminating the undesirable side effects of anodes.Hence,symmetric cells can operate stably for 3000 h(51.7-times increase in cycle life),and the full cells can operate stably for 5000 cycles(51.5-times increase in cycle life).This study provides valuable insights into the critical design of weakly solvated Zn^(2+) þand desolvation processes at heterointerfaces.展开更多
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
Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graph...Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.展开更多
Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The ...Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The iron atom precursor complex, bis（toluene）iron（0） formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, Mǒssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis（toluene）iron（0）, and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced γ-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.展开更多
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
order to assess the promotional effects of La3+ on CO hydrogenation of Co/SiO2 catalyst, solvated metal atom impregnation (SMAI) method was used to prepare unpromoted 10% (mass fraction) Co/SiO2 and a series of La3+-p...order to assess the promotional effects of La3+ on CO hydrogenation of Co/SiO2 catalyst, solvated metal atom impregnation (SMAI) method was used to prepare unpromoted 10% (mass fraction) Co/SiO2 and a series of La3+-promoted 10% (mass fraction) Co/SiO2 catalyst with different La/Co atomic ratios (0.1, 0.3, 0.5). X-ray diffraction (XRD), and CO chemisorption measurements show that the cobalt particle size decreases as the La/Co ratios increase. X-ray photoelectron spectrescopy indicates that cobalt is in zero-valent state for all the samples. Catalytic test shows that the catalytic activity of La3+-promoted Co/SiO2 in CO hydrogenation is higher than that of unpromoted Co/SiO2, and enhances with the La/Co ratios increase. La3+ promotion also causes the enhanced selectivity of Co/SiO2 catalyst for higher hydrocarbon products.展开更多
D-72 resin supported nickel-copper catalysts prepared by solvated metal atom impregnation (SMAI) were studied by magnetic measurements and X-ray photoelectron spectroscopy (XPS). The Ni particles on the catalysts are ...D-72 resin supported nickel-copper catalysts prepared by solvated metal atom impregnation (SMAI) were studied by magnetic measurements and X-ray photoelectron spectroscopy (XPS). The Ni particles on the catalysts are very highly dispersed and display superparamagnetic behaviour. Ni-Cu alloy clusters were found to be formed. The surface compositions are different from the bulk concentrations. In contrast with the surface enrichment in copper generally observed on conventional Ni-Cu catalysts, the surfaces of these catalysts are enriched in nickel. The nickel is in both zero and valent states, while copper is mainly in metallic state. Catalytic data show that the formation of Ni-Cu alloy clusters has a profound effect on the catalytic activities of the catalysts in the hydrogenation of furfural. The activity of the Ni:Cu ratio of one bimetallic catalysts is much higher than that of the Ni or Cu monometallic catalyst.展开更多
Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor comp...Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor complex, bis (toluene) iron(0) formed in the metal atom reactor, was impregnated into SiO2 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by THM, Mosbauer and chemisorption measurements, and the resules show that higher concentration of surface hydroxyl groups of SiO2-200 favours the formation of more positively charged support iron cluster Fen/SiO2-200 and the lower concentration of surface hydroxyl groups of SiO2-600 favours the formation of basically neutral supported iron cluster Fe2/SiO2-600. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the precursor complex,bis(toluene) fron(0), to decompose more rapidly, and favours the formation of relatively large iron cluster. As a consequence, these two kinds of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fe/SiO2-200 in F-T reaction is similar to that of the unreduced a-Fe2O2, while Fe2/SiO2 -600 is similar to that of reduced α-Fe2O2.展开更多
Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reac...Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.展开更多
Free radicals can improve the reaction rate,but most of them are unstable due to unpaired electrons.Simultaneously maintaining their stability and activity is challenging.Herein,taking sulfur(S)radicals as an example,...Free radicals can improve the reaction rate,but most of them are unstable due to unpaired electrons.Simultaneously maintaining their stability and activity is challenging.Herein,taking sulfur(S)radicals as an example,we propose a strategy in which solvated metal complexes constructed by Al(acetylacetonate)_(3) and different solvents can stabilize high concentrations of S radicals with good activity through ion–dipole interactions.Based on this strategy,it is first demonstrated that S_(4)^(·-) is selectively stabilized by controlling the configurations of the solvated complexes.As a result,the reaction rate of S↔Li_(2)S is increased by 8 times,and the energy efficiency and rate capability of the Li–S batteries are significantly improved,especially the 5-fold increase in cell capacities at a low electrolyte/sulfur ratio.This work provides an important strategy in which solvated metal complexes balance the activity and stability of free radicals to accelerate reactions and their application in various fields.展开更多
Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmemb...Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.展开更多
The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interfa...The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interface with a dendrite-free zinc anode is developed by adding acetone into the aqueous electrolyte.The as-formed water/acetone hybrid solvent effectively optimizes the Zn^(2+)solvation structure(coordinated water changes from 6 to 4)and induces the uniform zinc ion deposition through the high adsorption energy with the Zn(002)surface.It also stabilizes the zinc metal by reducing the corrosion reaction(hydrogen evolution)with water and the formation of a basic zinc salt by-product.As a result,the symmetrical cell with the acetone/water electrolyte exhibits a superior stability of 3700 h(154 days)at 1 mA cm^(-2).The battery with the Na_(2)V_(6)O_(16)·3H_(2)O cathode delivers an 84.1%capacity retention after 1000 cycles at 1.0 A g^(-1).The organic/aqueous electrolyte provides a new insight into understanding the relationship between solvation structure,electrode/electrolyte interface,and the performance of the zinc ion battery.展开更多
Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.H...Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.展开更多
Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle ...Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.展开更多
Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temp...Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.展开更多
Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditio...Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.展开更多
Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish...Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish Mg^(2+)transport kinetics at the electrode/electrolyte interface.Herein,we propose an electrolyte design strategy that modulates the Mg^(2+)solvation structure by introducing tetrahydrofuran(THF)as a co-solvent into a borate-based electrolyte,Mg[B(hfip)_(4)](MBF)in dimethoxyethane(DME).THF,selected from a series of linear and cyclic ethers,has a comparable dielectric constant and donor number to DME,but its cyclic structure introduces steric hindrance that induces competitive coordination with Mg^(2+).This competition weakens Mg^(2+)-solvent interactions,yielding a more labile solvation structure and enhanced desolvation kinetics.As a result,Mg||Mg cells employing the optimized MBF/1D1T electrolyte(DME:THF=1:1,v:v)exhibit a significantly reduced Mg plating/stripping overpotential of 120 mV at 10 mA cm^(-2),compared with 316 mV at 8 mA cm^(-2)with MBF/DME,along with exceptional cycling stability exceeding 1200 h.Furthermore,representative sulfide cathodes such as CuS and VS_(4)demonstrate faster activation and improved high-rate performance in the presence of MBF/1D1T.展开更多
High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery p...High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery performance is still a challenge.Herein,we propose a non-coordinating solvent anchoring strategy to regulate fluorinated amide electrolyte to enhance the stability and ionic conductivity of the interfaces.Specifically,hexafluorobenzene is employed to anchor fluorinated amide solvent by the robust dipole–dipole interactions,which weaken the coordination between fluorinated amide and Li^(+),facilitate more anions coordinating with Li^(+),and form more ion aggregates.Consequently,stable and highly conductive electrode/electrolyte interfaces enriched with LiF and Li_(3)N are constructed,drastically improving the interfacial stability and reducing interface impedance of Li metal anodes and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes.Such a rationally designed electrolyte demonstrates excellent flame retardancy,high oxidation stability(5.1 V vs.Li^(+)/Li),and enhanced low-temperature ionic conductivity.As a result,this electrolyte substantially enhances the high-voltage cycle stability(-4.8 V),rate capability(-50 C)and low-temperature cycle performance(-20℃)of Li||NCM811 cells,which retain 80.0%of the initial capacity over 600 cycles at 4.7 V.This research offers a promising strategy to design ideal electrolytes for highperformance Li metal batteries.展开更多
The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electr...The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.展开更多
