High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unpa...High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unparalleled performance,the relationships between multiple active sites and reaction intermediates are still obscure.Here,enlightened by theoretical screening,we tailor a high-entropy perovskite fluoride(KCoMnNiMgZnF_(3)-HEC)with various active sites to overcome the limitations of conventional catalysts in redox process.The entropy effect modulates the d-band center and d orbital occupancy of active centers,which optimizes the d–p hybridization between catalytic sites and key intermediates,enabling a moderate adsorption of LiO_(2)and thus reinforcing the reaction kinetics.As a result,the Li–O2 battery with KCoMnNiMgZnF_(3)-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability,preceding majority of traditional catalysts reported.These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.展开更多
Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the...Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.展开更多
Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells(PSCs).Dimethylamine oxalate has been proven as a multifunctional modulator,and is explored as...Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells(PSCs).Dimethylamine oxalate has been proven as a multifunctional modulator,and is explored as an efficient additive in manipulating the crystallization process of CsPbI_(3) perovskite films.On one hand,oxalate serves as the precipitator that facilitates the nucleation process of intermediate.The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite.On the other hand,in subsequent annealing process,the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation(DMA^(+))and Pb^(2+).Due to the optimized crystallization kinetics,the morphology and quality of CsPbI_(3) perovskite films are comprehensively improved with lower defect concentrations,and charge recombination loss is effectively suppressed.Benefiting from the optimized crystal quality of perovskite films,the carbon electrode-based CsPbI_(3) PSCs exhibit a champion efficiency of 18.48%.This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.展开更多
Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties.New Bi-based perovskite thin films Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)(BCT–PT...Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties.New Bi-based perovskite thin films Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)(BCT–PT) are deposited on Pt(111)/Ti/SiO_(2)/Si substrates in the present study by the traditional sol–gel method.Their structures and related ferroelectric and fatigue characteristics are studied in-depth.The BCT–PT thin films exhibit good crystallization within the phase-pure perovskite structure,besides,they have a predominant(100) orientation together with a dense and homogeneous microstructure.The remnant polarization(2P_(r)) values at 30 μC/cm^(2) and 16 μC/cm^(2) are observed in 0.1BCT–0.9PT and 0.2BCT–0.8PT thin films,respectively.More intriguingly,although the polarization values are not so high,0.2BCT–0.8PT thin films show outstanding polarization fatigue properties,with a high switchable polarization of 93.6% of the starting values after 10^(8) cycles,indicating promising applications in ferroelectric memories.展开更多
Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition...Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition,and lattice defects are still the key challenges limiting the quality of FAPbI_(3) films.Previous studies show that the introduction or adding of seeds in the precursor is effective to promote the nucleation and crystallization of perovskite films.Nevertheless,the seed-assisted approach focuses on heterogeneous seeds or hetero-composites,which inevitably induce a lattice-mismatch,the genera-tion of strain or defects,and the phase segregation in the perovskite films.Herein,we first demonstrate that high-quality perovskite films are controllably prepared using α-and δ-phases mixed FAPbI_(3) micro-crystal as the homogeneous seeds with the one-step antisolvent method.The partially dissolved seeds with suitable sizes improve the crystallinity of the perovskite flm with preferable orientation,improved carrier lifetime,and increased carrier mobility.More importantly,the α-phase-containing seeds promote the formation of α-phase FAPbI_(3) films,leading to the reduction of residual lattice strain and the suppres-sion of I-ion migration.Besides,the adding of dimethyl 2,6-pyridine dicarboxylate(DPD)into the pre-cursor further suppresses the generation of defects,contributing to the PCE of devices prepared in air ambient being significantly improved to 23.75%,among the highest PCEs for fully air-processed FAPbI_(3) solar cells.The unpackaged target devices possess a high stability,maintaining 80%of the initial PCE under simulated solar illumination exceeding 800 h.展开更多
