Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified W...Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.展开更多
The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising propert...The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.展开更多
Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via alte...Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via altering the solvating power of the solvent,but it is difficult to dissolve the majority of Li salts and fail to cycle at a cut-off voltage above 4.5 V.Herein,we present a new-type WSE that is regulated by the anion rather than the solvent,and the first realize stable cycling of dimethoxyethane(DME)at 4.6 V without the use of the“solvent-in-salt”strategy.The relationships between the degree of dissociation of salts,the solvation structure of electrolytes,and the electrochemical performance of LMBs were systematically investigated.We found that LiBF_(4),which has the lowest degree of dissociation,can construct an anion-rich inner solvation shell,resulting in anion-derived anode/cathode interphases.Thanks to such unusual solvation structure and interphasial chemistry,the Li-LiCoO_(2)full cell with LiBF_(4)-based WSE could deliver excellent rate performance(115 mAh g^(-1)at 10 C)and outstanding cycling stability even under practical conditions,including high loading(10.7 mg cm^(-2)),thin Li(50μm),and limited electrolyte(1.2μL mg^(-1)).展开更多
Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes...Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes fall behind the ever-growing demands for fast-charging,wide-temperature operation,and safety properties of Li batteries.Despite the great success of(localized)high-concentration electrolytes,they still suffer from disadvantages,such as low ionic conductivity and high cost.Weakly solvating electrolytes(WSEs),also known as low-solvating electrolytes,offer another solution to these challenges,and they have attracted intensive research interests in recent years.This contribution reviews the working mechanisms,design principles,and recent advances in the development of WSEs.A summary and perspective regarding future research directions in this field is also provided.The insights will benefit academic and industrial communities in the design of safe and high-performance next-generation Li batteries.展开更多
Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well o...Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well over temperature ranges.Here,we present a new electrolyte design that uses fluorosulfonyl carboxylate as a non-solvating solvent to form difluoroxalate borate(DFOB-)anion-rich solvation sheath,to realize high-performance working of temperature-tolerant LMBs.With this optimized electrolyte,favorable SEI and CEI chemistries on Li metal anode and nickel-rich cathode are achieved,respectively,leading to fast Li^(+)transfer kinetics,dendrite-free Li deposition and suppressed electrolyte deterioration.Therefore,Li||LiNi_(0.80)Co_(0.15)Al_(0.05)O_(2)batteries with a thin Li foil(50μm)show a long-term cycling lifespan over 400 cycles at 1C and a superior capacity retention of 90%after 200 cycles at 0.5C under 25℃.Moreover,this electrolyte extends the operating temperature from-10 to 30℃and significantly improve the capacity retention and Coulombic efficiency of batteries are improved at high temperature(60℃).Fluorosulfonyl carboxylates thus have considerable potential for use in high-performance and allweather LMBs,which broadens the new exploring of electrolyte design.展开更多
To boost the practical energy density of lithium-sulfur batteries,replacing conventional solvating electrolytes with sparingly solvating ones has shown promise by enabling solid-state sulfur conversion and reducing el...To boost the practical energy density of lithium-sulfur batteries,replacing conventional solvating electrolytes with sparingly solvating ones has shown promise by enabling solid-state sulfur conversion and reducing electrolyte consumption.However,this approach often compromises sulfur redox kinetics.This study reports a new sulfur conversion pathway distinct from both traditional solvated and sparingly solvated mechanisms.Specifically,sulfur is converted into a mixture of solid and solvated lithium polysulfides(LPSs).Such a hybrid solid/solvating conversion pathway is achieved using a newly formulated moderately solvating electrolyte,accomplishing both lean-electrolyte operation and fast conversion kinetics for lithium-sulfur batteries.Methoxyacetonitrile(MAN)is selected as the solvent to formulate the moderately solvating electrolyte due to its high relative permittivity(21)that contributes to a high Li+conductivity(11.7 mS cm^(-1) for 1M lithium bis(trifluoromethane sulfonyl)imide in MAN)and low donor number(14.6 kcal mol-1)that reduces the solubility to LPSs to 1/6 of that in mainstream solvating electrolytes.The as-formulated MAN electrolyte enables sulfur cathodes to operate at a low electrolyte-to-sulfur ratio of 2μL mg^(-1) and a low cathode porosity of 52%,displaying excellent prospects for boosting both gravimetric and volumetric energy density.展开更多
Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the us...Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.展开更多
Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating e...Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating electrolytes(HSEs)and sparingly solvating electrolytes(SSEs),with opposite nature towards the dissolution of polysulfides,have recently emerged as two effective solutions to decrease the E/S ratio and increase the overall practical energy density of Li-S batteries.HSEs featuring with high polysulfide solvation ability have the potential to reduce the E/S ratio by dissolving more polysulfides with less electrolyte,while SSEs alter the sulfur reaction pathway from a dissolution-precipitation mechanism to a quasi-solid mechanism,thereby independent on the use of electrolyte amount.Both HSEs and SSEs show respective effectiveness in lean-electrolyte Li-S batteries,but encounter different challenges to bring Li-S batteries into practical application.This review aims to present a comparative discussion on their unique features and basic electrochemical reaction mechanisms in practical lean-electrolyte Li-S batteries.Emphasis is focused on the current technical challenges and possible solutions for their future development.展开更多
Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(S...Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.展开更多
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
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
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
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
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
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
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
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
The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it t...The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it to polymer segmental motion.In this study,a low-content ionic plasticizer additive1-butyl-3-dimethylimidazolium bromide(BMImBr)was introduced into the PVDF-HFP/LiTFSI/DMF matrix to modulate the Li^(+)solvation environment.Unlike conventional dual-salt systems,the introduced Br-anions dynamically compete for Li^(+)coordination,disrupting the rigid Li^(+)-TFSI^(-)/DMF solvation shell and constructing a"statistically labile and diffuse ionic cloud"characterized by reduced coordination numbers,weakened binding energies,and a more diffuse electrostatic potential landscape.This restructured solvation environment facilitates partially decoupled Li^(+)transport,as evidenced by dielectric spectroscopy and molecular dynamics simulations.Furthermore,the in situ formation of a LiBr-rich solid electrolyte interphase(SEI)effectively stabilizes the Li-metal interface and significantly reduces interfacial resistance.As a result,the optimized polymer electrolyte delivers outstanding electrochemical performance,achieving a high ionic conductivity of 0.8×10^(-4) S/cm,ultra-stable symmetric cell cycling over 500 h,and superior capacity retention exceeding 94%after 150 cycles at 0.5 C.This study elucidates a dynamic ion transport mechanism driven by competitive anion coordination and provides a viable strategy for simultaneously addressing the conductivity-stability trade-off in solid-state lithium metal batteries.展开更多
基金supported by Hengyang City,Hunan Province Science and Technology Innovation Project(No.202250045319)the National Natural Science Foundation of China(Nos.11375084,21808125)the Scientific Research Planning Project of Jilin Provincial Education Department(No.JJKH20241249KJ)。
文摘Weakly solvating electrolyte(WSE)demonstrates superior compatibility with lithium(Li)metal batteries(LMBs).However,its application in fast-charging high-voltage LMBs is challenging.Here,we propose a diluent modified WSE for fast-charging high-voltage LMBs,which is formed by adding diluent of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether(TTE)into the tetrahydropyran(THP)based WSE.A relatively loose solvation structure is formed due to the formation of weak hydrogen bond between TTE and THP,which accelerates the de-solvation kinetics of Li~+.Besides,more anions are involved in solvation structure in the presence of TTE,yielding inorganic-rich interphases with improved stability.Li(30μm)||Li Ni_(0.5)Co_(0.2)Mn_(0.3)O_(2)(4.1 mAh/cm^(2))batteries with the TTE modified WSE retain over 64%capacity retention after 175 cycles under high rate of 3 C and high-voltage of 4.5 V,much better than that with pure THP based WSE.This work points out that the combination of diluent with weakly solvating solvent is a promising approach to develop high performance electrolytes for fast-charging high-voltage LMBs.
