Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of pro...Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe_(2)O_(3)-doped NiSO_(4)/Al_(2)O_(3) catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst demonstrates an enhanced reaction rate(48.5 mmol_(C3)/(g_(cat).·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO_(4)/Al_(2)O_(3) catalyst(C9:~24.1%).The incorporation of Fe_(2)O_(3) modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.展开更多
Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dy...Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dynamic evolution of 2D/3D interfaces under external stimuli such as thermal stress and long-term illumination significantly impacts device performance.In this study,we systematically investigate the role of intermolecular interactions in governing ion migration at 2D/3D interfaces by physically stacking three 2D perovskite,(BA)_(2)PbI_(4)(BA=butylammonium),(PEA)_(2)PbI_(4)(PEA=phenethylammonium),and(BDA)PbI_(4)(BDA=1,4-butane diammonium),with 3D perovskite-MAPbI_(3)(MA=methylammonium),followed by thermal annealing;and subsequent characterization was carried out using ultraviolet-visible(UV-Vis)absorption and femtosecond-transient absorption(fs-TA)spectra.Our findings reveal that small MA^(+)ions migrate from the 3D perovskite into the 2D perovskites,forming quasi-2D perovskites and introducing new decay pathways,while BA^(+)and PEA^(+)ions back-incorporate into the 3D lattice,causing a slight blue shift of 2-3 nm in exciton peaks.Notably,no significant ion migration is observed at the(BDA)PbI_(4)/MAPbI_(3)interface due to strong hydrogen bonds,demonstrating superior robustness against ion movement.Further analysis indicates that the stability of 2D/3D interface is governed by intermolecular interactions,following the order:hydrogen bonds>π-πstacking>van der Waals forces.These findings highlight the pivotal role of molecular interactions in modulating ion migration at 2D/3D interfaces and provide a clear design principle for constructing stable 2D/3D heterojunctions by selecting diammonium cations with robust hydrogen bonds,offering key insights for the rational design of stable perovskite interfaces.展开更多
Interfacial properties between perovskite layers and metal electrodes play a crucial role in the device performance and the long-term stability of perovskite solar cells.Here,we report a comprehensive study of the int...Interfacial properties between perovskite layers and metal electrodes play a crucial role in the device performance and the long-term stability of perovskite solar cells.Here,we report a comprehensive study of the interfacial degradation and ion migration at the interface between CH3NH3PbI3 perovskite layer and Ag electrode.Using in situ photoemission spectroscopy measurements,we found that the Ag electrode could induce the degradation of perovskite layers,leading to the formation of PbI2 and AgI species and the reduction of Pb^2+ions to metallic Pb species at the interface.The unconventional enhancement of the intensities of I 3d spectra provides direct experimental evidences for the migration of iodide ions from CH3NH3PbI3 subsurface to Ag electrode.Moreover,the contact of Ag electrode and perovskite layers induces an interfacial dipole of 0.3 eV at CH3NH3PbI3/Ag interfaces,which may further facilitate iodide ion diffusion,resulting in the decomposition of perovskite layers and the corrosion of Ag electrode.展开更多
Bauxite residue,a highly saline solid waste produced from digestion of bauxite for alumina production,is hazardous to the environment and restricts vegetation establishment in bauxite residue disposal areas.A novel wa...Bauxite residue,a highly saline solid waste produced from digestion of bauxite for alumina production,is hazardous to the environment and restricts vegetation establishment in bauxite residue disposal areas.A novel water leaching process proposed here was used to investigate the dynamic migration and vertical distribution of saline ions in bauxite residue.The results show that water leaching significantly reduced the salinity of bauxite residue,leaching both saline cations Na+,K+,Ca2+and anions CO32-,SO42-,HCO3-.Na+and K+migrated from 40-50 to 20-30 cm of the column,presenting a high migration capacity.The migration capacity of Ca2+was lower and accumulated at 30-40 cm of the column.CO32-initially distributed at 20-30 cm of the column,subsequently transported to 30-40 cm of the column,and finally returned to 20-30 cm of the column along with evaporation.SO42-was originally distributed at 40-50 cm,but finally migrated to 20-30 cm of the column.Nevertheless,HCO3-remained at the bottom of the column,and its migratory was less affected by evaporation.展开更多
The traditional von Neumann architecture faces inherent limitations due to the separation of memory and computa-tion,leading to high energy consumption,significant latency,and reduced operational efficiency.Neuromorph...The traditional von Neumann architecture faces inherent limitations due to the separation of memory and computa-tion,leading to high energy consumption,significant latency,and reduced operational efficiency.Neuromorphic computing,inspired by the architecture of the human brain,offers a promising alternative by integrating memory and computational func-tions,enabling parallel,high-speed,and energy-efficient information processing.Among various neuromorphic technologies,ion-modulated optoelectronic devices have garnered attention due to their excellent ionic tunability and the availability of multi-dimensional control strategies.This review provides a comprehensive overview of recent progress in ion-modulation optoelec-tronic neuromorphic devices.It elucidates the key mechanisms underlying ionic modulation of light fields,including ion migra-tion dynamics and capture and release of charge through ions.Furthermore,the synthesis of active materials and the proper-ties of these devices are analyzed in detail.The review also highlights the application of ion-modulation optoelectronic devices in artificial vision systems,neuromorphic computing,and other bionic fields.Finally,the existing challenges and future direc-tions for the development of optoelectronic neuromorphic devices are discussed,providing critical insights for advancing this promising field.展开更多
Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometal...Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometallic glycinate hybrid perovskitoid Pb_(2)CuGly_(2)X_(4)(Gly=-O_(2)C-CH_(2)-NH_(2);X=Cl,Br)single crystals(SCs),in which the adjacent lead halide layers are linked by large-sized Cu(Gly)_(2)pillars,are synthesized in water.The Cu(Gly)_(2)pillars in combination with face-/edge-shared inorganic skeleton are found able to synergistically suppress the ion migration,delivering a high ion migration activation energy(Ea)of 1.06 eV.The Pb_(2)CuGly_(2)Cl_(4)SC X-ray detector displays extremely low dark current drift of 1.20×10^(-9)nA mm^(-1)s^(-1)V^(-1)under high electric field(120 V mm^(-1))and continuous X-ray irradiation(2.86 Gy),and a high sensitivity of 9,250μC Gy^(-1)cm^(-2)is also achieved.More excitingly,the Pb_(2)CuGly_(2)Cl_(4)nanocrystal can be easily dispersed in water and directly blade-coated on thin-film transistor(TFT)array substrate,and the obtained Pb_(2)CuGly_(2)Cl_(4)-based TFT array detector offers an X-ray imaging capability with spatial resolution of 2.2 lp mm^(-1).展开更多
Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,ramp...Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.展开更多
The past decade has witnessed the rapid increasement in power conversion efficiency of perovskite solar cells(PSCs).However,serious ion migration hampers their operational stability.Although dopants composed of varied...The past decade has witnessed the rapid increasement in power conversion efficiency of perovskite solar cells(PSCs).However,serious ion migration hampers their operational stability.Although dopants composed of varied cations and anions are introduced into perovskite to suppress ion migration,the impact of cations or anions is not individually explored,which hinders the evaluation of different cations and further application of doping strategy.Here we report that a special group of sulfonic anions(like CF_(3)SO_(3)^(-))successfully introduce alkaline earth ions(like Ca^(2+))into perovskite lattice compared to its halide counterparts.Furthermore,with effective crystallization regulation and defect passivation of sulfonic anions,perovskite with Ca(CF_(3)SO_(3))_(2)shows reduced PbI2 residue and metallic Pb0 defects;thereby,corresponding PSCs show an enhanced PCE of 24.95%.Finally by comparing the properties of perovskite with Ca(CF_(3)SO_(3))_(2)and FACF_(3)SO_(3),we found that doped Ca^(2+)significantly suppressed halide migration with an activation energy of 1.246 eV which accounts for the improved operational stability of Ca(CF_(3)SO_(3))_(2-)doped PSCs,while no obvious impact of Ca^(2+)on trap density is observed.Combining the benefits of cations and anions,this study presents an effective method to decouple the effects of cations and anions and fabricate efficient and stable PSCs.展开更多
Metal halide perovskites are emerging as the most promising candidate for the next-generation Photovoltaics(PV)materials,due to their superior optoelectronic properties and low cost.However,the resulting Perovskite so...Metal halide perovskites are emerging as the most promising candidate for the next-generation Photovoltaics(PV)materials,due to their superior optoelectronic properties and low cost.However,the resulting Perovskite solar cells(PSCs)suffer from poor stability.In particular,the temperature and light activated ionic defects within the perovskite lattice,as well as electric-field-induced migration of ionic defects,make the PSCs unstable at operating condition,even with device encapsulation.There is no doubt that the investigation of ion migration is crucial for the development of PSCs with high intrinsic stability.In this review,we first briefly introduce the origin and pathways of ion migration,and also the essential characterization methods to identify ion migration.Next,we discuss the impact of ion migration on the perovskite films and cells with respect to photoelectric properties and stability.Then,several representative strategies to suppress ion migration are systematically summarized in the context of composition engineering,additive engineering and interface engineering,with an in-depth understanding on the underlying mechanisms which may provide more clues for further fabrication of PSCs with improved stability.Finally,a perspective with some suggestion on future research directions and chemical approaches are provided to alleviate ion migration in perovskite materials and the entire devices.展开更多
Metal halide perovskites have recently emerged as promising candidates for the next generation of X-ray detectors due to their excellent optoelectronic properties.Especially,two-dimensional(2D)perovskites afford many ...Metal halide perovskites have recently emerged as promising candidates for the next generation of X-ray detectors due to their excellent optoelectronic properties.Especially,two-dimensional(2D)perovskites afford many distinct properties,including remarkable structural diversity,high generation energy,and balanced large exciton binding energy.With the advantages of 2D materials and perovskites,it successfully reduces the decomposition and phase transition of perovskite and effectively suppresses ion migration.Meanwhile,the existence of a high hydrophobic spacer can block water molecules,thus making 2D perovskite obtain excellent stability.All of these advantages have attracted much attention in the field of X-ray detection.This review introduces the classification of 2D halide perovskites,summarizes the synthesis technology and performance characteristics of 2D perovskite X-ray direct detector,and briefly discusses the application of 2D perovskite in scintillators.Finally,this review also emphasizes the key challenges faced by 2D perovskite X-ray detectors in practical application and presents our views on its future development.展开更多
Introduction of vacancies is a widely practiced method to improve the performance of active materials in differentenergy systems,such as secondary batteries,electrocatalysis,and supercapacitors.Because vacancies can g...Introduction of vacancies is a widely practiced method to improve the performance of active materials in differentenergy systems,such as secondary batteries,electrocatalysis,and supercapacitors.Because vacancies can generateabundant localized electrons and unsaturated cations,the incorporation of vacancies will significantly improvethe electrical conductivity,ion migration,and provides additional active sites of energy storage materials.Thisarticle systematically reviews different methods to generate oxygen,nitrogen,or selenium vacancies,and techniques to characterize these vacancies.We summarize the specific roles that vacancies play for the active materials in each type of energy storage devices.Additionally,we provide insights into the research progress andchallenges associated with the future development of vacancies technology in various energy storage systems.展开更多
