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
Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hi...Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.展开更多
Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electro...Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.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
Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a s...Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.展开更多
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
In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar perce...In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar percentage of Na_(2)Ni_(2)Ti_(6)O_(16)(NNTO)within Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)(NMTO),with x values of 10,20,30,40,and 50.Both XPS(X-ray Photoelectron Spectroscopy)and EDX(Energy Dispersive X-ray Spectroscopy)analyses unequivocally validated the formation of the NNMTO-x solid solutions.It was observed that when x is below 40,the NNMTO-x solid solution retains the structural characteristics of the original NMTO.However,beyond this threshold,significant alterations in crystal morphology were noted,accompanied by a noticeable decline in photocatalytic activity.Notably,the absorption edge of NNMTO-x(x<40)exhibited a shift towards the visible-light spectrum,thereby substantially broadening the absorption range.The findings highlight that NNMTO-30 possesses the most pronounced photocatalytic activity for the reduction of CO_(2).Specifically,after a 6 h irradiation period,the production rates of CO and CH_(4)were recorded at 42.38 and 1.47μmol/g,respectively.This investigation provides pivotal insights that are instrumental in the advancement of highly efficient and stable photocatalysts tailored for CO_(2)reduction processes.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
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 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
Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion...Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.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 practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by ca...The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.展开更多
Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identifi...Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identified numerous crystal structures with the Li_(3)MX_(6)composition,although many remain unexplored across various chemical systems.In this research,we developed a comprehensive method to examine all conceivable space groups and structures within theLi-M-X system,where M includes In,Ga,and La,and X includes F,Cl,Br,and 1.Our findings revealed two metastable structures:Li_(3)InF_(6)with P3c1 symmetry and Li_(3)InI_(6)with C2/c symmetry,exhibiting ionic conductivities of 0.55 and 2.18mS/cm at 300K,respectively.Notably,the trigonal symmetry of Li3InF6 demonstrates that high ionic conductivities are not limited to monoclinic structures but can also be achieved with trigonal symmetries.The electrochemical stability windows,mechanical properties,and reaction energies of these materials with known cathodes suggest their potential for use in all-solid-state batteries.Additionally,we predicted the stability of novel materials,including Li_(5)InCl_(8),Li_(5)InBr_(8),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)I_(9).展开更多
The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theo...The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theory and density functional theory calculations.The material features a wide band gap of 4.0 eV and a considerable reduced Na^(+)migration barrier of 0.44 eV,a 1.26-eV decrease compared to pristine Na MgPO_(4)(~1.70 eV).Ab initio molecular dynamics simulations further reveal significantly enhanced ionic conductivity in the oxysulfide-based system compared to the pristine oxide structure.In addition,the calculated decomposition energy indicates that the modified material exhibits good moisture stability.Our findings suggest that sulfur-doping strategy can simultaneously achieve improved ionic conductivity and high moisture stability in oxide solid electrolytes,which could pave the way for designing high-performance solid electrolytes.展开更多
The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit e...The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.展开更多
Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the deve...Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the development of melt crystallization is hampered by lacking solid–liquid equilibrium (SLE) data for some isomers.Therefore,the SLE data of both binary and ternary mixtures of 2,3-dimethylphenol (2,3-DMP),3,5-dimethylphenol (3,5-DMP),and 3,4-dimethylphenol (3,4-DMP) were determined by using differential scanning calorimetry in this work.Additionally,crystallographic analysis was conducted to investigate the thermodynamic characteristics of these mixtures.The experimental results indicated that all the systems investigated in this research exhibited eutectic behavior.The experimentally obtained SLE data were well correlated with the Wilson and non-random two-liquid models.The excess thermodynamic functions were calculated to analyze the types and intensities of the molecular interactions occurring in the mixtures.Furthermore,this study developed a model for the correlation between the theoretical crystallization yield and the actual cooling yield and final yield in melt crystallization.This study has furnished reliable data essential for developing and optimizing the melt crystallization process of mixtures of 2,3-DMP,3,5-DMP,and 3,4-DMP.展开更多
Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical proper...Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.展开更多
This letter addresses challenges in the clinical translation of BIBR1532,a promising telomerase inhibitor,for the treatment of esophageal squamous cell carcinoma(ESCC).BIBR1532 exerts its anti-cancer effect by activat...This letter addresses challenges in the clinical translation of BIBR1532,a promising telomerase inhibitor,for the treatment of esophageal squamous cell carcinoma(ESCC).BIBR1532 exerts its anti-cancer effect by activating DNA damage response(ATR/CHK1 and ATM/CHK2)pathways and downregulating telomere-binding proteins.Although its therapeutic potential is limited by poor aqueous solubility,solid dispersion(SD)technology may overcome this obstacle.Systematic analysis using PubChem-derived simplified molecular input line entry system identifiers and artificial intelligence-driven FormulationDT platform evaluation(oral formulation feasibility index:0.38)revealed that the SD technology,with superior scalability(32 approved products by 2021)and lower production risks,outperforms lipid-based formulations as an optimal dissolution strategy.Material analysis revealed hydroxypropyl methylcellulose(HPMC)as the optimal carrier with lower hygroscopicity,higher temperature and no intestinal targeting,thus enabling ESCC therapy.HPMC-based SD enhances BIBR1532 solubility and bioavailability for effective ESCC treatment.Future studies should focus on pilot tests for SD fabrication.展开更多
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the financial support from the National Natural Science Foundation of China,China(Grant Nos.52502258 and 52162030)the Yunnan Fundamental Research Projects,China(Grant Nos.202501AT070298,202401AU070163 and 202401AT070368)+5 种基金the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects,China(Grant No.2023-XMDJ-00617107)the Expert Workstation Support Project of Yunnan Province,China(Grant Nos.202405AF140069 and 202505AF350019)the University Service Key Industry Project of Yunnan Province,China(Grant No.FWCY-ZD2024005)the Shenzhen Science and Technology Program,China(Grant No.KJZD20230923114107014)the Scientific Research Foundation of Kunming University of Science and Technology,China(20220122)the Analysis and Test Foundation of Kunming University of Science and Technology,China(Grant No.2023T20220122)。
文摘Weakly solvating electrolytes(WSEs)promote the formation of anion-driven solid electrolyte interphases(SEI),enabling stable lithium metal batteries.However,current strategies involving alkylated modification,steric hindrance incorporation,coordinated oxygen(O)regulation,and selective fluorination face poor-diversity interfacial chemistry,high cost,or environmental concerns.Here,we propose a heteroatom-substitution strategy to design a WSE composed of lithium bis(fluorosulfonyl)imide(LiFSI)and 1,4-oxathiane(OTA)as a single solvent.Substituting oxygen with sulfur in conventional 1,4-dioxane(1,4-DX)generates OTA with a modulated dipole and charge distribution,weakening Li^(+)-OTA coordination while promoting anion-involved solvation sheath.This unique solvation structure triggers the formation of an inorganic-rich SEI with sulfur-containing species,enabling high Li plating/stripping coulombic efficiency and stable Li‖Li symmetric cells cycling for 1000 h.Benefiting from the superior interfacial chemistry and wettability of the electrolyte to the LiFePO_(4) cathode,full cells exhibit exceptional cycling stability even at low negative-to-positive(N/P)ratios,A pouch cell coupled with3.58 mAh cm^(-2) LiFePO_(4) and 20μm Li(N/P~1.15)maintains 88.77%capacity after 150 cycles.This work shows a fluorine-free solvent design paradigm for advanced WSEs,providing novel insights toward stable LMBs.
基金supported by the National Natural Science Foundation of China(No.52472219,62133007)the project ZR2024ME073 supported by Shandong Provincial Natural Science Foundationthe Shenzhen Fundamental Research Program(No.JCYJ20220530141017039)。
文摘Despite the high energy density,lithium metal batteries(LMBs)face significant cycling instability and safety challenges,especially at subzero temperatures.Herein,we report a rationally designed lowconcentrated electrolyte system that employs a low-freezing-point diluent to compress solvation sheaths,enabling the formation of a compact anion-dominated solvation structure that enhances interfacial stability and safety.Molecular dynamics reveal the unique solvation structure with close packing of anions in this low-concentration electrolyte from the micro-mesoscopic scale.The optimized electrolyte combines cost-effectiveness,superior wettability,intrinsic nonflammability,and high stability,concurrently promoting a hybrid organic-inorganic solid electrolyte interphase(SEI)and cathode electrolyte interphase(CEI)for uniform lithium deposition.As a result,the Li‖LiFePO_(4)(LFP)full cells demonstrate stable cycling for 700 cycles at the current density of 4 C.Remarkably,the electrolyte demonstrates exceptional low-temperature performance,indicating broad operational viability.This work provides a promising electrolyte design strategy that addresses both safety and excellent electrochemical performance in high-energy-density metal-based batteries,including but not restricted to Li,Na,K and Zn multivalent ion systems.
