In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride ...In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride molten salt as the reaction medium at 923 K.The study assessed the effects of lithium thermochemical reduction and electrolytic reduction of ZnO.The volatilization behavior of metal oxides in molten salts,the equivalent of a reducing agent,reduction time,amount of molten salt,stirring time,and the method of reduction feed were investigated for their impacts on the reduction yield and product composition.X-ray powder diffraction(XRD)analysis of the products showed that lithium reduction of ZnO not only produced metallic Zn but also formed a LiZn alloy.Electrolytic reduction can be used to obtain the metallic Zn product by controlling the potential below-2.2 V(vs Ag/Ag^(+)).Moreover,sintered oxides and higher electrode potentials could enhance the efficiency of electrolysis.Under the optimal reaction conditions determined experimentally,the lithium reduction experiment achieved a yield of 77.2%after a 12-h test,and the electrolytic reduction reached a yield of 85.4%after a 6-h test.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and l...Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.展开更多
Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systemat...Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.展开更多
Coal serves not only as a crucial energy resource but also as a significant reservoir of critical metal elements,including Lithium(Li),Gallium(Ga),Germanium(Ge),and rare earth elements(REE).This paper provides a syste...Coal serves not only as a crucial energy resource but also as a significant reservoir of critical metal elements,including Lithium(Li),Gallium(Ga),Germanium(Ge),and rare earth elements(REE).This paper provides a systematic review of the enrichment characteristics,occurrence modes,and comprehensive utilization potential of these critical metals in coal.Globally,the distribution of these metal resources exhibits significant regional heterogeneity.While the concentration in most coals falls below industrial cut-off grades,anomalous enrichment in specific coal basins results in Li,Ga,Ge,and REE concentrations far exceeding global averages,highlighting their considerable potential as unconventional metal deposits.The occurrence modes of these metals are diverse:Li is primarily hosted in mineral phases;Ga exists in inorganic,organic,and complex forms;Ge shows a strong association with organic matter;and REE are mainly present in adsorbed/isomorphic forms within clay minerals,while also displaying organic affinity.Direct extraction of metals from raw coal is often cost-prohibitive;effective recovery is therefore more feasible when integrated with coal processing.Metals are further enriched in solid wastes such as coal gangue,fly ash,and bottom ash,from which recovery is more economically and technically viable.Current comprehensive utilization primarily employs integrated mineral processing-hydrometallurgy approaches.Future research should focus on elucidating the precise occurrence forms of metals in coal and solid wastes,optimizing pre-treatment methods,and selecting effective activators and leachants.Advancing the synergistic extraction and green recovery of multiple associated resources from coal and its by-products is essential for achieving high-value,comprehensive utilization of coal-based resources.展开更多
Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance ...Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.展开更多
With the widespread application of lithium batteries in electric vehicles and energy storage systems,battery-related safety and reliability issues have become increasingly prominent.Conventional monitoring methods oft...With the widespread application of lithium batteries in electric vehicles and energy storage systems,battery-related safety and reliability issues have become increasingly prominent.Conventional monitoring methods often struggle to address dynamic changes under complex operando.In recent years,flexible sensing technology has emerged as a promising solution for battery health monitoring due to its high adaptability and conformability to complex structures.Meanwhile,empowered by artificial intelligence(AI)for data analysis,the collected data enables efficient and accurate state assessment,offering robust support for accident prevention.Against this background,this paper first explores the integrated applications of flexible sensors in battery health monitoring and their unique advantages in addressing complex battery operating conditions,while analyzing the potential of AI in battery state analysis.Subsequently,it systematically reviews mainstream flexible sensing technologies(e.g.,film sensors,thermocouples,and optical fiber sensors),elucidating their mechanisms for revealing intricate internal battery processes during operation.Finally,the paper discusses AI’s role in enhancing monitoring efficiency and accuracy,and envisions future research directions and application prospects.This work aims to provide technical references for the battery health monitoring field as well as promote the application of flexible sensing technologies in improving battery system safety and reliability.展开更多
In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.He...To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.展开更多