基金the financial support provided by the National Natural Science Foundation of China(grant no.22373032)the open research fund of Songshan Lake Materials Laboratory(grant no.2023SLABFK06)。
文摘With the rapid growth of technologies requiring high-power energy storage,achieving long-term cyclic stability under ultra-high current density is a key challenge.Aqueous zinc-ion batteries(AZIBs)are promising candidates due to their intrinsic safety and low cost,but they suffer from severe interfacial instability at rates exceeding 10 mA cm^(-2),which drastically shortens their cycle life.Inspired by theoretical calculations,triglyme(TGDE)additive with strong electron-donating groups into Zn(OTf)_(2) electrolytes effectively disrupts the hydrogen-bond network among free water molecules,while the weak coordination of TGDE with Zn^(2+)promotes the entry of OTf-into the primary Zn^(2+)solvated sheath,thus decreasing the coordination number of water with Zn^(2+).As such,the hydrogen-bond network and the bulk solvated structure are reconstructed with better stability.Moreover,the strong adsorption of TGDE lying on the Zn(002)surface would induce Zn depositions along(002)together with the reduced exposed surface,further effectively inhibiting side reactions.Likewise,TGDE electrolyte induces the formation of such ZnF_(2)-ZnS dual-layer solid electrolyte interface(SEI)with superior chemical stability and ionic conductivity,thereby regulating Zn^(2+)flux with dendrite-free depositions.Based on this electrolyte,Zn‖Zn cells can be stably cycled for 1300 h at a limit of 10 mA cm^(-2) and 10 mAh cm^(-2).The assembled Zn‖V_(2)O_(5) full cells still maintain 99.9%capacity retention after 1000 cycles at 10 A g^(-1).This work provides a feasible approach for designing aqueous electrolytes to reconstruct the hydrogen-bond network and solvated structure,which can be extended to the applications of high-rate and high-temperature scenarios.
基金financially supported by the National Natural Science Foundation of China(51977097).
文摘Solvated zinc ions are prone to undergo desolvation at the electrode/electrolyte interfaces,and unstable H_(2)O molecules within the solvated sheaths tend to trigger hydrogen evolution reaction(HER),further accelerating interfaces decay.Herein,we propose for the first time a novel strategy to enhance the interfacial stabilities by insitu dynamic reconstruction of weakly solvated Zn2þduring the desolvation processes at heterointerfaces.Theoretical calculations indicate that,due to built-in electric field effects(BEFs),the plating/stripping mechanism shifts from[Zn(H_(2)O)_(6)]_(2)þto[Zn(H_(2)O)_(5)(SO_(4))^(2-)]_(2)þwithout additional electrolyte additives,reducing the solvation ability of H_(2)O,enhancing the competitive coordination of SO_(4)^(2-),essentially eliminating the undesirable side effects of anodes.Hence,symmetric cells can operate stably for 3000 h(51.7-times increase in cycle life),and the full cells can operate stably for 5000 cycles(51.5-times increase in cycle life).This study provides valuable insights into the critical design of weakly solvated Zn^(2+) þand desolvation processes at heterointerfaces.
基金supported by the National 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financially supported by the National Natural Science Foundation of China(21975251)。
文摘Graphite is a universal host material for ion intercalation. Li+-graphite intercalation compounds (GICs) have been successfully utilized as the anode material in commercial lithium-ion batteries.Similarly, anion-graphite intercalation compounds (AGICs) have been coming into their own in dual-ion batteries [1]. It is imperative to deepen an understanding of anion storage mechanisms in graphite electrode.
文摘Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The iron atom precursor complex, bis（toluene）iron（0） formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, Mǒssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis（toluene）iron（0）, and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced γ-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.
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.
文摘order to assess the promotional effects of La3+ on CO hydrogenation of Co/SiO2 catalyst, solvated metal atom impregnation (SMAI) method was used to prepare unpromoted 10% (mass fraction) Co/SiO2 and a series of La3+-promoted 10% (mass fraction) Co/SiO2 catalyst with different La/Co atomic ratios (0.1, 0.3, 0.5). X-ray diffraction (XRD), and CO chemisorption measurements show that the cobalt particle size decreases as the La/Co ratios increase. X-ray photoelectron spectrescopy indicates that cobalt is in zero-valent state for all the samples. Catalytic test shows that the catalytic activity of La3+-promoted Co/SiO2 in CO hydrogenation is higher than that of unpromoted Co/SiO2, and enhances with the La/Co ratios increase. La3+ promotion also causes the enhanced selectivity of Co/SiO2 catalyst for higher hydrocarbon products.