Hybrid halide perovskites have great potential for applications in optoelectronic devices.However,the typical ion migration in perovskite could lead to the non-repeatability of electrical measurement,instability of ma...Hybrid halide perovskites have great potential for applications in optoelectronic devices.However,the typical ion migration in perovskite could lead to the non-repeatability of electrical measurement,instability of material,and degradation of device performance.The basic current–voltage behavior of perovskite materials is intricate due to the mixed electronic–ionic characteristic,which is still poorly understood in these semiconductors.Developing novel measurement schematic is a promising solution to obtain the intrinsic electrical performance without the interference of ion migration.Herein,we explore the pulse-voltage(PV)method on methylammonium lead tribromide single crystals to protect the device from the ion migration.A guideline is summarized through the analysis of measurement history and condition parameters.The influence of the ion migration on current–voltage measurement,such as repeatability and hysteresis loop,is under controlled.An application of the PV method is demonstrated on the activation energy of conductivity.The abruption of activation energy still exists near the phase transition temperature despite the ion migration is excluded by the PV method,introducing new physical insight on the current–voltage behavior of perovskite materials.The guideline on PV method will be beneficial for measuring halide perovskite materials and developing optoelectronic applications with new technique schematic.展开更多
Benefiting from the excellent properties such as high photoluminescence quantum yield(PLQY), wide gamut range,and narrow emission linewidth, as well as low-temperature processability, metal halide perovskite quantum d...Benefiting from the excellent properties such as high photoluminescence quantum yield(PLQY), wide gamut range,and narrow emission linewidth, as well as low-temperature processability, metal halide perovskite quantum dots(QDs)have attracted wide attention from researchers. Despite tremendous progress has been made during the past several years,the commercialization of perovskite QDs-based LEDs(PeQLEDs) is still plagued by the instability. The ion migration in halide perovskites is recognized as the key factor causing the performance degradation of PeQLEDs. In this review, the elements species of ion migration, the effects of ion migration on device performance and stability, and effective strategies to hinder/mitigate ion migration in PeQLEDs are successively discussed. Finally, the forward insights on the future research are highlighted.展开更多
The device preconditioning dependent hysteresis and the consequential performance degradation hinder the actual performance and stability of the perovskite solar cells. Ion migration and charge trapping in the perovsk...The device preconditioning dependent hysteresis and the consequential performance degradation hinder the actual performance and stability of the perovskite solar cells. Ion migration and charge trapping in the perovskite with large contribution from grain boundaries are the most common interpretations for the hysteresis. Yet, the high performing devices often include intermediate hole and electron transporting layers, which can further complicate the dynamical process in the device. Here, by using Kelvin Probe Force Microscopy and Confocal Photoluminescence Microscopy, we elucidate the impact of chargetransporting layers and excess MAI on the spatial and temporal variations of the photovoltage on the MAPbI3-based solar cells. By studying the devices layer by layer, we found that the light-induced ion migration occurs predominantly in the presence of an imbalanced charge extraction in the solar cells, and the charge transporting layers play crucial role in suppressing it. Careful selection and processing of the electron and hole-transporting materials are thus essential for making perovskite solar cells free from the ion migration effect.展开更多
In the past 10 years,perovskite solar cells(PSCs)have undergone extremely rapid development,with a record certified power conversion efficiency(PCE)of 26.7%,which is very close to the limit efficiency.However,the inhe...In the past 10 years,perovskite solar cells(PSCs)have undergone extremely rapid development,with a record certified power conversion efficiency(PCE)of 26.7%,which is very close to the limit efficiency.However,the inherent instability caused by ion migration impedes the realization of long-term operationally stable PSCs.In this review,the types and mechanisms of ion migration occurring in various functional layers of negative-intrinsic-positive(n-i-p)PSCs are summarized.Additionally,methods of suppressing ion migration are systematically discussed.Finally,the prospects of current challenges and future development directions are proposed to advance the achievement of high-performance regular PSCs with high stability and PCE.展开更多