The proton exchange membrane fuel cell(PEMFC)and the hydrogen hybrid power system are studied by the fuzzy-PID(FPID)controlmethod and the fuzzy-PID controlmethod by Artificial Bee Colony algorithm(ABCFPID),respectivel...The proton exchange membrane fuel cell(PEMFC)and the hydrogen hybrid power system are studied by the fuzzy-PID(FPID)controlmethod and the fuzzy-PID controlmethod by Artificial Bee Colony algorithm(ABCFPID),respectively.The results reveal that compared with the FPID control method,the temperature overshoot of the PEMFC stack under the ABC-FPID control method is decreased by 0.6%.Moreover,the circulating water flow rate within the full operating envelope(about 3 min)is reduced by 19.46 L,which means the ABC-FPID control method is more effective in regulating the stack temperature.Then,the ABC-FPID control method is proposed to study the hydrogen hybrid power system,and the system output power matching,operating characteristic curve of the fuel cell,state of charge(SOC)of the lithium battery,system efficiency and hydrogen demand are obtained.The results indicate that the maximum system efficiency reaches 46.3%,the average system efficiency is 33.8%,and the average hydrogen demand is 0.192 kg/s.Overall,the ABC-FPID control method can efficiently ensure the stability of the fuel cell’s output power,and actively prompt the lithium battery to fulfill the function of“peak shaving and valley filling”under variable load power conditions.展开更多
The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24...The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24.3 MPa)bicontinuous porous poly(m-phthaloyl-m-phenylenediamine)(PMIA)membrane integrated into PEO/LiTFSI(PL),thus forming a PMIA/PEO/LiTFSI(PPL)composite electrolyte.Compared to the PL electrolyte,the PPL electrolyte reinforced by a bicontinuous porous PMIA membrane exhibits significantly enhanced mechanical strength,reaching 13.4 MPa.In addition,the amide groups on PMIA strongly coordinate with LiTFSI and form hydrogen bonds with PEO,promoting Li salt dissociation and reducing the Li^(+)migration barrier.This creates efficient,fast Li^(+)transport channels at the PMIA/PL interfaces,effectively promoting the uniform Li^(+)deposition and minimizing lithium dendrite formation.The PPL electrolyte achieves high ionic conductivity(1×10^(−4)S cm^(−1)at 30°C)and Li^(+)transference number(tLi^(+)=0.43).The assembled LiFePO_(4)/Li battery demonstrates excellent cycling stability,retaining 80%capacity after 2000 cycles at 2 C,while the Li/Li symmetric cell operates stably for over 900 h at 0.3 mA cm^(−2).Therefore,the scalable porous PMIA membrane effectively enhances both the mechanical strength and Li^(+)transport in PEO-based electrolytes,offering a viable strategy for their commercial-scale implementation.展开更多
High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instab...High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.展开更多
Structural instability and sluggish lithium-ion(Li+) kinetics of spinel NiCo_(2)O_(4) anodes severely hinder their applications in high-energy-density lithium-ion batteries.Mesocrystalline structures exhibit promising...Structural instability and sluggish lithium-ion(Li+) kinetics of spinel NiCo_(2)O_(4) anodes severely hinder their applications in high-energy-density lithium-ion batteries.Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics.However,their controlled synthesis mechanisms remain elusive.Herein,a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo_(2)O_(4) nanorods.Remarkably,mesocrystalline NiCo_(2)O_(4) exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g,attributed to its porous structure facilitating Li^(+) transport kinetics and unique stress-buffering effect validated by ex-situ TEM.Theoretical calculations and interfacial chemical analysis reveal that substratecrystal surface engineering regulates the nucleation-growth pathways:Acid-treated nickel foam enables epitaxial growth via lattice matching,acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization.In contrast,carbon cloth requires hightemperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy.This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis.The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.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
Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving...Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.展开更多
Lithium metal batteries(LMBs)have attracted huge attention due to super-high capacity and low reduction potential of lithium anode constructing high-energy/power density.However,the practical application of LMBs is si...Lithium metal batteries(LMBs)have attracted huge attention due to super-high capacity and low reduction potential of lithium anode constructing high-energy/power density.However,the practical application of LMBs is significantly constrained by lithium dendrite growth and high reactivity of lithium anode.Herein,a novel functionalized interlayer that SbF3 is tandem on HKUST-1 skeleton forming favorable Sb-terminated groups structure(HKSF@PE),which were proposed and fabricated to construct highly stable LMBs.Theoretical calculations demonstrate that the Sb-terminated groups structure in this configuration display strong interaction with lithium,which can act as a cation receptor and adsorption sites,thereby promoting lithium-ion desolvation and improving lithium-ion transport kinetics.Meanwhile,in-situ XRD,Raman,and DRT analyses indicate that the HKSF assist the formation of LiF-rich and lithiophilic Li3Sb alloys at SEI/Li interface,regulating lithium depo-sition morphology and reconstructing a reinforced SEI interlayer.Consequently,Li|HKSF@PE|Li symmetric cell exhibits exceptional stability over 2500 h at 2 mA cm^(-2) with 1 mAh cm^(-2),and Li|HKSF@PE|LFP full cell demonstrates a high-capacity retention of 92.0%after 220 cycles even at a high rate of 5C.This work reveals the important role of terminated groups to achieve homogeneous lithium deposition and provide a way to construct stable LMBs.展开更多
