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
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
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-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
Lithium-ion batteries(LIBs)are the most popular energy storage devices due to their high energy density,high operating voltage,and long cycle life.However,green and effective recycling methods are needed because LIBs ...Lithium-ion batteries(LIBs)are the most popular energy storage devices due to their high energy density,high operating voltage,and long cycle life.However,green and effective recycling methods are needed because LIBs contain heavy metals such as Co,Ni,and Mn and organic compounds inside,which seriously threaten human health and the environment.In this work,we review the current status of spent LIB recycling,discuss the traditional pyrometallurgical and hydrometallurgical recovery processes,and summarize the existing short-process recovery technologies such as salt-assisted roasting,flotation processes,and direct recycling.Finally,we analyze the problems and potential research prospects of the current recycling process,and point out that the multidisciplinary integration of recycling will become the mainstream technology for the development of spent LIBs.展开更多
The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separat...The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separators with improved mechanical and electrochemical characteristics.This review covers the improved mechanical and electrochemical performances as well as the advancements made in the design of separators utilizing a variety of techniques.In terms of electrolyte wettability and adhesion of the coating materials,we provide an overview of the current status of research on coated separators,in situ modified separators,and grafting modified separators,and elaborate additional performance parameters of interest.The characteristics of inorganics coated separators,organic framework coated separators and inorganic-organic coated separators from different fabrication methods are compared.Future directions regarding new modified materials,manufacturing process,quantitative analysis of adhesion and so on are proposed toward next-generation advanced lithium batteries.展开更多
The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate elect...The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.展开更多
The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolyt...The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.展开更多
Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properti...Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.展开更多
Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is l...Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.展开更多
The swelling behavior and stability in solid electrolyte interphase(SEI)have been proved to determine the battery cycle life.A high swollen,unstable SEI shows a high permeability to electrolyte,which results in the ra...The swelling behavior and stability in solid electrolyte interphase(SEI)have been proved to determine the battery cycle life.A high swollen,unstable SEI shows a high permeability to electrolyte,which results in the rapid battery performance degradation.Here,we customize two SEIs with different spatial structures(bilayer and mosaic)by simply regulating the proportion of additive fluoroethylene carbonate.Surprisingly,due to the uniform distribution of dense inorganic nano-crystals in the inner,the bilayer SEI exhibits low-swelling and excellent mechanical properties,so the undesirable side reactions of the electrolyte are effectively suppressed.In addition,we put forward the growth rate of swelling ratio(GSR)as a key indicator to reveal the swelling change in SEI.The GSR of bilayer SEI merely increases from1.73 to 3.16 after the 300th cycle,which enables the corresponding graphite‖Li battery to achieve longer cycle stability.The capacity retention is improved by 47.5% after 300 cycles at 0.5 C.The correlation among SEI spatial structure,swelling behavior,and battery performance provides a new direction for electrolyte optimization and interphase structure design of high energy density batteries.展开更多
In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-dept...In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.展开更多
