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
1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained ...1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained attention.The performance of routine LIBs is approaching the ceiling,particularly in terms of energy density,making it difficult to meet the ever-increasing demand for energy density[1].展开更多
Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese ...Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].展开更多
Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance ...Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance and safety.This review provides a comprehensive overview of the mechanisms behind lithium dendrite formation and the role of in situ/operando observation and phase field simulation in understanding and mitigating this issue,The key driving factors of dendrite growth,such as lithium-ion flux heterogeneity,surface defects,and localized stress,are explored through advanced experimental techniques,which enable real-time visualization of dendrite nucleation and growth dynamics.Complementarily,phase field simulations provide insights into subsurface and temporal evolution of dendrites by modeling thermodynamic and kinetic processes,while machine learning techniques optimize simulation accuracy through data-driven parameter refinement.The integration of experimental observations with simulation models holds great potential in improving understanding and predictive capabilities.Despite ongoing progress,challenges remain in resolving technical limitations in observation techniques,improving computational efficiency,and fostering interdisciplinary collaboration.This review highlights the synergy between experimental and computational strategies in advancing the development of LMBs and calls for continued research to overcome existing hurdles and unlock the full potential of lithium metal anodes.展开更多
The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin...The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin of this limitation has remained unresolved.Here,we uncover the origin of this behavior through a comprehensive analysis driven by artifact/damage-free direct cryogenic transmission electron microscopy,which enabled one of the most chemically specific and morphologically intuitive visualizations to date of intact solid-electrolyte interphases(SEIs)and lithium growth.Contrary to conventional interpretations centered on nitrogen-rich or single-component SEIs,we reveal that LiNO_(3) rapidly generates lithium hydroxide(LiOH)and lithium oxide(Li_(2)O)rich interphases,whose complementary functions—ionic transport through LiOH and mechanical robustness from Li_(2)O—synergistically suppress whisker nucleation and favor compact,particle-like growth.Over the extended plating,however,depletion of these species in combination with crystallographically favored orientations drives the particle-towhisker transition,explaining why the effectiveness of LiNO_(3) is inherently limited.This direct mechanistic visualization resolves a long-standing ambiguity regarding the transient efficacy of LiNO_(3) and reframes its function from a nitrogen-driven mechanism to a synergistic dual oxygen-interphase framework.Beyond mechanistic clarification,these findings establish that continuous regeneration of LiOH and Li_(2)O is essential for stable lithium deposition,offering a design principle for the development of durable electrolytes in high-performance anode-free lithium metal batteries.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
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
Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms lig...Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.展开更多
This paper introduces an innovative Multifunction Integrated Optic Circuit(MIOC)design utilizing thin-film lithium niobate,surpassing traditional bulk waveguide-based MIOCs in terms of size,half-wave voltage requireme...This paper introduces an innovative Multifunction Integrated Optic Circuit(MIOC)design utilizing thin-film lithium niobate,surpassing traditional bulk waveguide-based MIOCs in terms of size,half-wave voltage requirements,and integration capabilities.By implementing a sub-wavelength grating structure,we achieve a Po⁃larization Extinction Ratio(PER)exceeding 29 dB.Furthermore,our electrode design facilitates a voltage-length product(V_(π)L)below 2 V·cm,while a double-tapered coupling structure significantly reduces insertion loss.This advancement provides a pivotal direction for the miniaturization and integration of optical gyroscopes,marking a substantial contribution to the field.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(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 leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigat...The leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigated.Under optimized conditions,the leaching efficiencies of Li,K,Rb,Cs and Al are 92.02%,93.31%,88.59%,86.75%and 81.07%,respectively.Kinetics research results show that the leaching process conforms to the shrinking core model that is under the mixed control of chemical reaction and diffusion through the solid product layer.In addition,the contribution of solid product layer diffusion to the leaching gradually expands as the temperature rises,but it is still significantly less than the contribution of chemical reaction.Cost saving in the neutralizing agent and leaching processes makes hydrochloric acid an economical leaching agent for lepidolite.Finally,the Li2CO3 product with a purity of 99.89%was synthesized from the hydrochloric acid leachate.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
Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety ...Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety and cycle life,including lithium dendrite formation,solid electrolyte interphase degradation,dead lithium accumulation,and substantial volume fluctuations during cycling.These problems can be addressed by regulating lithium deposition and suppressing side reactions through the modification of copper current collectors using three classes of materials:metal and metal oxide,carbon,and polymer materials.This review comprehensively examines recent advances in the application of these materials as current collector coatings.Particularly,their distinct roles in the lithium deposition process are analyzed to understand how they mitigate the issues associated with the lithium metal anode.Furthermore,their inherent limitations are considered to inform future research directions.While each class of materials offers specific advantages,multifunctionality is required to effectively regulate lithium deposition.In prospect,a novel composite copper current collector design that integrates the merits of the aforementioned advanced materials is proposed.The insights from this review provide valuable guidance for the rational design of modified copper current collectors,which would significantly improve the safety and cycle life of LMBs and advance their commercialization.展开更多
Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte i...Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte interface.Functional protective coatings on lithium metal surfaces offer a viable solution to these challenges.Herein,an innovative adaptive protective layer for lithium metal anodes based on a thiourea H-bonded supramolecular polymer is developed for the first time.With dense thiourea H-bonding,the lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)incorporated poly(ether-thiourea)protective layer shows strong adhesion to the lithium metal surface and good adaptive properties.The unique viscoelastic and flow characteristics of the poly(ether-thiourea)coating facilitate uniform Li⁺flux,effectively suppressing dendrite formation at the solid electrolyte interface.Furthermore,this innovative polymer integrates in situ generated compounds,such as Li3N and Li_(2)O,significantly enhancing interfacial stability.A comprehensive analysis involving X-ray photoelectron spectroscopy,scanning electron microscopy,X-ray tomography,and COMSOL simulations elucidates the beneficial effects of the adaptive coating.Enhanced performances in Li||Cu,Li||Li,Li||LiFePO_(4),and Li||S cells demonstrate the effectiveness of the poly(ether-thiourea)coating and its undeniable capability to improve lithium deposition and cycling stability.This study highlights a promising new candidate for developing supramolecular materials capable of stabilizing lithium metal anodes.展开更多
Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral ...Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral techniques have achieved many exciting results in soil metal monitoring due to their advantages of being fast and non-destructive.However,insufficient attention has been paid to lithium in soil,and the feasibility of its estimation using hyperspectral techniques needs to be investigated.We studied 97 soil samples from claytype lithium mines in the Ertanggou area of the East Tianshan Mountains of Xinjiang to explore the effects of spectral resolution,fractional order derivatives(FOD),and characteristic band selection on the estimation accuracy of clay Li content,to obtain a fast and effective method for estimating clay Li content.Finally,we developed a new method for rapid and nondestructive estimation of soil lithium content.We have obtained some important results from the study.Spectral resolution exerts a significant impact on model performance,and its reduction usually leads to a decline in model performance.For the full band,the models constructed with low-order derivatives were superior to those with high-order derivatives,and the best model was obtained at the 0.4-order derivative(coefficient of determination(R^(2))and relative predictive deviation(RPD)of 0.777 and 2.118,respectively).In the characteristic bands,the lower order is sensitive to the visible-near-infrared range,and the higher order is sensitive to the short-wave infrared range,and the model constructed with the higher-order derivatives outperforms the lower-order derivatives.In this study,the combination of FOD and Random Forest(RF)can significantly improve the model performance,with R^(2),Relative Root Mean Squared Error(RRMSE),and RPD being 0.849,1.526,and 2.574,respectively.Therefore,this research provides a theoretical basis and technical reference for imaging hyperspectral exploration of anomalous areas of clay-type Li resources.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.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
Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous struct...Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.展开更多
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supported by the Beijing Natural Science Foundation(L243019)the National Natural Science Foundation of China(22393900,22393904)+3 种基金the National Key Research and Development Program(2021YFB2500300)the JBGS project from Ordos(JBGS2024001)the Tsinghua University Initiative Scientific Research Programthe“Shuimu Tsinghua Scholar Program of Tsinghua University”。
文摘1.Introduction Driven by the growing demand for energy storage systems in portable electronic devices,electric vehicles,and unmanned aerial vehicles,lithium-ion batteries(LIBs)have received considerable and sustained attention.The performance of routine LIBs is approaching the ceiling,particularly in terms of energy density,making it difficult to meet the ever-increasing demand for energy density[1].
基金supported by the National Natural Science Foundation of China(No.22479021).
文摘Solid-state lithium(Li)batteries are hailed as the nextgeneration energy storage technology,garnering significant attention for their potential high energy density and safety.Particularly when using Li-rich manganese layered oxide(LRMO)as cathodes(theoretical capacity exceeding250 mAh/g),energy densities over 600 Wh/kg can be theoretically achieved[1,2].