Due to complex ion-ion and ion-membrane interactions, creating innovative membrane structures to acquire favorable ion mixing effect and high separation performance remains a big challenge. Herein, we design covalent ...Due to complex ion-ion and ion-membrane interactions, creating innovative membrane structures to acquire favorable ion mixing effect and high separation performance remains a big challenge. Herein, we design covalent organic framework(COF) scaffold membrane with gate-lane nanostructure for efficient Li^(+)/Mg^(2+) separation. COF nanosheets, serving as the scaffold, are intercalated by polyethyleneimine(PEI) to form the permeating layer. Subsequently, PEI on the surface reacts with 1,4-phenylene diisocyanate to form the polyurea gating layer. The gating layer, bearing tailored smaller pore size,affords high rejection to co-ions(Mg^(2+)) and thus high Li^(+)/Mg^(2+) selectivity. The permeating layer, with asymmetric charge and spatial nanostructure for creating individual lanes of Li^(+) and Cl~-, facilitates Li^(+) transport and thus high Li^(+) permeability. The optimum COF scaffold membrane exhibits the permeance of 11.5 L m^(-2) h^(-1)/bar^(-1) and true selectivity of 231.9 with Li^(+) enrichment of 120.2% at the Mg^(2+)/Li^(+) mass ratio of 50, exceeding the ideal selectivity of 80.5 and outperforming all ever-reported positively charged nanofiltration membranes. Our work may stimulate the further thinking about how to design the hierarchical membrane structure to achieve favorable ion mixing effect and break the membrane permeability-selectivity trade-off in chemical separations.展开更多
The surfaces of brittle materials are susceptible to defects such as scratches,cracks,and chipping during con-ventional grinding processes,which significantly compromise surface quality and service performance.A flexi...The surfaces of brittle materials are susceptible to defects such as scratches,cracks,and chipping during con-ventional grinding processes,which significantly compromise surface quality and service performance.A flexible ball-end body-armor-like abrasive tool(BAAT)can effectively remove micro-convex peaks from the surfaces of brittle materials by employing a high tangential grinding force and a low normal grinding force,thereby achieving nano-level surface roughness and ultra-smooth mirror finishes.However,the surface contact me-chanism,pressure distribution pattern,and grinding force behavior between BAAT and workpiece remain in-adequately understood.This study examines the mechanism of liquid film formation and the distribution pattern of elastohydrodynamic pressure in high-shear and low-pressure grinding areas,drawing on the theories of elastohydrodynamic lubrication,non-Newtonian fluid dynamics,and material mechanics.A high-shear low-pressure grinding force model,which incorporates elastohydrodynamic liquid film thickness and abrasive grain size,was developed.The effects of the main grinding parameters(normal load,spindle rotational speed,and abrasive grain size)on the tangential grinding force were investigated through the processing of lithium niobate crystals using an intelligent precision-grinding system.The experimental results indicated that the relative error between the predicted and experimental values was 10.74%,thereby confirming the accuracy of the grinding force model.This study advances the understanding of elastohydrodynamic lubrication mechanisms in abrasive machining and provides a crucial theoretical foundation for the application of flexible ball-end BAAT.展开更多
Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
Photonic neural networks(PNNs)of sufficiently large physical dimensions and high operation accuracies are envisaged as ideal candidates for breaking the major bottlenecks in the current artificial intelligence archite...Photonic neural networks(PNNs)of sufficiently large physical dimensions and high operation accuracies are envisaged as ideal candidates for breaking the major bottlenecks in the current artificial intelligence architectures in terms of latency,energy efficiency,and computational power.To achieve this vision,it is of vital importance to scale up the PNNs while simultaneously reducing the high demand on the dimensions required by them.The underlying cause of this strategy is the enormous gap between the scales of photonic and electronic integrated circuits.Here,we demonstrate monolithically integrated optical convolutional processors on thin film lithium niobate(TFLN)that harness inherent parallelism in photonics to enable large-scale programmable convolution kernels and,in turn,greatly reduce the dimensions required by subsequent fully connected layers.Experimental validation achieves high classification accuracies of 96%(86%)on the MNIST(Fashion-MNIST)dataset and 84.6%on the AG News dataset while dramatically reducing the required subsequent fully connected layer dimensions to 196×10(from 784×10)and 175×4(from 800×4),respectively.Furthermore,our devices can be driven by commercial field-programmable gate array systems;a unique advantage in addition to their scalable channel number and kernel size.Our architecture provides a solution to build practical machine learning photonic devices.展开更多