Halide perovskites is a recently emerged platform for the creation of efficient memristors.In turn,single-crystal inorganic perovskite would be new low-cost and flexible memory devices because of their excellent resis...Halide perovskites is a recently emerged platform for the creation of efficient memristors.In turn,single-crystal inorganic perovskite would be new low-cost and flexible memory devices because of their excellent resistive switching(RS)properties,without risk of chemical and mechanical stress-generated degradation,compared with the operational instability of general thin-film perovskite memristors.Moreover,miniaturization of perovskite memristors would be useful for creating high-density memory devices.Here we demonstrate the smallest CsPbBr3 perovskite nanomemristor with volatile unipolar RS characteristics which depends on the size of a single-crystal as a resistive layer due to its overall structural stability and low sensitivity to atmosphere conditions that helps to keep the stable RS switching over 1500 times with the lowest consumption power of 70 nW.To better understand the RS mechanism,we provide a comprehensive simulation of the evolution of mixed ionic-electronic charge carriers under current-voltage(I-V)tests using a one-dimensional drift-diffusion model.Because of the nonreactive nature of the contacts,the main mechanism of resistive state switching is potential barrier modulation of the Schottky contacts through the accumulation of migrating ions at the interfaces.Our findings pave the way for ultracompact memristors as well as shed light on RS mechanism in non-filamentary perovskitebased memory devices.展开更多
Perovskite quantum dot light-emitting diodes(Pe-QLEDs)have shown immense application potential in display and lighting fields due to their narrow full-width at half maximum(FWHM)and high photoluminescence quantum yiel...Perovskite quantum dot light-emitting diodes(Pe-QLEDs)have shown immense application potential in display and lighting fields due to their narrow full-width at half maximum(FWHM)and high photoluminescence quantum yield(PLQY).Despite significant advancements in their performance,challenges such as defects and ion migration still hinder their long-term stability and operational efficiency.To address these issues,various optimization strategies,including ligand engineering,interface passivation,and self-assembly strategy,are being actively researched.This review focuses on the synthesis methods,challenges and optimization of perovskite quantum dots,which are critical for the commercialization and large-scale production of high-performance and stable Pe-QLEDs.展开更多
Through strategies such as process optimization,solvent selection,and component tuning,the crystallization of perovskite materials has been effectively controlled,enabling perovskite solar cells(PSCs)to achieve over 2...Through strategies such as process optimization,solvent selection,and component tuning,the crystallization of perovskite materials has been effectively controlled,enabling perovskite solar cells(PSCs)to achieve over 25%power conversion efficiency(PCE).However,as PCE continues to improve,interfacial issues within the devices have emerged as critical bottlenecks,hindering further performance enhancements.Recently,interfacial engineering has driven transformative progress,pushing PCEs to nearly 27%.Building upon these developments,this review first summarizes the pivotal role of interfacial modifications in elevating device performance and then,as a starting point,provides a comprehensive overview of recent advancements in normal,inverted,and tandem structure devices.Finally,based on the current progress of PSCs,preliminary perspectives on future directions are presented.展开更多
Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,th...Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.展开更多
文摘Propylene,a readily accessible and economically viable light olefin,has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes.The distribution of products is profoundly influenced by the catalyst structure.In this study,Fe_(2)O_(3)-doped NiSO_(4)/Al_(2)O_(3) catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions.Significantly,the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst demonstrates an enhanced reaction rate(48.5 mmol_(C3)/(g_(cat).·h)),alongside a high yield of C9(~32.2%),significantly surpassing the performance of the NiSO_(4)/Al_(2)O_(3) catalyst(C9:~24.1%).The incorporation of Fe_(2)O_(3) modifies the migration process of sulfate ions,altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution.This shift is primarily ascribed to the heightened energy barrier for theβ-H elimination reaction in the C6 alkyl intermediates on the doped catalyst,further promoting polymerization to yield a greater quantity of Type II C9.Furthermore,the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed.It is noteworthy that the 0.25Fe_(2)O_(3)-NiSO_(4)/Al_(2)O_(3) catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene.These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.
基金supported by the Beijing Natural Science Foundation(2252013)the National Natural Science Foundation of China(U2230203,12404491)+1 种基金the Beijing National Laboratory for Condensed Matter Physics(2024BNLCMPKF008)the Fundamental Research Funds for Central Universities.
文摘Passivating the surface defects of three-dimensional(3D)perovskite layers with two-dimensional(2D)perovskites is a critical strategy for achieving high efficiency and stability in perovskite solar cells.However,the dynamic evolution of 2D/3D interfaces under external stimuli such as thermal stress and long-term illumination significantly impacts device performance.In this study,we systematically investigate the role of intermolecular interactions in governing ion migration at 2D/3D interfaces by physically stacking three 2D perovskite,(BA)_(2)PbI_(4)(BA=butylammonium),(PEA)_(2)PbI_(4)(PEA=phenethylammonium),and(BDA)PbI_(4)(BDA=1,4-butane diammonium),with 3D perovskite-MAPbI_(3)(MA=methylammonium),followed by thermal annealing;and subsequent characterization was carried out using ultraviolet-visible(UV-Vis)absorption and femtosecond-transient absorption(fs-TA)spectra.Our findings reveal that small MA^(+)ions migrate from the 3D perovskite into the 2D perovskites,forming quasi-2D perovskites and introducing new decay pathways,while BA^(+)and PEA^(+)ions back-incorporate into the 3D lattice,causing a slight blue shift of 2-3 nm in exciton peaks.Notably,no significant ion migration is observed at the(BDA)PbI_(4)/MAPbI_(3)interface due to strong hydrogen bonds,demonstrating superior robustness against ion movement.Further analysis indicates that the stability of 2D/3D interface is governed by intermolecular interactions,following the order:hydrogen bonds>π-πstacking>van der Waals forces.These findings highlight the pivotal role of molecular interactions in modulating ion migration at 2D/3D interfaces and provide a clear design principle for constructing stable 2D/3D heterojunctions by selecting diammonium cations with robust hydrogen bonds,offering key insights for the rational design of stable perovskite interfaces.