文摘D-72 resin supported nickel-copper catalysts prepared by solvated metal atom impregnation (SMAI) were studied by magnetic measurements and X-ray photoelectron spectroscopy (XPS). The Ni particles on the catalysts are very highly dispersed and display superparamagnetic behaviour. Ni-Cu alloy clusters were found to be formed. The surface compositions are different from the bulk concentrations. In contrast with the surface enrichment in copper generally observed on conventional Ni-Cu catalysts, the surfaces of these catalysts are enriched in nickel. The nickel is in both zero and valent states, while copper is mainly in metallic state. Catalytic data show that the formation of Ni-Cu alloy clusters has a profound effect on the catalytic activities of the catalysts in the hydrogenation of furfural. The activity of the Ni:Cu ratio of one bimetallic catalysts is much higher than that of the Ni or Cu monometallic catalyst.
文摘Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor complex, bis (toluene) iron(0) formed in the metal atom reactor, was impregnated into SiO2 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by THM, Mosbauer and chemisorption measurements, and the resules show that higher concentration of surface hydroxyl groups of SiO2-200 favours the formation of more positively charged support iron cluster Fen/SiO2-200 and the lower concentration of surface hydroxyl groups of SiO2-600 favours the formation of basically neutral supported iron cluster Fe2/SiO2-600. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the precursor complex,bis(toluene) fron(0), to decompose more rapidly, and favours the formation of relatively large iron cluster. As a consequence, these two kinds of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fe/SiO2-200 in F-T reaction is similar to that of the unreduced a-Fe2O2, while Fe2/SiO2 -600 is similar to that of reduced α-Fe2O2.
基金the financial support by the National Natural Science Foundation of China(No.52573221,U2330124,U20A2072,52072352,21875226)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)+1 种基金the Scientific Research Funds for Central Universities(ZYGX2025XJ016)the Sichuan Science and Technology Program(2023ZYD0026)。
文摘Aqueous zinc-ion batteries have emerged as highly promising energy storage devices due to their high theoretical capacity,low cost,and high safety.However,they still suffer from dendrite growth and parasitic side reactions caused by reactive aqueous electrolytes,which not only compromise reversibility but may also lead to internal short circuits,severely limiting practical applications.Herein,inulin(INU),a hydroxyl-rich polysaccharide,is proposed as a multifunctional electrolyte additive.Experimental and density functional theory calculations reveal that INU molecules effectively disrupt the original hydrogen-bond network,facilitating Zn^(2+)desolvation and rapid migration,thereby effectively resisting hydrogen evolution reaction,Zn corrosion,and by-products formation.Additionally,INU preferentially adsorbs on the Zn(002)crystal plane,forming a hydrophobic protective layer and guiding uniform Zn^(2+)deposition,thus inhibiting random dendritic growth.The presence of INU also effectively retards the dissolution process of V_(2)O_(5).As a result,the Zn‖Zn symmetric cell assembled with INU-3 electrolyte achieves an extended cycling life of 2400 h at a current density of 0.5 mA cm^(-2) and an areal capacity of0.5 mAh m^(-2).Furthermore,the Zn‖V_(2)O_(5) full cell exhibits a high capacity of 386.0 mAh g^(-1) at0.5 A g^(-1) and a high capacity retention of 55.26%at 8 A g^(-1).The full cell maintains remarkable capacity retention of 73%after 500 cycles at 1 A g^(-1) and 91%after 1000 cycles at 3 A g^(-1).This work inspires the study of electrolyte additives for aqueous zinc-ion batteries.
基金This work was supported financially by the National Natural Science Foundation of China(22005085,U22A2043,21773055)Joint Fund of Science and Technology R&D Plan of Henan Province(222301420005)+1 种基金Project funded by China Postdoctoral Science Foundation(2020M682277)The authors gratefully acknowledge Dr.Rui Zhu for the discussion about modeling.
文摘Free radicals can improve the reaction rate,but most of them are unstable due to unpaired electrons.Simultaneously maintaining their stability and activity is challenging.Herein,taking sulfur(S)radicals as an example,we propose a strategy in which solvated metal complexes constructed by Al(acetylacetonate)_(3) and different solvents can stabilize high concentrations of S radicals with good activity through ion–dipole interactions.Based on this strategy,it is first demonstrated that S_(4)^(·-) is selectively stabilized by controlling the configurations of the solvated complexes.As a result,the reaction rate of S↔Li_(2)S is increased by 8 times,and the energy efficiency and rate capability of the Li–S batteries are significantly improved,especially the 5-fold increase in cell capacities at a low electrolyte/sulfur ratio.This work provides an important strategy in which solvated metal complexes balance the activity and stability of free radicals to accelerate reactions and their application in various fields.