基金the financial support of the National Natural Science Foundation of China(Nos.12172206 and 11972218)。
文摘Lithium metal batteries(LMBs)represent a promising solution for next-generation energy storage due to their high energy density,but the growth of lithium dendrites presents significant challenges to their performance and safety.This review provides a comprehensive overview of the mechanisms behind lithium dendrite formation and the role of in situ/operando observation and phase field simulation in understanding and mitigating this issue,The key driving factors of dendrite growth,such as lithium-ion flux heterogeneity,surface defects,and localized stress,are explored through advanced experimental techniques,which enable real-time visualization of dendrite nucleation and growth dynamics.Complementarily,phase field simulations provide insights into subsurface and temporal evolution of dendrites by modeling thermodynamic and kinetic processes,while machine learning techniques optimize simulation accuracy through data-driven parameter refinement.The integration of experimental observations with simulation models holds great potential in improving understanding and predictive capabilities.Despite ongoing progress,challenges remain in resolving technical limitations in observation techniques,improving computational efficiency,and fostering interdisciplinary collaboration.This review highlights the synergy between experimental and computational strategies in advancing the development of LMBs and calls for continued research to overcome existing hurdles and unlock the full potential of lithium metal anodes.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MSIT)(No.RS-2024-00406724(50%)RS-2023-00222411,RS-2025-24533073)+2 种基金the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Korea government(MOE)(RS-2024-00436346)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea government(MOTIE)(RS-2024-00417730,HRD Program for Industrial Innovation)the research fund of Hanyang University(HY-202100000003295)。
文摘The electrolyte additive,lithium nitrate(LiNO_(3)),is widely recognized for suppressing dendritic lithium growth in anode-free lithium metal batteries,yet its stabilizing effect is transient,and the mechanistic origin of this limitation has remained unresolved.Here,we uncover the origin of this behavior through a comprehensive analysis driven by artifact/damage-free direct cryogenic transmission electron microscopy,which enabled one of the most chemically specific and morphologically intuitive visualizations to date of intact solid-electrolyte interphases(SEIs)and lithium growth.Contrary to conventional interpretations centered on nitrogen-rich or single-component SEIs,we reveal that LiNO_(3) rapidly generates lithium hydroxide(LiOH)and lithium oxide(Li_(2)O)rich interphases,whose complementary functions—ionic transport through LiOH and mechanical robustness from Li_(2)O—synergistically suppress whisker nucleation and favor compact,particle-like growth.Over the extended plating,however,depletion of these species in combination with crystallographically favored orientations drives the particle-towhisker transition,explaining why the effectiveness of LiNO_(3) is inherently limited.This direct mechanistic visualization resolves a long-standing ambiguity regarding the transient efficacy of LiNO_(3) and reframes its function from a nitrogen-driven mechanism to a synergistic dual oxygen-interphase framework.Beyond mechanistic clarification,these findings establish that continuous regeneration of LiOH and Li_(2)O is essential for stable lithium deposition,offering a design principle for the development of durable electrolytes in high-performance anode-free lithium metal batteries.
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.
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.
文摘Herein,3‑aminopropyltriethoxysilane(APTES)was used to modify F‑containing silica slag(SS)by simple grafting and served as a multifunctional barrier layer.The amino group(—NH2)in the amino‑modified SS(NH2‑SS)forms ligand bonds or hydrogen bonds with sulfur ions in lithium polysulfides(LiPSs),thus inhibiting the shuttle effect.Electrochemical analyses demonstrated that lithium‑sulfur(Li‑S)batteries employing the NH2‑SS interlayer exhibited discharge specific capacities of 1048 and 789 mAh·g^(-1) at 0.2C and 2C,respectively,and even at 4C,the initial discharge specific capacity remained at 590 mAh·g^(-1),outperforming the Li‑S battery with unmodified SS as the interlayer.
基金Supported by the Beijing Municipal Natural Science Foundation(424206)the Youth Innovation Promotion Association,CAS(2021108).
文摘This paper introduces an innovative Multifunction Integrated Optic Circuit(MIOC)design utilizing thin-film lithium niobate,surpassing traditional bulk waveguide-based MIOCs in terms of size,half-wave voltage requirements,and integration capabilities.By implementing a sub-wavelength grating structure,we achieve a Po⁃larization Extinction Ratio(PER)exceeding 29 dB.Furthermore,our electrode design facilitates a voltage-length product(V_(π)L)below 2 V·cm,while a double-tapered coupling structure significantly reduces insertion loss.This advancement provides a pivotal direction for the miniaturization and integration of optical gyroscopes,marking a substantial contribution to the field.