基金supported by the National Natural Science Foundation of China (No.21473178, No.21773222, No.21503203)the National Key R&D program of China (2017YFA0403403)+1 种基金the Key Program of Research and Development of Hefei Science Center of CAS(2017HSC-KPRD001)the Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Interfacial properties between perovskite layers and metal electrodes play a crucial role in the device performance and the long-term stability of perovskite solar cells.Here,we report a comprehensive study of the interfacial degradation and ion migration at the interface between CH3NH3PbI3 perovskite layer and Ag electrode.Using in situ photoemission spectroscopy measurements,we found that the Ag electrode could induce the degradation of perovskite layers,leading to the formation of PbI2 and AgI species and the reduction of Pb^2+ions to metallic Pb species at the interface.The unconventional enhancement of the intensities of I 3d spectra provides direct experimental evidences for the migration of iodide ions from CH3NH3PbI3 subsurface to Ag electrode.Moreover,the contact of Ag electrode and perovskite layers induces an interfacial dipole of 0.3 eV at CH3NH3PbI3/Ag interfaces,which may further facilitate iodide ion diffusion,resulting in the decomposition of perovskite layers and the corrosion of Ag electrode.
基金Project(41371475)supported by the National Natural Science Foundation of ChinaProject(201509048)supported by the Environmental Protection’s Special Scientific Research for Chinese Public Welfare Industry
文摘Bauxite residue,a highly saline solid waste produced from digestion of bauxite for alumina production,is hazardous to the environment and restricts vegetation establishment in bauxite residue disposal areas.A novel water leaching process proposed here was used to investigate the dynamic migration and vertical distribution of saline ions in bauxite residue.The results show that water leaching significantly reduced the salinity of bauxite residue,leaching both saline cations Na+,K+,Ca2+and anions CO32-,SO42-,HCO3-.Na+and K+migrated from 40-50 to 20-30 cm of the column,presenting a high migration capacity.The migration capacity of Ca2+was lower and accumulated at 30-40 cm of the column.CO32-initially distributed at 20-30 cm of the column,subsequently transported to 30-40 cm of the column,and finally returned to 20-30 cm of the column along with evaporation.SO42-was originally distributed at 40-50 cm,but finally migrated to 20-30 cm of the column.Nevertheless,HCO3-remained at the bottom of the column,and its migratory was less affected by evaporation.
基金supported by National Natural Science Foundation of China(62174164,U23A20568,and U22A2075)National Key Research and Development Project(2021YFA1202600)+2 种基金Talent Plan of Shanghai Branch,Chinese Academy of Sciences(CASSHB-QNPD-2023-022)Ningbo Technology Project(2022A-007-C)Ningbo Key Research and Development Project(2023Z021).
文摘The traditional von Neumann architecture faces inherent limitations due to the separation of memory and computa-tion,leading to high energy consumption,significant latency,and reduced operational efficiency.Neuromorphic computing,inspired by the architecture of the human brain,offers a promising alternative by integrating memory and computational func-tions,enabling parallel,high-speed,and energy-efficient information processing.Among various neuromorphic technologies,ion-modulated optoelectronic devices have garnered attention due to their excellent ionic tunability and the availability of multi-dimensional control strategies.This review provides a comprehensive overview of recent progress in ion-modulation optoelec-tronic neuromorphic devices.It elucidates the key mechanisms underlying ionic modulation of light fields,including ion migra-tion dynamics and capture and release of charge through ions.Furthermore,the synthesis of active materials and the proper-ties of these devices are analyzed in detail.The review also highlights the application of ion-modulation optoelectronic devices in artificial vision systems,neuromorphic computing,and other bionic fields.Finally,the existing challenges and future direc-tions for the development of optoelectronic neuromorphic devices are discussed,providing critical insights for advancing this promising field.
基金financially supported by the National Natural Science Foundation of China (62004089,62374053, 62474187 and 12235006)the Special Zone Support Program for Outstanding Talents of Henan University+4 种基金the Shenzhen Basic Research Program (JCYJ20220818101612027)the Guangdong Basic and Applied Basic Research Foundation (2024A1515012494)the Henan Province Postdoctoral Science Foundation (J23029Y)the Natural Science Foundation of Henan Province (232300420412)the Science and Technology Tackling Project of Henan Province (242102210160)
文摘Although three-dimensional metal halide perovskites are promising candidates for direct X-ray detection,the ion migration of perovskites seriously affects the detector stability.Herein,face-/edge-shared 3D heterometallic glycinate hybrid perovskitoid Pb_(2)CuGly_(2)X_(4)(Gly=-O_(2)C-CH_(2)-NH_(2);X=Cl,Br)single crystals(SCs),in which the adjacent lead halide layers are linked by large-sized Cu(Gly)_(2)pillars,are synthesized in water.The Cu(Gly)_(2)pillars in combination with face-/edge-shared inorganic skeleton are found able to synergistically suppress the ion migration,delivering a high ion migration activation energy(Ea)of 1.06 eV.The Pb_(2)CuGly_(2)Cl_(4)SC X-ray detector displays extremely low dark current drift of 1.20×10^(-9)nA mm^(-1)s^(-1)V^(-1)under high electric field(120 V mm^(-1))and continuous X-ray irradiation(2.86 Gy),and a high sensitivity of 9,250μC Gy^(-1)cm^(-2)is also achieved.More excitingly,the Pb_(2)CuGly_(2)Cl_(4)nanocrystal can be easily dispersed in water and directly blade-coated on thin-film transistor(TFT)array substrate,and the obtained Pb_(2)CuGly_(2)Cl_(4)-based TFT array detector offers an X-ray imaging capability with spatial resolution of 2.2 lp mm^(-1).