文摘In order to explore the reduction pathways of zinc oxide in LiCl molten salt and the optimal process,experiments were conducted in an alumina crucible using metallic lithium as the reducing agent and lithium chloride molten salt as the reaction medium at 923 K.The study assessed the effects of lithium thermochemical reduction and electrolytic reduction of ZnO.The volatilization behavior of metal oxides in molten salts,the equivalent of a reducing agent,reduction time,amount of molten salt,stirring time,and the method of reduction feed were investigated for their impacts on the reduction yield and product composition.X-ray powder diffraction(XRD)analysis of the products showed that lithium reduction of ZnO not only produced metallic Zn but also formed a LiZn alloy.Electrolytic reduction can be used to obtain the metallic Zn product by controlling the potential below-2.2 V(vs Ag/Ag^(+)).Moreover,sintered oxides and higher electrode potentials could enhance the efficiency of electrolysis.Under the optimal reaction conditions determined experimentally,the lithium reduction experiment achieved a yield of 77.2%after a 12-h test,and the electrolytic reduction reached a yield of 85.4%after a 6-h test.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
基金supported by the Yunnan Fundamental Research Projects(Grant Nos.202401AU070163 and 202501AT070298)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)+5 种基金the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Expert Workstation Support Project of Yunnan Province(Grant No.202405AF140069)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Test Foundation of Kunming University of Science and Technology(Grant No.2023T20220122)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(Grant No.2025QN02057)the Ordos City Strategic Pioneering Science and Technology Special Program for New Energy(Grant No.DC2400003365).
文摘Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.
基金support of the National Natural Science Foundation of China(22075131 and 22078265)the Shaanxi Fundamental Science Research Project for Mathematics and Physics under Grants(No.22JSZ005)the State-Key Laboratory of Multiphase Complex Systems(No.MPCS-2021-A).
文摘Lithium-sulfur(Li-S)batteries require efficient catalysts to accelerate polysulfide conversion and mitigate the shuttle effect.However,the rational design of catalysts remains challenging due to the lack of a systematic strategy that rationally optimizes electronic structures and mesoscale transport properties.In this work,we propose an autogenously transformed CoWO_(4)/WO_(2) heterojunction catalyst,integrating a strong polysulfide-adsorbing intercalation catalyst with a metallic-phase promoter for enhanced activity.CoWO_(4) effectively captures polysulfides,while the CoWO_(4)/WO_(2) interface facilitates their S-S bond activation on heterogenous catalytic sites.Benefiting from its directional intercalation channels,CoWO_(4) not only serves as a dynamic Li-ion reservoir but also provides continuous and direct pathways for rapid Li-ion transport.Such synergistic interactions across the heterojunction interfaces enhance the catalytic activity of the composite.As a result,the CoWO_(4)/WO_(2) heterostructure demonstrates significantly enhanced catalytic performance,delivering a high capacity of 1262 mAh g^(−1) at 0.1 C.Furthermore,its rate capability and high sulfur loading performance are markedly improved,surpassing the limitations of its single-component counterparts.This study provides new insights into the catalytic mechanisms governing Li-S chemistry and offers a promising strategy for the rational design of high-performance Li-S battery catalysts.
基金supported by the Key Support Project of Regional Innovation and Development Joint Fund of the National Natural Science Foundation of China(No.U24A2095).
文摘Coal serves not only as a crucial energy resource but also as a significant reservoir of critical metal elements,including Lithium(Li),Gallium(Ga),Germanium(Ge),and rare earth elements(REE).This paper provides a systematic review of the enrichment characteristics,occurrence modes,and comprehensive utilization potential of these critical metals in coal.Globally,the distribution of these metal resources exhibits significant regional heterogeneity.While the concentration in most coals falls below industrial cut-off grades,anomalous enrichment in specific coal basins results in Li,Ga,Ge,and REE concentrations far exceeding global averages,highlighting their considerable potential as unconventional metal deposits.The occurrence modes of these metals are diverse:Li is primarily hosted in mineral phases;Ga exists in inorganic,organic,and complex forms;Ge shows a strong association with organic matter;and REE are mainly present in adsorbed/isomorphic forms within clay minerals,while also displaying organic affinity.Direct extraction of metals from raw coal is often cost-prohibitive;effective recovery is therefore more feasible when integrated with coal processing.Metals are further enriched in solid wastes such as coal gangue,fly ash,and bottom ash,from which recovery is more economically and technically viable.Current comprehensive utilization primarily employs integrated mineral processing-hydrometallurgy approaches.Future research should focus on elucidating the precise occurrence forms of metals in coal and solid wastes,optimizing pre-treatment methods,and selecting effective activators and leachants.Advancing the synergistic extraction and green recovery of multiple associated resources from coal and its by-products is essential for achieving high-value,comprehensive utilization of coal-based resources.