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(No.52122407)the National Key Research&Development Program of China(No.2022YF2906200)the Science and Technology Innovation Program of Hunan Province,China(No.2022RC3048)。
文摘The leaching process and kinetic behavior of lepidolite in hydrochloric acid were explored systematically.The influence of leaching conditions on the leaching efficiency of valuable metals in lepidolite was investigated.Under optimized conditions,the leaching efficiencies of Li,K,Rb,Cs and Al are 92.02%,93.31%,88.59%,86.75%and 81.07%,respectively.Kinetics research results show that the leaching process conforms to the shrinking core model that is under the mixed control of chemical reaction and diffusion through the solid product layer.In addition,the contribution of solid product layer diffusion to the leaching gradually expands as the temperature rises,but it is still significantly less than the contribution of chemical reaction.Cost saving in the neutralizing agent and leaching processes makes hydrochloric acid an economical leaching agent for lepidolite.Finally,the Li2CO3 product with a purity of 99.89%was synthesized from the hydrochloric acid leachate.
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 National Natural Science Foundation of China(grant numbers 52071225,22179143,and 22002176)the European Union’s Horizon Europe research and innovation program Electron Beam Emergent Additive Manufacturing(EBEAM)(grant number 101087143)+2 种基金a Norway Grant through the National Science Centre(project number 2019/34/H/ST8/00547)the National Key R&D Program of China(grant number 2021YFB3800300)the Jiangsu Funding Program for Excellent Postdoctoral Talent。
文摘Lithium metal batteries(LMBs)are promising candidates for next-generation high-energy-density storage devices.However,an unstable lithium metal anode poses significant issues that critically compromise battery safety and cycle life,including lithium dendrite formation,solid electrolyte interphase degradation,dead lithium accumulation,and substantial volume fluctuations during cycling.These problems can be addressed by regulating lithium deposition and suppressing side reactions through the modification of copper current collectors using three classes of materials:metal and metal oxide,carbon,and polymer materials.This review comprehensively examines recent advances in the application of these materials as current collector coatings.Particularly,their distinct roles in the lithium deposition process are analyzed to understand how they mitigate the issues associated with the lithium metal anode.Furthermore,their inherent limitations are considered to inform future research directions.While each class of materials offers specific advantages,multifunctionality is required to effectively regulate lithium deposition.In prospect,a novel composite copper current collector design that integrates the merits of the aforementioned advanced materials is proposed.The insights from this review provide valuable guidance for the rational design of modified copper current collectors,which would significantly improve the safety and cycle life of LMBs and advance their commercialization.
基金Yongsheng Zhang(CSC no.202106050027),Xiaolong He(CSC no.202106340039),Yinyu Xiang(CSC no.201806950083)acknowledge the financial support from the Chinese Scholarship Council(CSC)the Advanced Materials Research program of the Zernike Institute under the Bonus Incentive Scheme of the Dutch Ministry for Education,Culture and Science(OCW)the Battery NL-Next Generation Battery based on Understanding Materials Interfaces project(with project number NWA 1389.20.089)of the NWA research program“Research on Routes by Consortia(ORC)”funded by the Dutch Research Council(NWO)。
文摘Lithium metal is a promising anode material for high-energy-density batteries;however,its practical applications are significantly hindered by unstable lithium deposition and dendrite growth at the solid electrolyte interface.Functional protective coatings on lithium metal surfaces offer a viable solution to these challenges.Herein,an innovative adaptive protective layer for lithium metal anodes based on a thiourea H-bonded supramolecular polymer is developed for the first time.With dense thiourea H-bonding,the lithium bis(trifluoromethanesulfonyl)imide(Li TFSI)incorporated poly(ether-thiourea)protective layer shows strong adhesion to the lithium metal surface and good adaptive properties.The unique viscoelastic and flow characteristics of the poly(ether-thiourea)coating facilitate uniform Li⁺flux,effectively suppressing dendrite formation at the solid electrolyte interface.Furthermore,this innovative polymer integrates in situ generated compounds,such as Li3N and Li_(2)O,significantly enhancing interfacial stability.A comprehensive analysis involving X-ray photoelectron spectroscopy,scanning electron microscopy,X-ray tomography,and COMSOL simulations elucidates the beneficial effects of the adaptive coating.Enhanced performances in Li||Cu,Li||Li,Li||LiFePO_(4),and Li||S cells demonstrate the effectiveness of the poly(ether-thiourea)coating and its undeniable capability to improve lithium deposition and cycling stability.This study highlights a promising new candidate for developing supramolecular materials capable of stabilizing lithium metal anodes.