In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadin...In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadings.Here,we propose a novel separator structure with an interlayer composed of a vermiculite nanosheet combined with Ketjen Black(VMT@KB)for LSBs,facilitating efficient adsorption and rapid catalytic conversion toward lithium polysulfides(LiPSs).The VMT@KB nanosheets with an electrical double-layer structure and electronic conductivity are obtained through a high-temperature peeling process and Li^(+)exchange treatment in LiCl solution,followed by a mechanical combination process with KB.The results demonstrate that incorporating VMT@KB as an interlayer on a conventional separator enhances the conductivity and limits the LiPSs in the cathode region.The Li-S cell with VMT@KB interlayer shows satisfactory cycle and rate performance,especially in high sulfur loading.It exhibits a remarkable initial discharge capacity of 1225 mAh g^(-1)at 0.5 C and maintains a capacity of 816 mAh g^(-1)after 500 cycles.Besides,the discharge capacity remains 462 mAh g^(-1)even at 6 C.Moreover,the cell with high sulfur loading(8.2 mg cm^(-2))enables stable cycling for 100 cycles at 0.1 C with a discharge capacity of over1000 mAh g^(-1).展开更多
As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather tha...As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather than H_(2)upon decomposition.In this work,we report thatthe combination of AlH_(3)and LiNH_(2)through simple ball milling leads to partial reversibility of the AlH_(3)-LiNH_(2)system and the suppression of NH_(3)liberation.The negatively charged H^(δ-)in AlH_(3)will react with the positively charged H^(δ+)in LiNH_(2)through a redox reaction to form Li_(2)NH,AlN,and H_(2)at 120-170℃.After dehydrogenation at above 270℃,Li_(3)AlN_(2)is generated,which is crucial for the reversibility of this system.The more the Li3AlN2generated,the better the reversibility of this system.The dehydrogenation capacity of AlH_(3)+2LiNH_(2)at the third cycle(3.0 wt%)is higher than that of AlH_(3)+LiNH_(2)(1.2 wt%)due to the generation of more Li3AlN2.The role of AIH_(3)/Al in the AlH_(3)-LiNH_(2)system is to fix the nitrogen into the form of AIN and Li_(3)AlN_(2)and thus suppress the liberation of NH_(3).Therefore,the synergy of AlH_(3)and LiNH_(2)leads to the reversibility of the Li-Al-NH system and the suppression of NH_(3).展开更多
Lithium argyrodites with high ionic conductivity and low cost are considered as one of the most prospective solid electrolytes for all-solid-state lithium batteries.However,the poor chemical stability and compatibilit...Lithium argyrodites with high ionic conductivity and low cost are considered as one of the most prospective solid electrolytes for all-solid-state lithium batteries.However,the poor chemical stability and compatibility with lithium metal limit their application.Herein,Li_(5.4)PS_(4.4)Cl1.4I0.2solid electrolyte with high ionic conductivity of 11.49 m S ccm^(-1)and improved chemical stability is synthesized by iodine doping.An ultra-thin Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)membrane with thickness of 10μm can be obtained by wet coating process,exhibiting a high ionic conductivity of 2.09 mS ccm^(-1)and low areal resistance of 1.17Ωcm^(-2).Moreover,iodine doping could in-situ form LiI at the lithium/electrolyte interface and improve the critical current density of Li_(5.4)PS_(4.4)Cl_(1.6)from 0.8 to 1.35 mA cm^(-2).The resultant LiCoO_(2)/Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)/Li battery shows excellent cycling stability at 1 C,with a reversible specific capacity of 110.1 mA h g^(-1)and a retention of 80.5% after 1000 cycles.In addition,the assembled LiCoO_(2)/Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)membrane/Li pouch cell delivers an initial discharge capacity of 110.4 mA h g^(-1)and 80.5% capacity retention after 100 cycles.展开更多
The efficient recycling of spent lithium iron phosphate(LiFePO_(4),also referred to as LFP)should convert Fe(Ⅱ)to Fe(Ⅲ),which is key to the extraction of Li and separation of Fe and is not well understood.Herein,we ...The efficient recycling of spent lithium iron phosphate(LiFePO_(4),also referred to as LFP)should convert Fe(Ⅱ)to Fe(Ⅲ),which is key to the extraction of Li and separation of Fe and is not well understood.Herein,we systematically study the oxidation of LiFePO_(4)in the air and in the solution containing oxidants such as H_(2)O_(2)and the effect of oxidation on the leaching behaviors of LFP.In the air,O_(2)breaks down the LFP olivine structure at 550℃for 1 h by oxidizing Fe(Ⅱ)to Fe(Ⅲ)in terms of converting LFP to Li_(3)Fe_(2)(PO_(4))_(3)and Fe_(2)O_(3).After that,Li is leached in 0.5 M sulfuric acid solution and is further recycled as Li_(3)PO_(4)with a Li recovery efficiency of 97.48%.Meanwhile,Fe is recovered as FePO_(4)and Fe_(2)O_(3).Compared with H_(2)SO_(4)-H_(2)O_(2),the air oxidation saves H_(2)O_(2)but increases the leaching efficiency of Fe and H_(2)SO_(4)consumption.The discrepancy of Fe leaching efficiency can be attributed to the different leaching mechanisms involving the solid-to-solid and solid-to-liquid-to-solid conversions.Furthermore,the results of the Everbatt model analysis show that the air roasting-H_(2)SO_(4)leaching method has low emission and potentially high income,which is simple and safe.Overall,this work will deepen the understanding of acid leaching of LFP and favorably stimulate the maturation of the LFP recycling technique.展开更多