基金financially supported by National Natural Science Foundation of China(52003231,22065037)Yunnan Fundamental Research Projects(202201AW070015)。
文摘The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.
基金supported by the Key Program for International S&T Cooperation Projects of China(No.2017YFE0124300)National Natural Science Foundation of China(Nos.51971002,52171205 and 52171197)+1 种基金Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0393)Anhui Provincial Natural Science Foundation for Excellent Youth Scholars(No.2108085Y16).
文摘Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via altering the solvating power of the solvent,but it is difficult to dissolve the majority of Li salts and fail to cycle at a cut-off voltage above 4.5 V.Herein,we present a new-type WSE that is regulated by the anion rather than the solvent,and the first realize stable cycling of dimethoxyethane(DME)at 4.6 V without the use of the“solvent-in-salt”strategy.The relationships between the degree of dissociation of salts,the solvation structure of electrolytes,and the electrochemical performance of LMBs were systematically investigated.We found that LiBF_(4),which has the lowest degree of dissociation,can construct an anion-rich inner solvation shell,resulting in anion-derived anode/cathode interphases.Thanks to such unusual solvation structure and interphasial chemistry,the Li-LiCoO_(2)full cell with LiBF_(4)-based WSE could deliver excellent rate performance(115 mAh g^(-1)at 10 C)and outstanding cycling stability even under practical conditions,including high loading(10.7 mg cm^(-2)),thin Li(50μm),and limited electrolyte(1.2μL mg^(-1)).
基金supported by the Hong Kong Polytechnic University(No.CDBJ)Z.Wang thanks the funding support from the Centrally Funded Postdoctoral Fellowship Scheme of the Hong Kong Polytechnic University(No.1-YXAU).
文摘Lithium(Li)batteries are major players in the power source market of electric vehicles and portable electronic devices.Electrolytes are critical to determining the performance of Li batteries.Conventional electrolytes fall behind the ever-growing demands for fast-charging,wide-temperature operation,and safety properties of Li batteries.Despite the great success of(localized)high-concentration electrolytes,they still suffer from disadvantages,such as low ionic conductivity and high cost.Weakly solvating electrolytes(WSEs),also known as low-solvating electrolytes,offer another solution to these challenges,and they have attracted intensive research interests in recent years.This contribution reviews the working mechanisms,design principles,and recent advances in the development of WSEs.A summary and perspective regarding future research directions in this field is also provided.The insights will benefit academic and industrial communities in the design of safe and high-performance next-generation Li batteries.
基金the support from the Key-Area Research and Development Program of Guangdong Province (2020B090919003)the Yunnan Major Scientific and Technological Projects (202202AG050003)+4 种基金the Natural Science Foundation of China (22202078, 51904135,52162030)the Department of Education of Guangdong Province(2020KQNCX082)the Applied Basic Research Foundation of Yunnan Province (202103AA080019)the National Key R&D Program of China (2018YFB01040)the support of the supported by the Testing Technology Center of Materials and Devices of Tsinghua Shenzhen International Graduate School (SIGS)
文摘Advanced electrolyte engineering is an important strategy for developing high-efficacy lithium(Li)metal batteries(LMBs).Unfortunately,the current electrolytes limit the scope for creating batteries that perform well over temperature ranges.Here,we present a new electrolyte design that uses fluorosulfonyl carboxylate as a non-solvating solvent to form difluoroxalate borate(DFOB-)anion-rich solvation sheath,to realize high-performance working of temperature-tolerant LMBs.With this optimized electrolyte,favorable SEI and CEI chemistries on Li metal anode and nickel-rich cathode are achieved,respectively,leading to fast Li^(+)transfer kinetics,dendrite-free Li deposition and suppressed electrolyte deterioration.Therefore,Li||LiNi_(0.80)Co_(0.15)Al_(0.05)O_(2)batteries with a thin Li foil(50μm)show a long-term cycling lifespan over 400 cycles at 1C and a superior capacity retention of 90%after 200 cycles at 0.5C under 25℃.Moreover,this electrolyte extends the operating temperature from-10 to 30℃and significantly improve the capacity retention and Coulombic efficiency of batteries are improved at high temperature(60℃).Fluorosulfonyl carboxylates thus have considerable potential for use in high-performance and allweather LMBs,which broadens the new exploring of electrolyte design.