基金Sponsored the National Natural Science Foundation of China(42502088)the National Major Science and Technology Project of China(2025ZD1007504-1)+2 种基金the Special Research Fund of Natural Science(Special Post)of Guizhou University(X202402)the Guizhou Provincial Science and Technology Projects(QKHJC[2024]youth 153)the Xinjiang Uygur Autonomous Region Natural Science Foundation(2024D01A147)。
文摘Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral techniques have achieved many exciting results in soil metal monitoring due to their advantages of being fast and non-destructive.However,insufficient attention has been paid to lithium in soil,and the feasibility of its estimation using hyperspectral techniques needs to be investigated.We studied 97 soil samples from claytype lithium mines in the Ertanggou area of the East Tianshan Mountains of Xinjiang to explore the effects of spectral resolution,fractional order derivatives(FOD),and characteristic band selection on the estimation accuracy of clay Li content,to obtain a fast and effective method for estimating clay Li content.Finally,we developed a new method for rapid and nondestructive estimation of soil lithium content.We have obtained some important results from the study.Spectral resolution exerts a significant impact on model performance,and its reduction usually leads to a decline in model performance.For the full band,the models constructed with low-order derivatives were superior to those with high-order derivatives,and the best model was obtained at the 0.4-order derivative(coefficient of determination(R^(2))and relative predictive deviation(RPD)of 0.777 and 2.118,respectively).In the characteristic bands,the lower order is sensitive to the visible-near-infrared range,and the higher order is sensitive to the short-wave infrared range,and the model constructed with the higher-order derivatives outperforms the lower-order derivatives.In this study,the combination of FOD and Random Forest(RF)can significantly improve the model performance,with R^(2),Relative Root Mean Squared Error(RRMSE),and RPD being 0.849,1.526,and 2.574,respectively.Therefore,this research provides a theoretical basis and technical reference for imaging hyperspectral exploration of anomalous areas of clay-type Li resources.
基金supported by the National Natural Science Foundation of China(No.42272044)the High-performance Computing Platform of China University of Geosciences Beijing。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes.Here,we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions,which self-assemble into flower-like spherulites with radially aligned lamellar crystals.This unique structure creates continuous Li^(+)transport highways through densely packed crystalline domains,achieving a record-high ionic conductivity of 1.70×10^(-4) S/cm at 25℃ for pristine PEO-based systems.Strategic incorporation of lithium montmorillonite(MMTli,10 wt%)further optimizes the composite electrolyte,balancing high ionic conductivity(1.47×10^(-4) S/cm)with enhanced electrochemical stability(4.99 V vs.Li^(+)/Li),elevated Li^(+)transference number(0.62),and mechanical robustness.The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO_(4)||Li solid-state batteries with 82%capacity retention after 200 cycles at 0.2 C under ambient conditions.This work pioneers a scalable processing paradigm for crystalline polymer electrolytes,offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
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supported by the National Natural Science Foundation of China(Grant No.22479046,22461142135)。
文摘Cellulose,the most abundant and renewable biopolymer,offers a sustainable and cost-effective solution for regulating lithium electrodeposition toward safer lithium metal batteries,thanks to its high nanofibrous structure and intrinsic lithiophilic property.In this work,we introduce interface-engineered cellulose-based separators by converting intrinsic hydroxyl groups on cellulose nanofibers(CNFs)to nitrogen functionalities through a trace conducting polymer coating.Both experimental and theoretical results reveal that the nitrogen moieties disrupt the compact hydrogen bond network within hydroxyl cellulose,enabling multiple nitrogen-lithium interactions that enhance lithium ion transport.In addition to an extraordinary Li^(+)transference number of 0.86 and a high ionic conductivity of 1.1 mS cm^(-1),the nitrogen-functionalized CNF contributes to a uniform electric field and Li^(+)concentration distribution across the lithium metal surface.This facilitates the formation of a LiF-rich solid electrolyte interface and suppresses Li dendrite growth.Consequently,Li‖Li cells demonstrate stable plating/stripping cycles for approximately 3000 h at a current density of 1 mA cm^(-2) with a fixed capacity of 1 mAh cm^(-2),while maintaining a low overpotential of 15 mV.Our work provides valuable insights into the surface functionalization of natural biomass for advancing sustainable energy storage technologies.