基金the financial support from the National Natural Science Foundation of China(22408182)the Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT24024)the Natural Science Foundation of Inner Mongolia Autonomous Region(2023QN02007 and 2025QN02009)。
文摘Lithium(Li)dendrites,resulting from poor ion desolvation and transport behavior at the anode/electrolyte interface during electrodeposition,severely impede the practicality of Li metal anodes.Inspired by the transmembrane cascade transport mechanism of biological ion pumps,we design a biomimetic dual-cascade separator(BDS)based on gradient pore core–shell Gd_(2)O_(3)@ZIF-7 nanoparticles to stabilize Li metal anodes.The mesoporous Gd_(2)O_(3)core,via Lewis acidic surface,weakens Li^(+) -solvent interactions,thereby reconstructing the solvation structure and achieving pre-desolvation.The microporous ZIF-7 shell then promotes final desolvation through strong confinement effect and N-rich site coordination,while its nanochannels homogenize Li^(+) transport.This synergistic meso/microporous gradient creates a unique dual-cascade effect for ion desolvation and transport.Consequently,BDS achieves a low desolvation energy barrier,a high Li^(+) transference number(0.71),and dendrite-free Li deposition.The average Coulombic efficiency rises from 72.7%to 98.4%,the cycling performance of the Li||Li symmetrical cell improves by 3.2 times,and the capacity retention of LiFePO_4(LFP)||Li full cell increases from 38.3%to73.4%after 500 cycles.This work offers a novel separator design concept,deepens Li deposition understanding,and guides separators from passive protection to active regulation.
基金supported by the National Natural Science Foundation of China(52202118)the Henan Provincial Department of Education(232301420050)+1 种基金the China Postdoctoral Science Foundation(2020TQ0275)the Postdoctoral Science Foundation of Zhengzhou University(22120027).
文摘The uncontrollable growth of zinc metal dendrites and the water-induced parasitic reaction in pure aqueous electrolyte cause the poor cycling stability of zinc ion battery.Herein,a stable electrode/electrolyte interface with a dendrite-free zinc anode is developed by adding acetone into the aqueous electrolyte.The as-formed water/acetone hybrid solvent effectively optimizes the Zn^(2+)solvation structure(coordinated water changes from 6 to 4)and induces the uniform zinc ion deposition through the high adsorption energy with the Zn(002)surface.It also stabilizes the zinc metal by reducing the corrosion reaction(hydrogen evolution)with water and the formation of a basic zinc salt by-product.As a result,the symmetrical cell with the acetone/water electrolyte exhibits a superior stability of 3700 h(154 days)at 1 mA cm^(-2).The battery with the Na_(2)V_(6)O_(16)·3H_(2)O cathode delivers an 84.1%capacity retention after 1000 cycles at 1.0 A g^(-1).The organic/aqueous electrolyte provides a new insight into understanding the relationship between solvation structure,electrode/electrolyte interface,and the performance of the zinc ion battery.
基金supported by the National Key R&D Program of China(No.2022YFB3803400)National Natural Science Foundation of China(Nos.52102054,52020105010,51927803,52188101 and 52072378)+1 种基金Liaoning Province Science and Technology Planning Project(No.2022-BS-007)Fujian Science and Technology Program(No.2023T3025).