Thermal stability of perovskite materials is an issue impairing the long-term operation of inverted perovskite solar cells(PSCs). Herein, the thermal attenuation mechanism of the MAPb I3films that deposited on two dif...Thermal stability of perovskite materials is an issue impairing the long-term operation of inverted perovskite solar cells(PSCs). Herein, the thermal attenuation mechanism of the MAPb I3films that deposited on two different hole transport layers(HTL), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS) and poly(3,4-ethylenedioxythiophene)(PEDOT), is comprehensively studied by applying a heat treatment at 85℃. The thermal stress causes the mutual ions migration of I, Pb and Ag through the device, which leads to the thermal decomposition of perovskite to form Pb I2. Interestingly, we find that I ions tend to migrate more towards electron transport layer(ETL) during heating, which is different with the observation of I ions migration towards HTL when bias pressure is applied. Moreover, the use of electrochemical deposited PEDOT as HTL significantly decreases the defect density of MAPb I3films as compared to PEDOT:PSS supported one. The electrochemical deposition PEDOT has good carrier mobility and low acidity, which avoids the drawbacks of aqueous PEDOT:PSS. Accordingly, the inverted PSCs based on PEDOT show superior durability than that with PEDOT:PSS. Our results reveal detailed degradation routes of a new kind of inverted PSCs which can contribute to the understanding of the failure of thermal-aged inverted PSCs.展开更多
Perovskite solar cells(PSCs)have been demonstrated to be one of the most promising technologies in the field of renewable energy.However,the presence of the defects in the perovskite films greatly limits the efficienc...Perovskite solar cells(PSCs)have been demonstrated to be one of the most promising technologies in the field of renewable energy.However,the presence of the defects in the perovskite films greatly limits the efficiency and the stability of the PSCs.The additive engineering is one of the most effective approaches to overcome this problem.Most of the successful additives are extracted from the petroleum-based materials,while the research on the biomass-based additives is still lagging behind.In this paper,two ecofriendly hydroxyalkyl cellulose additives,i.e.,hydroxyethyl cellulose(HEC)and hydroxylpropyl cellulose(HPC),are investigated on the performance of the MAPbl_(3)-based inverted PSCs.Due to the strong interaction between the hydroxyl groups of the cellulose and the divalent cations of the perovskite,these additives enhance the crystal grain orientation and significantly repair the defects of the perovskite films.Working as the additives,these two cellulose derivatives show a strong passivation ability,which significantly reduces the trap density and improves the optoelectronic feature of the PSCs.Compared with the average power conversion efficiency(PCE)of the control device(19.19%),an enhancement of~10%is achieved after the addition of HEC.The optimized device(PCE=21.25%)with a long-term stability(10:80 h,PCE=20.93%)is achieved by the incorporation of the HEC additives into the precursor solution.It is the best performance among the PSCs with the cellulose additives up to now.This research provides a novel choice to develop a cost-effective and renewable additive for the PSCs with high efficiency and excellent long-term stability.展开更多
All-inorganic CsPbI_3 quantum dots(QDs) have demonstrated promising potential in photovoltaic(PV) applications. However, these colloidal perovskites are vulnerable to the deterioration of surface trap states, leading ...All-inorganic CsPbI_3 quantum dots(QDs) have demonstrated promising potential in photovoltaic(PV) applications. However, these colloidal perovskites are vulnerable to the deterioration of surface trap states, leading to a degradation in efficiency and stability. To address these issues, a facile yet effective strategy of introducing hydroiodic acid(HI) into the synthesis procedure is established to achieve high-quality QDs and devices. Through an in-depth experimental analysis, the introduction of HI was found to convert PbI_2 into highly coordinated [PbI_m]~(2-m), enabling control of the nucleation numbers and growth kinetics. Combined optical and structural investigations illustrate that such a synthesis technique is beneficial for achieving enhanced crystallinity and a reduced density of crystallographic defects. Finally, the effect of HI is further reflected on the PV performance. The optimal device demonstrated a significantly improved power conversion efficiency of 15.72% along with enhanced storage stability. This technique illuminates a novel and simple methodology to regulate the formed species during synthesis, shedding light on ofurther understanding solar cell performance, and aiding the design of future novel synthesis protocols for high-performance optoelectronic devices.展开更多