基金supported by the National Natural Science Foundation of China(22479022)the Natural Science Foundation of Liaoning Province(2020-MS-021)。
文摘Aqueous zinc metal batteries(ZMBs)are vital to potable electronics and electric energy infrastructures because of their high energy conversion efficiency,high energy density,and environmental friendliness.However,rampant zinc dendrite growth and side reactions on the Zn anode seriously impede the practical application of ZMBs.In this work,morpholine-crosslinked polyacrylamide hydrogel electrolytes(ploy(acrylamide),6m-PAM)are successfully developed to simultaneously regulate solvation shell to suppress side reactions and homogenize Zn^(2+)ion migration for dendrite-free ZMBs.Notably,the 6m-PAM electrolyte exhibits excellent mechanical strength of 50.6 kPa,high Zn^(2+)ion conductivity of 52 mS cm^(-1)at room temperature,and fast self-healing ability,providing stable and adaptable electrolyte-anode interfaces.Experimental and theoretical calculation results reveal that Zn^(2+)-N(morpholine)coordination interaction effectively reshapes the primary solvation shell of Zn^(2+),suppressing the activity of free water and Zn dendrites.As a result,the 6m-PAM electrolyte endows symmetric zinc cells with a long-term cycling life of 2000 h at 7.5 mA cm^(-2).Notably,Zn/Polyaniline(PANI)batteries equipped with 6m-PAM electrolytes also exhibit a high capacity of 124 mA h g^(-1)at 1 A g^(-1)and a long cycling life of 4000 times with a high-capacity retention of 98.3%,This functional crosslinked hydrogel electrolyte paves a new way to construct durable dendrite-free ZMBs.
基金support from the National Key Research and Development Program of China(No.2022YFE0137400)the National Natural Science Foundation of China(Grant No.62274040).
文摘The past decade has witnessed the rapid increasement in power conversion efficiency of perovskite solar cells(PSCs).However,serious ion migration hampers their operational stability.Although dopants composed of varied cations and anions are introduced into perovskite to suppress ion migration,the impact of cations or anions is not individually explored,which hinders the evaluation of different cations and further application of doping strategy.Here we report that a special group of sulfonic anions(like CF_(3)SO_(3)^(-))successfully introduce alkaline earth ions(like Ca^(2+))into perovskite lattice compared to its halide counterparts.Furthermore,with effective crystallization regulation and defect passivation of sulfonic anions,perovskite with Ca(CF_(3)SO_(3))_(2)shows reduced PbI2 residue and metallic Pb0 defects;thereby,corresponding PSCs show an enhanced PCE of 24.95%.Finally by comparing the properties of perovskite with Ca(CF_(3)SO_(3))_(2)and FACF_(3)SO_(3),we found that doped Ca^(2+)significantly suppressed halide migration with an activation energy of 1.246 eV which accounts for the improved operational stability of Ca(CF_(3)SO_(3))_(2-)doped PSCs,while no obvious impact of Ca^(2+)on trap density is observed.Combining the benefits of cations and anions,this study presents an effective method to decouple the effects of cations and anions and fabricate efficient and stable PSCs.
基金supported by the National Key Research and Development Program of China(2017YFA0206701,2020YFB1506400)the National Natural Science Foundation of China(51972004,21975028)the China Postdoctoral Science Foundation(2020M670040)。
文摘Metal halide perovskites are emerging as the most promising candidate for the next-generation Photovoltaics(PV)materials,due to their superior optoelectronic properties and low cost.However,the resulting Perovskite solar cells(PSCs)suffer from poor stability.In particular,the temperature and light activated ionic defects within the perovskite lattice,as well as electric-field-induced migration of ionic defects,make the PSCs unstable at operating condition,even with device encapsulation.There is no doubt that the investigation of ion migration is crucial for the development of PSCs with high intrinsic stability.In this review,we first briefly introduce the origin and pathways of ion migration,and also the essential characterization methods to identify ion migration.Next,we discuss the impact of ion migration on the perovskite films and cells with respect to photoelectric properties and stability.Then,several representative strategies to suppress ion migration are systematically summarized in the context of composition engineering,additive engineering and interface engineering,with an in-depth understanding on the underlying mechanisms which may provide more clues for further fabrication of PSCs with improved stability.Finally,a perspective with some suggestion on future research directions and chemical approaches are provided to alleviate ion migration in perovskite materials and the entire devices.
基金This work was funded by the National Natural Science Foundation of China(22279049 and 12247101)the Fundamental Research Funds for the Central Universities(lzujbky-2021-it31,lzujbky-2021-ct15 and lzujbky-2021-sp69)+1 种基金the calculation work was supported by Supercomputing Center of Lanzhou Universitythe Gansu Province Outstanding Doctoral Student Program(22JR5RA435).