Silicon is believed to be a critical anode material for approaching the roadmap of lithium-ion batteries due to its high specific capacity. But this aim has been hindered by the quick capacity fading of its electrodes...Silicon is believed to be a critical anode material for approaching the roadmap of lithium-ion batteries due to its high specific capacity. But this aim has been hindered by the quick capacity fading of its electrodes during repeated charge–discharge cycles. In this work, a “soft-hard”double-layer coating has been proposed and carried out on ball-milled silicon particles. It is composed of inside conductive pathway and outside elastic coating, which is achieved by decomposing a conductive graphite layer on the silicon surface and further coating it with a polymer layer.The incorporation of the second elastic coating on the inside carbon coating enables silicon particles strongly interacted with binders, thereby making the electrodes displaying an obviously improved cycling stability. As-obtained double-coated silicon anodes deliver a reversible capacity of 2280 m Ah g^(-1)at the voltage of 0.05–2 V, and maintains over 1763 mAh g^(-1)after 50 cycles. The double-layer coating does not crack after the repeated cycling, critical for the robust performance of the electrodes. In addition, as-obtained silicon particles are mixed with commercial graphite to make actual anodes for lithium-ion batteries. A capacity of 714 mAh g^(-1)has been achieved based on the total mass of the electrodes containing 10 wt.% double-coated silicon particles. Compared with traditional carbon coating or polymeric coating, the double-coating electrodes display a much better performance. Therefore, the double-coating strategy can give inspiration for better design and synthesis of silicon anodes, as well as other battery materials.展开更多
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 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 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.
基金financial support by the National Natural Science Foundation of China(No.52374293)Zhongyuan Science and Technology Innovation Leading Talent Project,China(No.224200510025)+1 种基金the Science and Technology Innovation Program of Hunan Province,China(No.2022RC1123)One of the authors,Hong-bo ZENG,gratefully acknowledges the support from the Natural Sciences and Engineering Research Council of Canada(NSERC)and the Canada Research Chairs Program.
文摘Lithium-ion batteries(LIBs)are the most popular energy storage devices due to their high energy density,high operating voltage,and long cycle life.However,green and effective recycling methods are needed because LIBs contain heavy metals such as Co,Ni,and Mn and organic compounds inside,which seriously threaten human health and the environment.In this work,we review the current status of spent LIB recycling,discuss the traditional pyrometallurgical and hydrometallurgical recovery processes,and summarize the existing short-process recovery technologies such as salt-assisted roasting,flotation processes,and direct recycling.Finally,we analyze the problems and potential research prospects of the current recycling process,and point out that the multidisciplinary integration of recycling will become the mainstream technology for the development of spent LIBs.
基金the Center of Lithium Battery Membrane Materials jointly established by School of Chemistry and Chemical Engineering of Huazhong University of Science and Technology and Shenzhen Senior Technology Material Co.Ltd.,the National Natural Science Foundation of China(52020105012,52303084)the Young Scientists Fund of Natural Science Foundation of Hubei Province(2023AFB220)for the support of this work.
文摘The growing demands for energy storage systems,electric vehicles,and portable electronics have significantly pushed forward the need for safe and reliable lithium batteries.It is essential to design functional separators with improved mechanical and electrochemical characteristics.This review covers the improved mechanical and electrochemical performances as well as the advancements made in the design of separators utilizing a variety of techniques.In terms of electrolyte wettability and adhesion of the coating materials,we provide an overview of the current status of research on coated separators,in situ modified separators,and grafting modified separators,and elaborate additional performance parameters of interest.The characteristics of inorganics coated separators,organic framework coated separators and inorganic-organic coated separators from different fabrication methods are compared.Future directions regarding new modified materials,manufacturing process,quantitative analysis of adhesion and so on are proposed toward next-generation advanced lithium batteries.