基金supported by the National Key Research and Development Program of China(2023YFA1508004)the National Natural Science Foundation of China(T2293692,22502164,92472203,22222903,52271229,22472074,22272069,22361132532,and 22021001)+6 种基金the Industry-University-Research Joint Innovation Project of Fujian Province(2023H6029)the Beijing National Laboratory for Molecular Sciences(BNLMS202305)the Scientific and Technological Project of Yunnan Precious Metals Laboratory(YPML-20240502063)the Liaoning Binhai Laboratory(Grant No.2024-05)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF 2401)the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20240897the China Postdoctoral Science Foundation(No.2025M770016).
文摘Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.
基金supported by the grant of State Key Laboratory of Space Environment Interaction with Matters,the Science and Technology on Vacuum Technology and Physics Laboratory Fund(HTKJ2023KL510008)Key Program of the National Natural Science Foundation of China(No.62433017)+6 种基金the National Natural Science Foundation of China(No.62274140)the Fundamental Research Funds for the Central Universities(20720230030)the Xiaomi Young Talents Program/Xiaomi Foundation,Shenzhen Science and Technology Program(JCYJ20230807091401003)the Young Elite Scientist Sponsorship Program by Cast(No.YESS20230523)the State Key Laboratory of Space Environment Interaction with Matters(WDZC-HGD-2022-08)the Gansu Provincial Science and Technology Major Project(2244ZZDD1133GGAA000077)the China Aerospace Science and Technology Group Corporation Young Top Talents.
文摘With the widespread application of lithium batteries in electric vehicles and energy storage systems,battery-related safety and reliability issues have become increasingly prominent.Conventional monitoring methods often struggle to address dynamic changes under complex operando.In recent years,flexible sensing technology has emerged as a promising solution for battery health monitoring due to its high adaptability and conformability to complex structures.Meanwhile,empowered by artificial intelligence(AI)for data analysis,the collected data enables efficient and accurate state assessment,offering robust support for accident prevention.Against this background,this paper first explores the integrated applications of flexible sensors in battery health monitoring and their unique advantages in addressing complex battery operating conditions,while analyzing the potential of AI in battery state analysis.Subsequently,it systematically reviews mainstream flexible sensing technologies(e.g.,film sensors,thermocouples,and optical fiber sensors),elucidating their mechanisms for revealing intricate internal battery processes during operation.Finally,the paper discusses AI’s role in enhancing monitoring efficiency and accuracy,and envisions future research directions and application prospects.This work aims to provide technical references for the battery health monitoring field as well as promote the application of flexible sensing technologies in improving battery system safety and reliability.
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金the National Natural Science Foundation of China(22479047,22409058)the Outstanding Youth Scientist Foundation of Hunan Province(2022JJ10023)the Provincial Natural Science Foundation of Guangdong(2023A1515011745)for financial support of this research。
文摘To ease the scarcity of lithium(Li)resource and cut down on environmental pollution,an efficient,selective,inexpensive and sustainable Li recycling process from waste batteries is needed,which is yet to be achieved.Here,we report a low-potential photoelectrochemical(PEC)system that selectively and efficiently extracts Li metals from multi-cation electrolytes under 1 sun illumination.Based on the difference of redox potential,we can get rid of the disturbance of other cations(i.e.,Fe,Co and Ni ions)by a bias-free PEC device to realize the extraction of high-purity Li metals on a coplanar Si-based photocathode-TiO_(2) photoanode tandem device at 2 V of applied bias(far less than the redox potentials of Li^(+)/Li).In such system,the extraction rate of Li metals(purity>99.5%)exceeds 1.35 g h^(-1)m^(-2)with 90%of Faradaic efficiency.Long-term experiments,different electrode/electrolyte tests,and various price assessments further demonstrate the stability,compatibility and economy of PEC extraction system,enabling a solar-driven pathway for the recycling of critical metal resources.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231445)Aeronautical Science Foundation of China(20230028052001).
文摘The proton exchange membrane fuel cell(PEMFC)and the hydrogen hybrid power system are studied by the fuzzy-PID(FPID)controlmethod and the fuzzy-PID controlmethod by Artificial Bee Colony algorithm(ABCFPID),respectively.The results reveal that compared with the FPID control method,the temperature overshoot of the PEMFC stack under the ABC-FPID control method is decreased by 0.6%.Moreover,the circulating water flow rate within the full operating envelope(about 3 min)is reduced by 19.46 L,which means the ABC-FPID control method is more effective in regulating the stack temperature.Then,the ABC-FPID control method is proposed to study the hydrogen hybrid power system,and the system output power matching,operating characteristic curve of the fuel cell,state of charge(SOC)of the lithium battery,system efficiency and hydrogen demand are obtained.The results indicate that the maximum system efficiency reaches 46.3%,the average system efficiency is 33.8%,and the average hydrogen demand is 0.192 kg/s.Overall,the ABC-FPID control method can efficiently ensure the stability of the fuel cell’s output power,and actively prompt the lithium battery to fulfill the function of“peak shaving and valley filling”under variable load power conditions.