文摘Metal halide perovskites have recently emerged as promising candidates for the next generation of X-ray detectors due to their excellent optoelectronic properties.Especially,two-dimensional(2D)perovskites afford many distinct properties,including remarkable structural diversity,high generation energy,and balanced large exciton binding energy.With the advantages of 2D materials and perovskites,it successfully reduces the decomposition and phase transition of perovskite and effectively suppresses ion migration.Meanwhile,the existence of a high hydrophobic spacer can block water molecules,thus making 2D perovskite obtain excellent stability.All of these advantages have attracted much attention in the field of X-ray detection.This review introduces the classification of 2D halide perovskites,summarizes the synthesis technology and performance characteristics of 2D perovskite X-ray direct detector,and briefly discusses the application of 2D perovskite in scintillators.Finally,this review also emphasizes the key challenges faced by 2D perovskite X-ray detectors in practical application and presents our views on its future development.
基金supported by the National Natural Science Foundation of China(No.52372176)Sichuan Science and Technology Program(2023YFH0026).
文摘Introduction of vacancies is a widely practiced method to improve the performance of active materials in differentenergy systems,such as secondary batteries,electrocatalysis,and supercapacitors.Because vacancies can generateabundant localized electrons and unsaturated cations,the incorporation of vacancies will significantly improvethe electrical conductivity,ion migration,and provides additional active sites of energy storage materials.Thisarticle systematically reviews different methods to generate oxygen,nitrogen,or selenium vacancies,and techniques to characterize these vacancies.We summarize the specific roles that vacancies play for the active materials in each type of energy storage devices.Additionally,we provide insights into the research progress andchallenges associated with the future development of vacancies technology in various energy storage systems.
基金Project supported by the National Natural Science Foundation of China(Grant No.61805263)Shanghai Sailing Program,China(Grant No.18YF1426400).
文摘Hybrid halide perovskites have great potential for applications in optoelectronic devices.However,the typical ion migration in perovskite could lead to the non-repeatability of electrical measurement,instability of material,and degradation of device performance.The basic current–voltage behavior of perovskite materials is intricate due to the mixed electronic–ionic characteristic,which is still poorly understood in these semiconductors.Developing novel measurement schematic is a promising solution to obtain the intrinsic electrical performance without the interference of ion migration.Herein,we explore the pulse-voltage(PV)method on methylammonium lead tribromide single crystals to protect the device from the ion migration.A guideline is summarized through the analysis of measurement history and condition parameters.The influence of the ion migration on current–voltage measurement,such as repeatability and hysteresis loop,is under controlled.An application of the PV method is demonstrated on the activation energy of conductivity.The abruption of activation energy still exists near the phase transition temperature despite the ion migration is excluded by the PV method,introducing new physical insight on the current–voltage behavior of perovskite materials.The guideline on PV method will be beneficial for measuring halide perovskite materials and developing optoelectronic applications with new technique schematic.
基金supported by the Natural Natural Science Foundation of China (Grant Nos.61904081 and 51672132)the Natural Science Foundation of Jiangsu Province,China (Grant No.BK20190449)the Postdoctoral Research Funding Program of Jiangsu Province,China (Grant No.2020Z144)。
文摘Benefiting from the excellent properties such as high photoluminescence quantum yield(PLQY), wide gamut range,and narrow emission linewidth, as well as low-temperature processability, metal halide perovskite quantum dots(QDs)have attracted wide attention from researchers. Despite tremendous progress has been made during the past several years,the commercialization of perovskite QDs-based LEDs(PeQLEDs) is still plagued by the instability. The ion migration in halide perovskites is recognized as the key factor causing the performance degradation of PeQLEDs. In this review, the elements species of ion migration, the effects of ion migration on device performance and stability, and effective strategies to hinder/mitigate ion migration in PeQLEDs are successively discussed. Finally, the forward insights on the future research are highlighted.
基金supported by the MEYS project, Czech Republic [No.CZ.02.1.01/0.0/0.0/15_003/0000464 (CAP)]the ’Severo Ochoa’ program for Centers of Excellence in R&D [MINECO, Grant SEV2016-0686]+3 种基金the Natural Science Foundation of Jiangsu Province, China [BK20180601]the Fundamental Research Funds for the Central Universities [JUSRP11834, JUSRP11834B]the Jiangsu Postdoctoral Science Foundation [2018K112C, 2018K113C]funding from the Lab and Equipment Management of Jiangnan University (JDSYS201906)。
文摘The device preconditioning dependent hysteresis and the consequential performance degradation hinder the actual performance and stability of the perovskite solar cells. Ion migration and charge trapping in the perovskite with large contribution from grain boundaries are the most common interpretations for the hysteresis. Yet, the high performing devices often include intermediate hole and electron transporting layers, which can further complicate the dynamical process in the device. Here, by using Kelvin Probe Force Microscopy and Confocal Photoluminescence Microscopy, we elucidate the impact of chargetransporting layers and excess MAI on the spatial and temporal variations of the photovoltage on the MAPbI3-based solar cells. By studying the devices layer by layer, we found that the light-induced ion migration occurs predominantly in the presence of an imbalanced charge extraction in the solar cells, and the charge transporting layers play crucial role in suppressing it. Careful selection and processing of the electron and hole-transporting materials are thus essential for making perovskite solar cells free from the ion migration effect.