基金supported by the National Key R&D Program of China(2021YFB2400300)the National Natural Science Foundation of China(52272203)the Fundamental Research Funds for the Central Universities(2021GCRC001).
文摘To boost the practical energy density of lithium-sulfur batteries,replacing conventional solvating electrolytes with sparingly solvating ones has shown promise by enabling solid-state sulfur conversion and reducing electrolyte consumption.However,this approach often compromises sulfur redox kinetics.This study reports a new sulfur conversion pathway distinct from both traditional solvated and sparingly solvated mechanisms.Specifically,sulfur is converted into a mixture of solid and solvated lithium polysulfides(LPSs).Such a hybrid solid/solvating conversion pathway is achieved using a newly formulated moderately solvating electrolyte,accomplishing both lean-electrolyte operation and fast conversion kinetics for lithium-sulfur batteries.Methoxyacetonitrile(MAN)is selected as the solvent to formulate the moderately solvating electrolyte due to its high relative permittivity(21)that contributes to a high Li+conductivity(11.7 mS cm^(-1) for 1M lithium bis(trifluoromethane sulfonyl)imide in MAN)and low donor number(14.6 kcal mol-1)that reduces the solubility to LPSs to 1/6 of that in mainstream solvating electrolytes.The as-formulated MAN electrolyte enables sulfur cathodes to operate at a low electrolyte-to-sulfur ratio of 2μL mg^(-1) and a low cathode porosity of 52%,displaying excellent prospects for boosting both gravimetric and volumetric energy density.
基金financial support from the National Key Research and Development Program of China(No.2022YFB2404300)the National Natural Science Foundation of China(Nos.22409153 and 52101269).
文摘Ether electrolytes for potassium-ion batteries exhibit a broader electrochemical window and greater applicability,yet most of them are high-concentration electrolytes with elevated cost.In this study,we propose the use of a weakly solvating cyclic ether electrolyte with tetrahydropyran(THP)as the solvent.This approach induces the formation of a thin and dense inorganic-rich solid electrolyte interphase(SEI)film,which is accompanied by a decrease in the activation energy of electrode interfacial reactions due to the weak ligand binding of THP with K^(+).Density functional theory(DFT)simulations also corroborate the hypothesis that K^(+)has a lower binding energy with THP.During potassium storage process,the phenomenon of solvent co-intercalation of graphite does not occur,which greatly reduces the destruction of the graphite structure and enables a superior electrochemical performance and enhanced cycling stability at a lower concentration(2 M).At a current density of 0.2 C(55.8 mA·g^(-1)),the battery can be stably cycled for 800 cycles(approximately 8 months)with a specific capacity of 171.8 mAh·g^(-1).This study provides a new ether-based electrolyte for potassium ion batteries and effectively reduces the electrolyte cost,which is expected to inspire further development of energy storage batteries.
基金The authors acknowledge the support from the National Natural Science Foundation of China(Nos.U2002213 and 51972219)the Science and Technology Development Fund Macao SAR(No.0077/2021/A2),the Collaborative Innovation Center of Suzhou Nano Science and Technology,the 111 Project,and the Joint International Research Laboratory of Carbon-based Functional Materials and Devices.