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.
基金supported by the Natural Science Foundation of China(22379073,52373275)the Natural Science Foundation of Tianjin,China(18JCZDJC31400)the Ministry of Education Innovation Team(IRT13022).
文摘Quasi-solid polymer electrolytes(QSPEs)have been attracted significant attentions due to their benefits for simultaneously improved safety and energy density of batteries.Developing electrolytes capable of forming a stable solid electrolyte interphase(SEI)layer is a great challenge for QSPE-based lithium(Li)metal batteries(LMBs).Herein,unlike previously reports that the reconstruction of Li^(+)solvation structures in QSPE requires time-consuming bottom-up polymer synthesis,in current study,a facile approach has been developed to reconstruct the Li^(+)solvation structures in QSPE by adjustment of the salt concentrations.The high proportion of Li^(+)-anion complexes can effectively accelerate interfacial Li^(+)diffusion,mitigate the decompositions of organic solvents and induce the formation of a LiF-rich SEI layer,contributing to suppressed Li-dendrite growth.As a result,the Li/QSPE-3/LiFePO_(4)(LFP)cell performs an ultralong lifespan with capacity retention of 77.4%over 3000 cycles at 1 C.With a high-voltage LiCoO_(2)cathode,the cell can stably cycle over 200 cycles at 25℃(capacity retention of∼83.8%).With accelerated ion transport dynamics due to the reconstructed Li^(+)solvation structure,the QSPE-3(the salt concentration is 3 M)is applicable in a wide temperature range.The Li/QSPE-3/LFP full cell exhibits 58.1%and 102.6%of discharge capacity at−15 and 90℃,respectively,compared to those operated at 25℃This study demonstrates a facile yet effective approach on enhancing electrode/electrolyte interfacial stability,enabling the LMBs with simultaneously enhanced safety and high energy density.
基金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Supported by the Doctoral Research Start-up Project of Yuncheng University(YQ-2023067)Project of Shanxi Natural Science Foundation(202303021211189)+1 种基金Fund Program for the Scientific Activities of Selected Returned Overseas Professionals in Shanxi Provinces(20220036)Shanxi ProvinceIntelligent Optoelectronic Sensing Application Technology Innovation Center and Shanxi Province Optoelectronic Information Science and TechnologyLaboratory,Yuncheng University.
文摘In this study,a straightforward one-step hydrothermal method was successfully utilized to synthesize the solid solution Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)-Na_(2)Ni_(2)Ti_(6)O_(16)(NNMTO-x),where x denotes the molar percentage of Na_(2)Ni_(2)Ti_(6)O_(16)(NNTO)within Na_(0.9)Mg_(0.45)Ti_(3.55)O_(8)(NMTO),with x values of 10,20,30,40,and 50.Both XPS(X-ray Photoelectron Spectroscopy)and EDX(Energy Dispersive X-ray Spectroscopy)analyses unequivocally validated the formation of the NNMTO-x solid solutions.It was observed that when x is below 40,the NNMTO-x solid solution retains the structural characteristics of the original NMTO.However,beyond this threshold,significant alterations in crystal morphology were noted,accompanied by a noticeable decline in photocatalytic activity.Notably,the absorption edge of NNMTO-x(x<40)exhibited a shift towards the visible-light spectrum,thereby substantially broadening the absorption range.The findings highlight that NNMTO-30 possesses the most pronounced photocatalytic activity for the reduction of CO_(2).Specifically,after a 6 h irradiation period,the production rates of CO and CH_(4)were recorded at 42.38 and 1.47μmol/g,respectively.This investigation provides pivotal insights that are instrumental in the advancement of highly efficient and stable photocatalysts tailored for CO_(2)reduction processes.