基金supported by the Lithium Resources and Lithium Materials Key Laboratory of Sichuan Province(LRMKF202405)the National Natural Science Foundation of China(52402226)+3 种基金the Natural Science Foundation of Sichuan Province(2024NSFSC1016)the Scientific Research Startup Foundation of Chengdu University of Technology(10912-KYQD2023-10240)the opening funding from Key Laboratory of Engineering Dielectrics and Its Application(Harbin University of Science and Technology)(KFM202507,Ministry of Education)the funding provided by the Alexander von Humboldt Foundation。
文摘The properties of electrolytes are critical for fast-charging and stable-cycling applications in lithium metal batteries(LMBs).However,the slow kinetics of Li^(+)transport and desolvation in commercial carbonate electrolytes,cou pled with the formation of unstable solid electrolyte interphases(SEI),exacerbate the degradation of LMB performance at high current densities.Herein,we propose a versatile electrolyte design strategy that incorporates cyclohexyl methyl ether(CME)as a co-solvent to reshape the Li^(+)solvation environment by the steric-hindrance effect of bulky molecules and their competitive coordination with other solvent molecules.Simulation calculations and spectral analysis demonstrate that the addition of CME molecules reduces the involvement of other solvent molecules in the Li solvation sheath and promotes the formation of Li^(+)-PF_(6)^(-)coordination,thereby accelerating Li^(+)transport kinetics.Additionally,this electrolyte composition improves Li^(+)desolvation kinetics and fosters the formation of inorganic-rich SEI,ensuring cycle stability under fast charging.Consequently,the Li‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)battery with the modified electrolyte retains 82% of its initial capacity after 463 cycles at 1 C.Even under the extreme fast-charging condition of 5 C,the battery can maintain 80% capacity retention after 173 cycles.This work provides a promising approach for the development of highperformance LMBs by modulating solvation environment of electrolytes.
文摘The rising need for efficient and sustainable energy storage systems has led to increased interest in the use of advanced electrolytes consisting of deep eutectic solvents(DESs) and ionic liquids(ILs).These electrolytes are appealing candidates for supercapacitors,next-generation lithium-ion batteries,and different energy storage systems because of their special features including non-flammability,low volatility,lowtoxicity,good electrochemical stability,and good thermal and chemical stability.This review explores the advantages of the proposed electrolytes by examining their potential to address the critical challenges in lithium battery technology,including safety concerns,energy density limitations,and operational stability.To achieve this,a comprehensive overview of the lithium salts commonly employed in rechargeable lithium battery electrolytes is presented.Moreover,key physicochemical and functional attributes of ILs and DESs,such as electrochemical stability,ionic conductivity,nonflammability,and viscosity are also discussed with a focus on how these features impact battery performance.The integration of lithium salts with ILs and DESs in modern lithium battery technologies,including lithium-ion(Li-ion) batteries,lithium-oxygen(Li-O_(2)) batteries,and lithium-sulfur(Li-S) batteries,are further examined in the study.Various electrochemical performance metrics including cycling stability,charge/discharge profiles,retention capacity and battery's couiombic efficiency(CE) are also analyzed for the above-mentioned systems.By summarizing recent advances and challenges,this review also highlights the potential of electrolytes consisting of DESs and ILs to enhance energy density,durability,and safety in future energy storage applications.Additionally future research directions,including the molecular optimization of ILs and DESs,optimizing lithium salt compositions,and developing scalable synthesis methods to accelerate their practical implementation in next-generation energy storage applications are also explored.
基金supported by the Australian Research Council Centre of Excellence in Optical Microcombs for Breakthrough Science COMBS(CE230100006)the Australian Research Council grants DP220100488 and DE230100964funded by the Australian Government.