基金supported by the National Natural Science Foundation of China(52273059,52203066,52403046 and 52473219)the Science and Technology Plans of Tianjin(22JCYBJC01030)+3 种基金the Tianjin Natural Science Foundation(23JCYBJC00660)the Tianjin Enterprise Science and Technology Commissioner Project(23YDTPJC00490)the China Postdoctoral Science Foundation Grant(2023M742135,2024T170525)the State Key Laboratory of Membrane and Membrane Separation,Tiangong University.
文摘The low ionic conductivity and poor mechanical strength of polyethylene oxide(PEO)-based electrolytes severely restrict their practical application.To address this problem,this work designs a scalable,high-strength(24.3 MPa)bicontinuous porous poly(m-phthaloyl-m-phenylenediamine)(PMIA)membrane integrated into PEO/LiTFSI(PL),thus forming a PMIA/PEO/LiTFSI(PPL)composite electrolyte.Compared to the PL electrolyte,the PPL electrolyte reinforced by a bicontinuous porous PMIA membrane exhibits significantly enhanced mechanical strength,reaching 13.4 MPa.In addition,the amide groups on PMIA strongly coordinate with LiTFSI and form hydrogen bonds with PEO,promoting Li salt dissociation and reducing the Li^(+)migration barrier.This creates efficient,fast Li^(+)transport channels at the PMIA/PL interfaces,effectively promoting the uniform Li^(+)deposition and minimizing lithium dendrite formation.The PPL electrolyte achieves high ionic conductivity(1×10^(−4)S cm^(−1)at 30°C)and Li^(+)transference number(tLi^(+)=0.43).The assembled LiFePO_(4)/Li battery demonstrates excellent cycling stability,retaining 80%capacity after 2000 cycles at 2 C,while the Li/Li symmetric cell operates stably for over 900 h at 0.3 mA cm^(−2).Therefore,the scalable porous PMIA membrane effectively enhances both the mechanical strength and Li^(+)transport in PEO-based electrolytes,offering a viable strategy for their commercial-scale implementation.
基金supported by the National Key R&D Program of China(2021YFB3800300).
文摘High-nickel cathode,LiNi0.8Co0.1Mn0.1O_(2)(NCM811),and sulfide-solid electrolyte are a promising combination for all-solid-state lithium batteries(ASSLBs).However,this combination faces the issue of interfacial instability between the cathode and electrolyte.Given the surface alkalinity of NCM811,we propose a strategy to construct a solid-polymer-electrolyte(SPE)interphase on NCM811 surface by leveraging the surface alkaline residues to nucleophilically initiate the in-situ ring-opening polymerization of cyclic organic molecules.As a proof-of-concept,this study demonstrates that the ring-opening copolymerization of 1,3-dioxolane and maleic anhydride produces a homogeneous,compact,and conformal SPE layer on NCM811 surface to prevent the cathode from contact and reaction with Li6PS5Cl solid-state electrolyte.Consequently,the SPE-modified-NCM811 in ASSLBs exhibits high capacities of 193.5 mA h g^(-1) at 0.2 C,160.9 mA h g^(-1) at 2.0 C and 112.3 mA h g^(-1) at 10 C,and particularly,excellent long-term cycling stabilities over 11000 cycles with a 71.95%capacity retention at 10 C at 25℃,as well as a remained capacity of 117.9 mA h g^(-1) after 8000 cycles at 30 C at 60℃,showing a great application prospect.This study provides a new route for creating electrochemically and structurally stable solid-solid interfaces for ASSLBs.