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 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 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the National Natural Science Foundation of China(No.22379047)Yinzhou R&D Team(X.W.)+2 种基金Guangdong Basic and Applied Basic Research Foundation(2022B1515120019)the Project Funded by the China Scholarship Council(No.202108320278)the support from the Vacuum Interconnected Nanotech Workstation(Nano-X)from Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO)。
文摘Aqueous zinc-ion batteries(AZIBs)offer a safe,cost-effective,and high-capacity energy storage solution,yet their performance is hindered by interfacial challenges at the Zn anode,including hydrogen evolution,corrosion,and dendritic Zn growth.While most studies focus on regulating Zn~(2+)solvation structures in bulk electrolytes,the evolution of interfacial solvation—where Zn~(2+)undergoes desolvation and deposition—remains insufficiently explored.Here,we introduce sulfated nanocellulose(SNC),an anion-rich biopolymer,to tailor the interfacial solvation structure without altering the bulk electrolyte composition.Using in situ attenuated total reflection Fourier transform infrared spectroscopy and fluorescence interface-extended X-ray absorption fine structure,we reveal that SNC facilitates the formation of a low-coordinated Zn~(2+)solvation shell at the interface by weakening H_(2)O coordination.This transformation is driven by electrostatic interactions between Zn~(2+)and anchored sulfate groups,thereby reducing water activity,improving interfacial stability during charge/discharge,and suppressing parasitic reactions.Consequently,a high average coulombic efficiency of 99.6%over 500 cycles in Zn|Ti asymmetric cells and 1.5 Ah pouch cells(13.4 mg cm^(-2)loading,remained stable over 250 cycles)were achieved in SNC-induced AZIBs.This work underscores the importance of interfacial solvation structure engineering—beyond traditional bulk electrolyte design—in enabling practical,high-performance AZIBs.
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 Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2023-00217581)supported by the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(RS-2024-00406724)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(RS-2025-25430676)。
文摘The practical deployment of lithium metal batteries remains severely constrained,especially under elevated temperatures.Although metal-organic frameworks(MOFs)improve the thermal stability of liquid electrolytes by capturing them in well-ordered sub-nanopores,interparticle voids between MOF particles readily absorb liquid electrolyte,obscuring our understanding of the intrinsic role of nanopores in directing Li^(+)transport.To address this challenge,we introduce a one-dimensional(1D)MOF model architecture that eliminates interparticle effects and enables direct observation of Li^(+)solvation and de-solvation dynamics.Comparative studies of 1D HKUST-1 and ZIF-8 uncover distinct transport behaviors,supported by both experimental measurements and neural network potential-based molecular dynamics simulations.Building on these insights,we construct a hierarchical core-shell MOF architecture by integrating ZIF-8(core)and HKUST-1(shell)onto a hybrid fiber scaffold.This design harnesses the complementary strengths of both MOFs to achieve continuous ion pathways,directional Li^(+)conduction,and improved thermal and electrochemical resilience.
基金supported by the Higher Education and Science Committee of Armenia in the frames of the research projects 20TTSG-2F010, 23AA-2F033 and ANSEF (EN-matsc-2660) grant.
文摘Halide solid-state electrolytes have gained significant attention in recent years due to their high ionic conductivity,making them promising candidates for future all-solid-state batteries.Recent studies have identified numerous crystal structures with the Li_(3)MX_(6)composition,although many remain unexplored across various chemical systems.In this research,we developed a comprehensive method to examine all conceivable space groups and structures within theLi-M-X system,where M includes In,Ga,and La,and X includes F,Cl,Br,and 1.Our findings revealed two metastable structures:Li_(3)InF_(6)with P3c1 symmetry and Li_(3)InI_(6)with C2/c symmetry,exhibiting ionic conductivities of 0.55 and 2.18mS/cm at 300K,respectively.Notably,the trigonal symmetry of Li3InF6 demonstrates that high ionic conductivities are not limited to monoclinic structures but can also be achieved with trigonal symmetries.The electrochemical stability windows,mechanical properties,and reaction energies of these materials with known cathodes suggest their potential for use in all-solid-state batteries.Additionally,we predicted the stability of novel materials,including Li_(5)InCl_(8),Li_(5)InBr_(8),Li_(5)InI_(8),LiIn_(2)Cl_(9),LiIn_(2)Br_(9),and LiIn_(2)I_(9).