文摘Lithium niobate(LN)has remained at the forefront of academic research and industrial applications due to its rich material properties,which include second-order nonlinear optic,electro-optic,and piezoelectric properties.A further aspect of LN’s versatility stems from the ability to engineer ferroelectric domains with micro and even nano-scale precision in LN,which provides an additional degree of freedom to design acoustic and optical devices with improved performance and is only possible in a handful of other materials.In this review paper,we provide an overview of the domain engineering techniques developed for LN,their principles,and the typical domain size and pattern uniformity they provide,which is important for devices that require high-resolution domain patterns with good reproducibility.It also highlights each technique's benefits,limitations,and adaptability for an application,along with possible improvements and future advancement prospects.Further,the review provides a brief overview of domain visualization methods,which is crucial to gain insights into domain quality/shape and explores the adaptability of the proposed domain engineering methodologies for the emerging thin-film lithium niobate on an insulator platform,which creates opportunities for developing the next generation of compact and scalable photonic integrated circuits and high frequency acoustic devices.
基金the Natural Sci-ence Foundation of Shandong Province(Nos.ZR2022QE014,ZR2021QH237)the Guangdong Provincial Key Laboratory of Elec-tronic Functional Materials and Devices(No.EFMD2022017M)+1 种基金the National Natural Science Foundation of China(Grant Nos.52401221,51971120,U1902221)the Medical StaffScience and Technology Plan of Shandong Province(No.SDYWZGKCJH2022073).
文摘Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature.However,the use of Succinonitrile is limited due to its corrosion of Li metal.Herein,we report a solid polymer electrolyte with high ionic conductivity(2.17×10^(−3)S cm^(−1),35°C)enhanced by Ti_(3)C_(2)T_(x).Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti_(3)C_(2)T_(x).Meanwhile,the coordination environment of Li^(+)is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte,resulting in efficient Li^(+)conduction.Furthermore,the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti_(3)C_(2)T_(x)to suppress the growth of Li dendrites.Therefore,Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28°C.LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g^(−1)with a capacity retention of 99.3%after 300 cycles.This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple,feasible,and scalable strategy for high-performance Li metal batteries.
基金supported by the National Natural Science Foundation of China(22369011)the Gansu Key Research and Development Program(23YFGA0053 and 24YFGA025)the Hongliu Outstanding Youth Talent Support Program of Lanzhou University of Technology and Postgraduate research exploration project of Lanzhou University of Technology(256017)。
文摘The swelling behavior and stability in solid electrolyte interphase(SEI)have been proved to determine the battery cycle life.A high swollen,unstable SEI shows a high permeability to electrolyte,which results in the rapid battery performance degradation.Here,we customize two SEIs with different spatial structures(bilayer and mosaic)by simply regulating the proportion of additive fluoroethylene carbonate.Surprisingly,due to the uniform distribution of dense inorganic nano-crystals in the inner,the bilayer SEI exhibits low-swelling and excellent mechanical properties,so the undesirable side reactions of the electrolyte are effectively suppressed.In addition,we put forward the growth rate of swelling ratio(GSR)as a key indicator to reveal the swelling change in SEI.The GSR of bilayer SEI merely increases from1.73 to 3.16 after the 300th cycle,which enables the corresponding graphite‖Li battery to achieve longer cycle stability.The capacity retention is improved by 47.5% after 300 cycles at 0.5 C.The correlation among SEI spatial structure,swelling behavior,and battery performance provides a new direction for electrolyte optimization and interphase structure design of high energy density batteries.
基金supported by Natural Science Foundation of Shandong Province(Nos.ZR2022YQ42,ZR2021JQ15,ZR2021QE011,ZR2021ZD20,2022GJJLJRC-01)Innovative Team Project of Jinan(No.2021GXRC019)the National Natural Science Foundation of China(Nos.52022037,52202366).
文摘In contrast to research on active sites in nanomaterials,lithium tantalate single crystals,known for their exceptional optical properties and long-range ordered lattice structure,present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry.Typically,the isotropy of a specific facet provides a perfect support for studying heteroatom doping.Herein,this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals.The presence of iron not only modifies the electronic structure of lithium tantalate,improving its light absorption capacity,but also functions as an active site for the nitrogen adsorption and activation.The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95μg cm^(−2)h^(−1),which is three times higher than that of undoped lithium tantalate.The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating.This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.