文摘Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures,bringing challenges to the application of lithium-ion batteries(LIBs)at low temperatures.Herein,the ester solvent of methyl propionate(MP)with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes.Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions.The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied.As a result,methyl pentafluoropropionate(M5F)with five fluorine atoms was selected for its optimal interactions with both Li+and MP solvent in the primary solvation structure,contributing to desired solvation structure for fast interfacial transport.The LiFePO_(4)(LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8%after 120 cycles and retained 81.2%of room-temperature capacity when charged and discharged at−30℃.1 Ah LFP||graphite pouch cell with high cathode loading(20 mg/cm^(2))in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at−20℃.This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
基金supported by the National Natural Science Foundation of China (Grant No. U21A20332)support from the Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Lithium-mediated nitrogen reduction reaction(LMNRR)is a promising route for sustainable ammonia synthesis,but the generation of excessive solid electrolyte interphase(SEI)severely limits its efficiency.Here,we tackle this challenge by introducing n-hexane as an electrolyte additive to weaken LiClO4 ionization,achieving minimized dissociation via squeezed solvation shells with compact ion pairs.Molecular dynamics simulations and experimental characterizations reveal that n-hexane enriches anion coordination around Li+,endowing the electrolyte with robust anti-reduction capability.This suppresses SEI overgrowth,reduces interfacial resistance,and accelerates N2 diffusion.Consequently,a thinner,inorganic-rich SEI is formed,enabling high nitrogen flux and rapid active Li3N generation kinetics.Consequently,the proof-of-concept system achieves unprecedentedly high Faradaic efficiency of 53.8%±8.2%at 10 mA cm^(−2)and NH_(3) yield rate of 88.57±9.5 nmol s^(−1)cm^(−2)under ambient conditions,making a giant step further toward industrializing the electrochemical ammonia production.
基金the financial support from the Key Project of Shaanxi Provincial Natural Science Foundation-Key Project of Laboratory(2025SYS-SYSZD-117)the Natural Science Basic Research Program of Shaanxi(2025JCYBQN-125)+8 种基金Young Talent Fund of Xi'an Association for Science and Technology(0959202513002)the Key Industrial Chain Technology Research Program of Xi'an(24ZDCYJSGG0048)the Key Research and Development Program of Xianyang(L2023-ZDYF-SF-077)Postdoctoral Fellowship Program of CPSF(GZC20241442)Shaanxi Postdoctoral Science Foundation(2024BSHSDZZ070)Research Funds for the Interdisciplinary Projects,CHU(300104240913)the Fundamental Research Funds for the Central Universities,CHU(300102385739,300102384201,300102384103)the Scientific Innovation Practice Project of Postgraduate of Chang'an University(300103725063)the financial support from the Australian Research Council。
文摘Lithium-ion batteries(LIBs),while dominant in energy storage due to high energy density and cycling stability,suffer from severe capacity decay,rate capability degradation,and lithium dendrite formation under low-temperature(LT)operation.Therefore,a more comprehensive and systematic understanding of LIB behavior at LT is urgently required.This review article comprehensively reviews recent advancements in electrolyte engineering strategies aimed at improving the low-temperature operational capabilities of LIBs.The study methodically examines critical performance-limiting mechanisms through fundamental analysis of four primary challenges:insufficient ionic conductivity under cryogenic conditions,kinetically hindered charge transfer processes,Li+transport limitations across the solidelectrolyte interphase(SEI),and uncontrolled lithium dendrite growth.The work elaborates on innovative optimization approaches encompassing lithium salt molecular design with tailored dissociation characteristics,solvent matrix optimization through dielectric constant and viscosity regulation,interfacial engineering additives for constructing low-impedance SEI layers,and gel-polymer composite electrolyte systems.Notably,particular emphasis is placed on emerging machine learning-guided electrolyte formulation strategies that enable high-throughput virtual screening of constituent combinations and prediction of structure-property relationships.These artificial intelligence-assisted rational design frameworks demonstrate significant potential for accelerating the development of next-generation LT electrolytes by establishing quantitative composition-performance correlations through advanced data-driven methodologies.
基金supported by the Key Laboratory of Sichuan Province for Lithium Resources Comprehensive Utilization and New Lithium Based Materials for Advanced Battery Technology(LRMKF202405)the National Natural Science Foundation of China(52402226)the Sichuan Provincial Natural Science Foundation (2024NSFSC1016)
文摘Lithium metal batteries(LMBs)have emerged as pivotal energy storage solutions for electric vehicles and portable electronics.However,their operation under extreme conditions(high-temperature and fast-charging conditions)faces significant challenges,including accelerated electrolyte decomposition,interfacial instability,and potential thermal runaway risks.To address these challenges,we present a solvation-interphase synergistic regulation strategy using 2-fluorobenzenesulfonamide(2-FBS)as a multifunctional electrolyte additive.The 2-FBS molecule effectively modulates the Li^(+)solvation structure by reducing the coordination of ethylene carbonate(EC)solvent.This transformation suppresses EC-induced parasitic reactions while scavenging superoxide radicals,thereby mitigating gas evolution at electrode interfaces.Upon preferential decomposition,2-FBS further promotes the formation of a robust LiF-Li_(3)N-Li_(2)S-rich interphase with exceptional mechanical strength(Young’s modulus:39.4 GPa).This inorganic-rich hybrid interphase simultaneously enables dendrite-free lithium plating and enhances cathode thermal stability.Consequently,2-FBS-modified electrolyte empowers LiCoO_(2)//Li cells to deliver 82.8%capacity retention after 800 cycles at 55°C and sustain 81.2%capacity retention after 1500 cycles at 4 C.Moreover,practical validation through nail penetration tests confirms the effectiveness of the electrolyte in preventing thermal propagation in fully charged pouch cells.This work establishes a paradigm for enabling reliable battery operation under extreme conditions through synergistic solvation and interphase engineering.