基金financially supported by the National Nature Science Foundation of China (No.52401273)Science and Technology Department of Henan (Nos.242102241007,252102320178 and 252102321067)Training Program for Young Backbone Teachers in Higher Education Institutions in Henan Province (No.2024GGJS101)。
文摘Structural instability and sluggish lithium-ion(Li+) kinetics of spinel NiCo_(2)O_(4) anodes severely hinder their applications in high-energy-density lithium-ion batteries.Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics.However,their controlled synthesis mechanisms remain elusive.Herein,a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo_(2)O_(4) nanorods.Remarkably,mesocrystalline NiCo_(2)O_(4) exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g,attributed to its porous structure facilitating Li^(+) transport kinetics and unique stress-buffering effect validated by ex-situ TEM.Theoretical calculations and interfacial chemical analysis reveal that substratecrystal surface engineering regulates the nucleation-growth pathways:Acid-treated nickel foam enables epitaxial growth via lattice matching,acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization.In contrast,carbon cloth requires hightemperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy.This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis.The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
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the financial support from the National Natural Science Foundation of China(52203123 and 52473248)State Key Laboratory of Polymer Materials Engineering(sklpme2024-2-04)+1 种基金the Fundamental Research Funds for the Central Universitiessponsored by the Double First-Class Construction Funds of Sichuan University。
文摘Composite polymer electrolytes(CPEs)offer a promising solution for all-solid-state lithium-metal batteries(ASSLMBs).However,conventional nanofillers with Lewis-acid-base surfaces make limited contribution to improving the overall performance of CPEs due to their difficulty in achieving robust electrochemical and mechanical interfaces simultaneously.Here,by regulating the surface charge characteristics of halloysite nanotube(HNT),we propose a concept of lithium-ion dynamic interface(Li^(+)-DI)engineering in nano-charged CPE(NCCPE).Results show that the surface charge characteristics of HNTs fundamentally change the Li^(+)-DI,and thereof the mechanical and ion-conduction behaviors of the NCCPEs.Particularly,the HNTs with positively charged surface(HNTs+)lead to a higher Li^(+)transference number(0.86)than that of HNTs-(0.73),but a lower toughness(102.13 MJ m^(-3)for HNTs+and 159.69 MJ m^(-3)for HNTs-).Meanwhile,a strong interface compatibilization effect by Li^(+)is observed for especially the HNTs+-involved Li^(+)-DI,which improves the toughness by 2000%compared with the control.Moreover,HNTs+are more effective to weaken the Li^(+)-solvation strength and facilitate the formation of Li F-rich solid-electrolyte interphase of Li metal compared to HNTs-.The resultant Li|NCCPE|LiFePO4cell delivers a capacity of 144.9 m Ah g^(-1)after 400 cycles at 0.5 C and a capacity retention of 78.6%.This study provides deep insights into understanding the roles of surface charges of nanofillers in regulating the mechanical and electrochemical interfaces in ASSLMBs.
基金supported by National Natural Science Foundation of China(52372180,92572105)The Natural Science Foundation of Jiangsu Province(BK20250069)+3 种基金Project on Carbon Emission Peak and Neutrality of Jiangsu Province(BE2022031-4)the Fundamental Research Funds for the Central Universities(2242022K40001)The Start-up Research Fund of Southeast University(RF1028623081)Natural Science Foundation of Chongqing(CSTB2025NSCQ-GPX0662).
文摘Lithium metal batteries(LMBs)have attracted huge attention due to super-high capacity and low reduction potential of lithium anode constructing high-energy/power density.However,the practical application of LMBs is significantly constrained by lithium dendrite growth and high reactivity of lithium anode.Herein,a novel functionalized interlayer that SbF3 is tandem on HKUST-1 skeleton forming favorable Sb-terminated groups structure(HKSF@PE),which were proposed and fabricated to construct highly stable LMBs.Theoretical calculations demonstrate that the Sb-terminated groups structure in this configuration display strong interaction with lithium,which can act as a cation receptor and adsorption sites,thereby promoting lithium-ion desolvation and improving lithium-ion transport kinetics.Meanwhile,in-situ XRD,Raman,and DRT analyses indicate that the HKSF assist the formation of LiF-rich and lithiophilic Li3Sb alloys at SEI/Li interface,regulating lithium depo-sition morphology and reconstructing a reinforced SEI interlayer.Consequently,Li|HKSF@PE|Li symmetric cell exhibits exceptional stability over 2500 h at 2 mA cm^(-2) with 1 mAh cm^(-2),and Li|HKSF@PE|LFP full cell demonstrates a high-capacity retention of 92.0%after 220 cycles even at a high rate of 5C.This work reveals the important role of terminated groups to achieve homogeneous lithium deposition and provide a way to construct stable LMBs.