基金financially supported by the National Natural Science Foundation of China(52172245)the Key Scientific and Technological Innovation Project of Shandong(2023CXGC010302)the Qingdao Flexible Materials Precision Die-cutting Technology Innovation Center。
文摘In lithium-sulfur batteries(LSBs),the limited utilization of sulfur and the sluggish kinetics of redox reaction significantly hinder their electrochemical performance,especially under high rates and high sulfur loadings.Here,we propose a novel separator structure with an interlayer composed of a vermiculite nanosheet combined with Ketjen Black(VMT@KB)for LSBs,facilitating efficient adsorption and rapid catalytic conversion toward lithium polysulfides(LiPSs).The VMT@KB nanosheets with an electrical double-layer structure and electronic conductivity are obtained through a high-temperature peeling process and Li^(+)exchange treatment in LiCl solution,followed by a mechanical combination process with KB.The results demonstrate that incorporating VMT@KB as an interlayer on a conventional separator enhances the conductivity and limits the LiPSs in the cathode region.The Li-S cell with VMT@KB interlayer shows satisfactory cycle and rate performance,especially in high sulfur loading.It exhibits a remarkable initial discharge capacity of 1225 mAh g^(-1)at 0.5 C and maintains a capacity of 816 mAh g^(-1)after 500 cycles.Besides,the discharge capacity remains 462 mAh g^(-1)even at 6 C.Moreover,the cell with high sulfur loading(8.2 mg cm^(-2))enables stable cycling for 100 cycles at 0.1 C with a discharge capacity of over1000 mAh g^(-1).
基金financially supported by the National Natural Science Foundation of China(Nos.22379030,52001079,52261038)the Science and Technology Department of Guangxi Zhuang Autonomous(Nos.2024JJG160001,GuiKeAD21238022)the Innovation Project of Guangxi Graduate Education(No.YCBZ2023011)
文摘As a hydrogen storage material,both AlH_(3)and LiNH_(2)possess a high hydrogen capacity.However,the dehydrogenated AlH_(3)can hardly absorb hydrogen under normal conditions,while LiNH_(2)will generate NH_(3)rather than H_(2)upon decomposition.In this work,we report thatthe combination of AlH_(3)and LiNH_(2)through simple ball milling leads to partial reversibility of the AlH_(3)-LiNH_(2)system and the suppression of NH_(3)liberation.The negatively charged H^(δ-)in AlH_(3)will react with the positively charged H^(δ+)in LiNH_(2)through a redox reaction to form Li_(2)NH,AlN,and H_(2)at 120-170℃.After dehydrogenation at above 270℃,Li_(3)AlN_(2)is generated,which is crucial for the reversibility of this system.The more the Li3AlN2generated,the better the reversibility of this system.The dehydrogenation capacity of AlH_(3)+2LiNH_(2)at the third cycle(3.0 wt%)is higher than that of AlH_(3)+LiNH_(2)(1.2 wt%)due to the generation of more Li3AlN2.The role of AIH_(3)/Al in the AlH_(3)-LiNH_(2)system is to fix the nitrogen into the form of AIN and Li_(3)AlN_(2)and thus suppress the liberation of NH_(3).Therefore,the synergy of AlH_(3)and LiNH_(2)leads to the reversibility of the Li-Al-NH system and the suppression of NH_(3).
基金National Key R&D Program of China (grant no. 2022YFB3807700)National Natural Science Foundation of China (Grant No. U1964205, U21A2075, 52172253,52102326, 52250610214, 22309194, 52372244)+4 种基金Ningbo S&T Innovation 2025 Major Special Programme (Grant No.2019B10044, 2021Z122, 2023Z106)Zhejiang Provincial Key R&D Program of China (Grant No. 2022C01072, 2024C01095)Jiangsu Provincial S&T Innovation Special Programme for carbon peak and carbon neutrality (Grant No. BE2022007)Baima Lake Laboratory Joint Funds of the Zhejiang Provincial Natural Science Foundation of China (LBMHD24E020001)Youth Innovation Promotion Association CAS (Y2021080)。
文摘Lithium argyrodites with high ionic conductivity and low cost are considered as one of the most prospective solid electrolytes for all-solid-state lithium batteries.However,the poor chemical stability and compatibility with lithium metal limit their application.Herein,Li_(5.4)PS_(4.4)Cl1.4I0.2solid electrolyte with high ionic conductivity of 11.49 m S ccm^(-1)and improved chemical stability is synthesized by iodine doping.An ultra-thin Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)membrane with thickness of 10μm can be obtained by wet coating process,exhibiting a high ionic conductivity of 2.09 mS ccm^(-1)and low areal resistance of 1.17Ωcm^(-2).Moreover,iodine doping could in-situ form LiI at the lithium/electrolyte interface and improve the critical current density of Li_(5.4)PS_(4.4)Cl_(1.6)from 0.8 to 1.35 mA cm^(-2).The resultant LiCoO_(2)/Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)/Li battery shows excellent cycling stability at 1 C,with a reversible specific capacity of 110.1 mA h g^(-1)and a retention of 80.5% after 1000 cycles.In addition,the assembled LiCoO_(2)/Li_(5.4)PS_(4.4)Cl_(1.4)I_(0.2)membrane/Li pouch cell delivers an initial discharge capacity of 110.4 mA h g^(-1)and 80.5% capacity retention after 100 cycles.