基金supported by the National Natural Science Foundation of China(NSFC,Grant Nos.52222211 and 52472209)the State Key Laboratory of Materials-Oriented Chemical Engineering(Grant No.SKL-MCE-23A05)+1 种基金“333”Project of Jiangsu Provincethe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Magnesium batteries are attracting growing interest as next-generation energy storage technology due to their high safety,cost-effectiveness,and resource abundance.However,their development remains limited by sluggish Mg^(2+)transport kinetics at the electrode/electrolyte interface.Herein,we propose an electrolyte design strategy that modulates the Mg^(2+)solvation structure by introducing tetrahydrofuran(THF)as a co-solvent into a borate-based electrolyte,Mg[B(hfip)_(4)](MBF)in dimethoxyethane(DME).THF,selected from a series of linear and cyclic ethers,has a comparable dielectric constant and donor number to DME,but its cyclic structure introduces steric hindrance that induces competitive coordination with Mg^(2+).This competition weakens Mg^(2+)-solvent interactions,yielding a more labile solvation structure and enhanced desolvation kinetics.As a result,Mg||Mg cells employing the optimized MBF/1D1T electrolyte(DME:THF=1:1,v:v)exhibit a significantly reduced Mg plating/stripping overpotential of 120 mV at 10 mA cm^(-2),compared with 316 mV at 8 mA cm^(-2)with MBF/DME,along with exceptional cycling stability exceeding 1200 h.Furthermore,representative sulfide cathodes such as CuS and VS_(4)demonstrate faster activation and improved high-rate performance in the presence of MBF/1D1T.
基金supported by the Science Foundation of High-Level Talents of Wuyi University(2019AL017,2021AL002)。
文摘High-voltage Li metal batteries hold great promise for next-generation energy storage,but constructing robust and highly conductive electrode/electrolyte interfaces via electrolyte engineering to enhance the battery performance is still a challenge.Herein,we propose a non-coordinating solvent anchoring strategy to regulate fluorinated amide electrolyte to enhance the stability and ionic conductivity of the interfaces.Specifically,hexafluorobenzene is employed to anchor fluorinated amide solvent by the robust dipole–dipole interactions,which weaken the coordination between fluorinated amide and Li^(+),facilitate more anions coordinating with Li^(+),and form more ion aggregates.Consequently,stable and highly conductive electrode/electrolyte interfaces enriched with LiF and Li_(3)N are constructed,drastically improving the interfacial stability and reducing interface impedance of Li metal anodes and LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathodes.Such a rationally designed electrolyte demonstrates excellent flame retardancy,high oxidation stability(5.1 V vs.Li^(+)/Li),and enhanced low-temperature ionic conductivity.As a result,this electrolyte substantially enhances the high-voltage cycle stability(-4.8 V),rate capability(-50 C)and low-temperature cycle performance(-20℃)of Li||NCM811 cells,which retain 80.0%of the initial capacity over 600 cycles at 4.7 V.This research offers a promising strategy to design ideal electrolytes for highperformance Li metal batteries.
基金supported by the National Natural Science Foundation of China(Nos.U21A20311 and 52400163).
文摘The high voltage of Li||LiCoO_(2) battery can increase the energy density.However,the cycling performance associated with cathode structural stability remains challenging.To address this question,we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO_(2) battery by using trimethylsilyl isocyanate(TMIS)as electrolyte additive.The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI.By the synergistic action,the Co3+dissolution problem of the LiCoO_(2) cathode was effectively curbed.Furthermore,TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li^(+).As expected,the 4.6 V Li||LiCoO_(2) battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