基金Project supported by the National Natural Science Foundation of China(Grant Nos.22473010,22303114,and 12474372)the Fundamental Research Funds for the Central Universities,Jilin University,the National Key Research and Development Program of China(Grant No.SQ2023YFB2805600)+4 种基金the Natural Science Foundation of Beijing Municipality(Grant No.Z210004)the Fund from the State Key Laboratory of Information Photonics and Optical Communications(Grant No.IPOC2021ZT01)Beijing Nova Program from Beijing Municipal Science and Technology Commission(Grant No.20230484433)Beijing University of Posts and Telecommunications Excellent Ph.D.Students Foundation(Grant No.CX20241078)Beijing Natural Science Foundation(Undergraduate Program)(Grant No.QY24218)。
文摘The development of high-performance solid electrolytes is pivotal for advancing solid-state battery technologies.In this work,we design an oxysulfide-based solid electrolyte Na MgPO_(3)S by combining bond valence theory and density functional theory calculations.The material features a wide band gap of 4.0 eV and a considerable reduced Na^(+)migration barrier of 0.44 eV,a 1.26-eV decrease compared to pristine Na MgPO_(4)(~1.70 eV).Ab initio molecular dynamics simulations further reveal significantly enhanced ionic conductivity in the oxysulfide-based system compared to the pristine oxide structure.In addition,the calculated decomposition energy indicates that the modified material exhibits good moisture stability.Our findings suggest that sulfur-doping strategy can simultaneously achieve improved ionic conductivity and high moisture stability in oxide solid electrolytes,which could pave the way for designing high-performance solid electrolytes.
基金supported by the National Key R&D Program of China(Grant No.2022YFE0207300)the National Natural Science Foundation of China(Grant Nos.22179142 and 22075314)+1 种基金Jiangsu Provincial Science and Technology Program(Grant No.BG 2024020).XPSWAXS and TOF-SIMS characterizations were supported by Nano-X(Vacuum Interconnected Nanotech Workstation,Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences(SINANO),Suzhou 215123,China)。
文摘The practical application of lithium metal batteries(LMBs)requires electrolytes that simultaneously ensure high safety and interfacial stability.Although locally concentrated ionic liquid electrolytes(LCILEs)exhibit exceptional electrochemical stability and compatibility with electrode electrolyte interfaces(EEIs),two major challenges persist:(i)safety risks caused by excessive low-flash-point diluents,and(ii)insufficient understanding of how diluents modulate solvation structures.Herein,we introduce a low-diluent-content LCILE system composed of lithium bis(fluorosulfonyl)imide(LiFSI)salt,N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide(Pyr_(13)FSI)ionic liquid,and trifluoromethanesulfonate(TFS)diluent.The TFS diluent strengthens ion-ion interactions by lowering the dielectric constant of the electrolyte,resulting in the formation of a unique nanometric anion aggregates(N-AGGs)reinforced solvation structure.These large anionic clusters exhibit accelerated redox decomposition kinetics,facilitating the rapid formation of a thin,dense,and low-impedance EEI.Consequently,the Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)coin cell achieves 87.8%capacity retention over 300 cycles at 4.3 V,while a practical 1.4 Ah Li/NCM622 pouch cell retains 84.5%capacity after 80 cycles at 4.5 V.Furthermore,the electrolyte demonstrates exceptional safety,and 2 Ah Li metal pouch cells successfully pass rigorous nail penetration tests without any ignition or explosion.This work not only provides a design strategy for intrinsically safe and high-performance electrolytes but also highlights the critical role of anion cluster decomposition kinetics in shaping EEI formation.
基金funded by the National Natural Science Foundation of China(22308358,22208346,22421003)IPE Project for Frontier Basic Research(QYJC-2023-05)CAS Project for Young Scientists in Basic Research(YSBR-038).