基金supported by the Chilwee Group(No.CWDY-ZH-YJY-202101-001)the Fundamental Research Funds for the Central Universities(No.2042023kf0214)the Starting Funding from Wuhan University.
文摘The efficient recycling of spent lithium iron phosphate(LiFePO_(4),also referred to as LFP)should convert Fe(Ⅱ)to Fe(Ⅲ),which is key to the extraction of Li and separation of Fe and is not well understood.Herein,we systematically study the oxidation of LiFePO_(4)in the air and in the solution containing oxidants such as H_(2)O_(2)and the effect of oxidation on the leaching behaviors of LFP.In the air,O_(2)breaks down the LFP olivine structure at 550℃for 1 h by oxidizing Fe(Ⅱ)to Fe(Ⅲ)in terms of converting LFP to Li_(3)Fe_(2)(PO_(4))_(3)and Fe_(2)O_(3).After that,Li is leached in 0.5 M sulfuric acid solution and is further recycled as Li_(3)PO_(4)with a Li recovery efficiency of 97.48%.Meanwhile,Fe is recovered as FePO_(4)and Fe_(2)O_(3).Compared with H_(2)SO_(4)-H_(2)O_(2),the air oxidation saves H_(2)O_(2)but increases the leaching efficiency of Fe and H_(2)SO_(4)consumption.The discrepancy of Fe leaching efficiency can be attributed to the different leaching mechanisms involving the solid-to-solid and solid-to-liquid-to-solid conversions.Furthermore,the results of the Everbatt model analysis show that the air roasting-H_(2)SO_(4)leaching method has low emission and potentially high income,which is simple and safe.Overall,this work will deepen the understanding of acid leaching of LFP and favorably stimulate the maturation of the LFP recycling technique.
基金supported by the National Natural Science Foundation of China (No. 22008256)。
文摘Silicon is believed to be a critical anode material for approaching the roadmap of lithium-ion batteries due to its high specific capacity. But this aim has been hindered by the quick capacity fading of its electrodes during repeated charge–discharge cycles. In this work, a “soft-hard”double-layer coating has been proposed and carried out on ball-milled silicon particles. It is composed of inside conductive pathway and outside elastic coating, which is achieved by decomposing a conductive graphite layer on the silicon surface and further coating it with a polymer layer.The incorporation of the second elastic coating on the inside carbon coating enables silicon particles strongly interacted with binders, thereby making the electrodes displaying an obviously improved cycling stability. As-obtained double-coated silicon anodes deliver a reversible capacity of 2280 m Ah g^(-1)at the voltage of 0.05–2 V, and maintains over 1763 mAh g^(-1)after 50 cycles. The double-layer coating does not crack after the repeated cycling, critical for the robust performance of the electrodes. In addition, as-obtained silicon particles are mixed with commercial graphite to make actual anodes for lithium-ion batteries. A capacity of 714 mAh g^(-1)has been achieved based on the total mass of the electrodes containing 10 wt.% double-coated silicon particles. Compared with traditional carbon coating or polymeric coating, the double-coating electrodes display a much better performance. Therefore, the double-coating strategy can give inspiration for better design and synthesis of silicon anodes, as well as other battery materials.