文摘Lithium-sulfur(Li-S)batteries hold great promise to be the next-generation candidate for high-energy-density secondary batteries but in the prerequisite of using low electrolyte-to-sulfur(E/S)ratios.Highly solvating electrolytes(HSEs)and sparingly solvating electrolytes(SSEs),with opposite nature towards the dissolution of polysulfides,have recently emerged as two effective solutions to decrease the E/S ratio and increase the overall practical energy density of Li-S batteries.HSEs featuring with high polysulfide solvation ability have the potential to reduce the E/S ratio by dissolving more polysulfides with less electrolyte,while SSEs alter the sulfur reaction pathway from a dissolution-precipitation mechanism to a quasi-solid mechanism,thereby independent on the use of electrolyte amount.Both HSEs and SSEs show respective effectiveness in lean-electrolyte Li-S batteries,but encounter different challenges to bring Li-S batteries into practical application.This review aims to present a comparative discussion on their unique features and basic electrochemical reaction mechanisms in practical lean-electrolyte Li-S batteries.Emphasis is focused on the current technical challenges and possible solutions for their future development.
基金supported by the National Key Research and Development Program of China(2019YFA0705603)the National Natural Science Foundation of China(22078341)+1 种基金the Natural Science Foundation of Hebei Province(B2020103028)financial support from York University。
文摘Li^(+) solvation structures have a decisive influence on the electrode/electrolyte interfacial properties and battery performances.Reduced salt concentration may result in an organic rich solid electrolyte interface(SEI)and catastrophic cycle stability,which makes low concentration electrolytes(LCEs)rather challenging.Solvents with low solvating power bring in new chances to LCEs due to the weak salt-solvent interactions.Herein,an LCE with only 0.25 mol L^(-1) salt is prepared with fluoroethylene carbonate(FEC)and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)).Molecular dynamics simulations and experiments prove that the low solvating power solvent FEC not only renders reduced desolvation energy to Li^(+) and improves the battery kinetics,but also promotes the formation of a LiF-rich SEI that hinders the electrolyte consumption.Li||Cu cell using the LCE shows a high coulombic efficiency of 99.20%,and LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)||Li cell also exhibits satisfying capacity retention of 89.93%in 200 cycles,which demonstrates the great potential of solvating power regulation in LCEs development.
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 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(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 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 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 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 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.
基金the China Scholarship Council(CSC)for a doctoral scholarship(Grant Nos.202006310030,202108530138 and 202108530139)。
文摘The performance of polymer electrolytes in lithium metal batteries(LMBs)is often hindered by strong Li^(+)-ligand coordination,which leads to tightly bound solvation shells and restricts ion transport by coupling it to polymer segmental motion.In this study,a low-content ionic plasticizer additive1-butyl-3-dimethylimidazolium bromide(BMImBr)was introduced into the PVDF-HFP/LiTFSI/DMF matrix to modulate the Li^(+)solvation environment.Unlike conventional dual-salt systems,the introduced Br-anions dynamically compete for Li^(+)coordination,disrupting the rigid Li^(+)-TFSI^(-)/DMF solvation shell and constructing a"statistically labile and diffuse ionic cloud"characterized by reduced coordination numbers,weakened binding energies,and a more diffuse electrostatic potential landscape.This restructured solvation environment facilitates partially decoupled Li^(+)transport,as evidenced by dielectric spectroscopy and molecular dynamics simulations.Furthermore,the in situ formation of a LiBr-rich solid electrolyte interphase(SEI)effectively stabilizes the Li-metal interface and significantly reduces interfacial resistance.As a result,the optimized polymer electrolyte delivers outstanding electrochemical performance,achieving a high ionic conductivity of 0.8×10^(-4) S/cm,ultra-stable symmetric cell cycling over 500 h,and superior capacity retention exceeding 94%after 150 cycles at 0.5 C.This study elucidates a dynamic ion transport mechanism driven by competitive anion coordination and provides a viable strategy for simultaneously addressing the conductivity-stability trade-off in solid-state lithium metal batteries.