文摘Dimethylphenols serve as important intermediates in synthesizing pharmaceuticals and agrochemicals,yet traditional distillation struggles to separate their isomers due to minimal boiling point differences,and the development of melt crystallization is hampered by lacking solid–liquid equilibrium (SLE) data for some isomers.Therefore,the SLE data of both binary and ternary mixtures of 2,3-dimethylphenol (2,3-DMP),3,5-dimethylphenol (3,5-DMP),and 3,4-dimethylphenol (3,4-DMP) were determined by using differential scanning calorimetry in this work.Additionally,crystallographic analysis was conducted to investigate the thermodynamic characteristics of these mixtures.The experimental results indicated that all the systems investigated in this research exhibited eutectic behavior.The experimentally obtained SLE data were well correlated with the Wilson and non-random two-liquid models.The excess thermodynamic functions were calculated to analyze the types and intensities of the molecular interactions occurring in the mixtures.Furthermore,this study developed a model for the correlation between the theoretical crystallization yield and the actual cooling yield and final yield in melt crystallization.This study has furnished reliable data essential for developing and optimizing the melt crystallization process of mixtures of 2,3-DMP,3,5-DMP,and 3,4-DMP.
基金supported by the Basic Science Research Program(RS-2024-00455177)through the National Research Foundation of Korea(NRF)funded by the Ministry of Science,ICT.
文摘Aqueous zinc ion batteries(AZIBs)are considered promising candidates owing to their inherent safety and low cost.However,the conventional glass fiber(GF)separator used in AZIBs suffers from poor physicochemical properties,leading to uncontrolled zinc(Zn)dendrite formation and undesirable side reactions.To address these limitations and enhance the electrochemical performance of AZIBs,a precisely designed functional separator is developed by incorporating UiO-66-(COOH)_(2)into a poly(vinylidene fluoride)(PVDF)framework(U-PVDF)via a direct in situ growth method.This approach enables uniform distribution of UiO-66-(COOH)_(2)both on the surface and within the PVDF backbone,without increasing separator thickness.Owing to the strong interaction between Zn^(2+)and the abundant carboxyl groups in UiO-66-(COOH)_(2),the U-PVDF separator regulates the Zn^(2+)solvation structure toward a contact ion pair-dominated structure by reducing coordinated water molecules,which effectively mitigates water-induced parasitic reactions and promotes compact Zn deposition.Consequently,a Zn/Zn symmetric cell employing the U-PVDF separator demonstrates superior cycling stability over 1500 cycles without internal short-circuiting at a current density of 6 mA cm^(−2)and an areal capacity of 2 mAh cm^(−2).Moreover,Zn/NaV_(3)O_(8)·xH_(2)O(NVO)cell with the U-PVDF separator exhibits markedly improved cyclability and rate performance compared with those using conventional GF separator.
基金Supported by“Continuation”Project of Excellent Doctors,Guangdong Basic and Applied Basic Research Foundation,No.2025A04J5082Guangdong Basic and Applied Basic Research Foundation,No.2024A1515011236.
文摘This letter addresses challenges in the clinical translation of BIBR1532,a promising telomerase inhibitor,for the treatment of esophageal squamous cell carcinoma(ESCC).BIBR1532 exerts its anti-cancer effect by activating DNA damage response(ATR/CHK1 and ATM/CHK2)pathways and downregulating telomere-binding proteins.Although its therapeutic potential is limited by poor aqueous solubility,solid dispersion(SD)technology may overcome this obstacle.Systematic analysis using PubChem-derived simplified molecular input line entry system identifiers and artificial intelligence-driven FormulationDT platform evaluation(oral formulation feasibility index:0.38)revealed that the SD technology,with superior scalability(32 approved products by 2021)and lower production risks,outperforms lipid-based formulations as an optimal dissolution strategy.Material analysis revealed hydroxypropyl methylcellulose(HPMC)as the optimal carrier with lower hygroscopicity,higher temperature and no intestinal targeting,thus enabling ESCC therapy.HPMC-based SD enhances BIBR1532 solubility and bioavailability for effective ESCC treatment.Future studies should focus on pilot tests for SD fabrication.