基金financially supported by the National Natural Sci-ence Foundation of China(62274018,52462031)the Xinjiang Construction Corps Key Areas of Science and Technology Research Project(2023AB029)+1 种基金the Tianchi Talent Program of Xinjiang Uygur Autonomous Region(2024,Jiangzhao Chen)the Key Project of Chongqing Overseas Students Returning to China Entrepreneurship and Innovation Support Plan(cx2023006).
文摘In the past 10 years,perovskite solar cells(PSCs)have undergone extremely rapid development,with a record certified power conversion efficiency(PCE)of 26.7%,which is very close to the limit efficiency.However,the inherent instability caused by ion migration impedes the realization of long-term operationally stable PSCs.In this review,the types and mechanisms of ion migration occurring in various functional layers of negative-intrinsic-positive(n-i-p)PSCs are summarized.Additionally,methods of suppressing ion migration are systematically discussed.Finally,the prospects of current challenges and future development directions are proposed to advance the achievement of high-performance regular PSCs with high stability and PCE.
基金supported by the Russian Science Foundation(project number 24-62-00022)for data analysis and by Priority 2030 Federal Academic Leadership Program for samples synthesis.
文摘Halide perovskites is a recently emerged platform for the creation of efficient memristors.In turn,single-crystal inorganic perovskite would be new low-cost and flexible memory devices because of their excellent resistive switching(RS)properties,without risk of chemical and mechanical stress-generated degradation,compared with the operational instability of general thin-film perovskite memristors.Moreover,miniaturization of perovskite memristors would be useful for creating high-density memory devices.Here we demonstrate the smallest CsPbBr3 perovskite nanomemristor with volatile unipolar RS characteristics which depends on the size of a single-crystal as a resistive layer due to its overall structural stability and low sensitivity to atmosphere conditions that helps to keep the stable RS switching over 1500 times with the lowest consumption power of 70 nW.To better understand the RS mechanism,we provide a comprehensive simulation of the evolution of mixed ionic-electronic charge carriers under current-voltage(I-V)tests using a one-dimensional drift-diffusion model.Because of the nonreactive nature of the contacts,the main mechanism of resistive state switching is potential barrier modulation of the Schottky contacts through the accumulation of migrating ions at the interfaces.Our findings pave the way for ultracompact memristors as well as shed light on RS mechanism in non-filamentary perovskitebased memory devices.
文摘Perovskite quantum dot light-emitting diodes(Pe-QLEDs)have shown immense application potential in display and lighting fields due to their narrow full-width at half maximum(FWHM)and high photoluminescence quantum yield(PLQY).Despite significant advancements in their performance,challenges such as defects and ion migration still hinder their long-term stability and operational efficiency.To address these issues,various optimization strategies,including ligand engineering,interface passivation,and self-assembly strategy,are being actively researched.This review focuses on the synthesis methods,challenges and optimization of perovskite quantum dots,which are critical for the commercialization and large-scale production of high-performance and stable Pe-QLEDs.
基金supported by National Natural Science Foundation of China(52302229,62404072)the Key Lab of Modern Optical Technologies of Education Ministry of China,Soochow University(KJS2425)+1 种基金Doctoral Foundation of Henan Polytech-nic University(B2024-72)Science and Technology Research Project of Jiangxi Provincial Department of Education(Grant No.GJJ2400702).
文摘Through strategies such as process optimization,solvent selection,and component tuning,the crystallization of perovskite materials has been effectively controlled,enabling perovskite solar cells(PSCs)to achieve over 25%power conversion efficiency(PCE).However,as PCE continues to improve,interfacial issues within the devices have emerged as critical bottlenecks,hindering further performance enhancements.Recently,interfacial engineering has driven transformative progress,pushing PCEs to nearly 27%.Building upon these developments,this review first summarizes the pivotal role of interfacial modifications in elevating device performance and then,as a starting point,provides a comprehensive overview of recent advancements in normal,inverted,and tandem structure devices.Finally,based on the current progress of PSCs,preliminary perspectives on future directions are presented.
基金support of the National Natural Science Foundation of China(Grant No.22225801,22178217 and 22308216)supported by the Fundamental Research Funds for the Central Universities,conducted at Tongji University.
文摘Rechargeable magnesium batteries(RMBs)have been considered a promising“post lithium-ion battery”system to meet the rapidly increasing demand of the emerging electric vehicle and grid energy storage market.However,the sluggish diffusion kinetics of bivalent Mg^(2+)in the host material,related to the strong Coulomb effect between Mg^(2+)and host anion lattices,hinders their further development toward practical applications.Defect engineering,regarded as an effective strategy to break through the slow migration puzzle,has been validated in various cathode materials for RMBs.In this review,we first thoroughly understand the intrinsic mechanism of Mg^(2+)diffusion in cathode materials,from which the key factors affecting ion diffusion are further presented.Then,the positive effects of purposely introduced defects,including vacancy and doping,and the corresponding strategies for introducing various defects are discussed.The applications of defect engineering in cathode materials for RMBs with advanced electrochemical properties are also summarized.Finally,the existing challenges and future perspectives of defect engineering in cathode materials for the overall high-performance RMBs are described.