基金financial support from the National Natural Science Foundation of China (22338011, 22378299)Hainan Province Science and Technology Special Fund (ZDYF2025SHFZ025)+1 种基金Ningbo Key Research and Development Project (2022Z121)the China Postdoctoral Science Foundation (2025M771194)。
文摘Due to complex ion-ion and ion-membrane interactions, creating innovative membrane structures to acquire favorable ion mixing effect and high separation performance remains a big challenge. Herein, we design covalent organic framework(COF) scaffold membrane with gate-lane nanostructure for efficient Li^(+)/Mg^(2+) separation. COF nanosheets, serving as the scaffold, are intercalated by polyethyleneimine(PEI) to form the permeating layer. Subsequently, PEI on the surface reacts with 1,4-phenylene diisocyanate to form the polyurea gating layer. The gating layer, bearing tailored smaller pore size,affords high rejection to co-ions(Mg^(2+)) and thus high Li^(+)/Mg^(2+) selectivity. The permeating layer, with asymmetric charge and spatial nanostructure for creating individual lanes of Li^(+) and Cl~-, facilitates Li^(+) transport and thus high Li^(+) permeability. The optimum COF scaffold membrane exhibits the permeance of 11.5 L m^(-2) h^(-1)/bar^(-1) and true selectivity of 231.9 with Li^(+) enrichment of 120.2% at the Mg^(2+)/Li^(+) mass ratio of 50, exceeding the ideal selectivity of 80.5 and outperforming all ever-reported positively charged nanofiltration membranes. Our work may stimulate the further thinking about how to design the hierarchical membrane structure to achieve favorable ion mixing effect and break the membrane permeability-selectivity trade-off in chemical separations.
基金Supported by National Natural Science Foundation of China(Grant Nos.52575516,51875329)Taishan Scholar Special Foundation of Shandong Province(Grant Nos.tstp20240826,tsqn201812064)+2 种基金Shandong Provincial Natural Science Foundation(Grant No.ZR2023ME112)Key Research and Development Project of the Ningxia Hui Autonomous Region(Grant No.2024BEE02019)Innovation Capacity Improvement Programme for High-tech SMEs of Shandong Province(Grant Nos.2022TSGC1333,2022TSGC1261).
文摘The surfaces of brittle materials are susceptible to defects such as scratches,cracks,and chipping during con-ventional grinding processes,which significantly compromise surface quality and service performance.A flexible ball-end body-armor-like abrasive tool(BAAT)can effectively remove micro-convex peaks from the surfaces of brittle materials by employing a high tangential grinding force and a low normal grinding force,thereby achieving nano-level surface roughness and ultra-smooth mirror finishes.However,the surface contact me-chanism,pressure distribution pattern,and grinding force behavior between BAAT and workpiece remain in-adequately understood.This study examines the mechanism of liquid film formation and the distribution pattern of elastohydrodynamic pressure in high-shear and low-pressure grinding areas,drawing on the theories of elastohydrodynamic lubrication,non-Newtonian fluid dynamics,and material mechanics.A high-shear low-pressure grinding force model,which incorporates elastohydrodynamic liquid film thickness and abrasive grain size,was developed.The effects of the main grinding parameters(normal load,spindle rotational speed,and abrasive grain size)on the tangential grinding force were investigated through the processing of lithium niobate crystals using an intelligent precision-grinding system.The experimental results indicated that the relative error between the predicted and experimental values was 10.74%,thereby confirming the accuracy of the grinding force model.This study advances the understanding of elastohydrodynamic lubrication mechanisms in abrasive machining and provides a crucial theoretical foundation for the application of flexible ball-end BAAT.
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
基金supported by the National Natural Science Foundation of China (Grant Nos.12192251,12334014,62335019,12134001,1230441812474378)+1 种基金the Quantum Science and Technology National Science and Technology Major Project(Grant No.2021ZD0301403)the Shanghai Municipal Science and Technology Major Project (Grant No.2019SHZDZX01)。
文摘Photonic neural networks(PNNs)of sufficiently large physical dimensions and high operation accuracies are envisaged as ideal candidates for breaking the major bottlenecks in the current artificial intelligence architectures in terms of latency,energy efficiency,and computational power.To achieve this vision,it is of vital importance to scale up the PNNs while simultaneously reducing the high demand on the dimensions required by them.The underlying cause of this strategy is the enormous gap between the scales of photonic and electronic integrated circuits.Here,we demonstrate monolithically integrated optical convolutional processors on thin film lithium niobate(TFLN)that harness inherent parallelism in photonics to enable large-scale programmable convolution kernels and,in turn,greatly reduce the dimensions required by subsequent fully connected layers.Experimental validation achieves high classification accuracies of 96%(86%)on the MNIST(Fashion-MNIST)dataset and 84.6%on the AG News dataset while dramatically reducing the required subsequent fully connected layer dimensions to 196×10(from 784×10)and 175×4(from 800×4),respectively.Furthermore,our devices can be driven by commercial field-programmable gate array systems;a unique advantage in addition to their scalable channel number and kernel size.Our architecture provides a solution to build practical machine learning photonic devices.