In the past period of time, perovskite solar cells have gained tremendous developments in improving photovoltaic performance, but they still face severe challenges. Defects in perovskite layers, especially at grain bo...In the past period of time, perovskite solar cells have gained tremendous developments in improving photovoltaic performance, but they still face severe challenges. Defects in perovskite layers, especially at grain boundaries, severely limit the stabilization and efficiency of solar cells. In this work, we adopt 3-carboxyphenylboronic acid(CPBA) for modifying defects in perovskite thin films. Through the interaction among the carboxyl group, boronic acid and lead ions in the perovskite film, the crystallization effect of the perovskite molecular is greatly optimized. Moreover, the film defects are spontaneously passivated and the band gap is reduced, increasing the open circuit voltage and fill factor. Therefore,power conversion efficiency has been increased from 17.25% to 20.20%. This discovery provides a potential strategy for passivating the trap states in perovskite and enhancing the properties of devices.展开更多
Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by gra...Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by grain boundaries,which seriously hinder the further improvement of power conversion efficiency and stability.Herein,a novel carbon nitride C_(3)N_(3) incorporated into the perovskite precursor solution is a multifunctional strategy,which not only increases the light absorption strength,grain size,and hydrophobicity of the perovskite film,but also effectively passivates the bulk and interfacial defects of perovskite and verified by the first-principles density functional theory calculations.As a result,the efficiency and stability of perovskite solar cells are improved.The device with 0.075 mg mL^(-1) C_(3)N_(3) additive delivers a champion power conversion efficiency of 19.91%with suppressed hysteresis,which is significantly higher than the 18.16% of the control device.In addition,the open-circuit voltage of the modified device with the maximum addition as high as 1.137 V is 90.96% of the Shockley–Queisser limit(1.25 V).Moreover,the power conversion efficiency of the modified device without encapsulation can maintain nearly 90% of its initial value after being stored at 25℃ and 60% relative humidity for 500 h.This work provides a new idea for developing additives to improve the power conversion efficiency and stability of perovskite solar cells.展开更多
All-inorganic CsPbI_(3) perovskite has attracted wide attention due to its desirable optical bandgap(Eg:∼1.7 eV)as well as high chemical stability.Nevertheless,the photovoltaic performance of CsPbI_(3) perovskite sol...All-inorganic CsPbI_(3) perovskite has attracted wide attention due to its desirable optical bandgap(Eg:∼1.7 eV)as well as high chemical stability.Nevertheless,the photovoltaic performance of CsPbI_(3) perovskite solar cells(PSCs)was limited by severe nonradiative charge recombination due to high defect density at the grain boundary and surface of perovskitefilms.To address this issue,a pyrrolidinium iodide(PyI)molecule was introduced to modify the surface and grain boundary of CsPbI_(3) perovskitefilms to passivate defects,which improves the quality of CsPbI_(3) perovskitefilms as well as induces the generation of a quasi-2D Py_(2)CsPb_(2)I_(7) capping layer between per-ovskite layer and hole transport layer.Such quasi-2D Py_(2)CsPb_(2)I_(7) capping layer optimizes interface contact between CsPbI_(3) perovskite layer and hole transport layer and blocks the electron transfer from CsPbI_(3) perovskite photoactive layer to the hole transport layer.As a result,the performance of CsPbI_(3) PSCs is well improved to 17.87%for power conversion efficiency(PCE)with an ultra-high fill factor(FF)of 0.84.In addition,the PyI mole-cule modified CsPbI_(3) perovskite devices exhibit excellent stability,which remains its initial PCE almost unchanged after aging for 35 days under the dry air atmosphere(temperature:20℃–30℃,control relative humid-ity(RH):<10%).展开更多
The exploitation of fossil resources to meet humanity’s energy needs is the root cause of the climate warming phenomenon facing the planet. In this context, non-carbon-based energies, such as photovoltaic energy, are...The exploitation of fossil resources to meet humanity’s energy needs is the root cause of the climate warming phenomenon facing the planet. In this context, non-carbon-based energies, such as photovoltaic energy, are identified as crucial solutions. Organic perovskites MAPbI<sub>3</sub> and FAPbI<sub>3</sub>, characterized by their abundance, low cost, and ease of synthesis, are emerging as candidates for study to enhance their competitiveness. It is within this framework that this article presents a comparative analysis of the performances of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> perovskites in the context of photovoltaic devices. The analysis focuses on the optoelectronic characteristics and stability of these high-potential materials. The optical properties of perovskites are rigorously evaluated, including band gaps, photoluminescence, and light absorption, using UV-Vis spectroscopy and photoluminescence techniques. The crystal structure is characterized by X-ray diffraction, while film morphology is examined through scanning electron microscopy. The results reveal significant variations between the two types of perovskites, directly impacting the performance of resulting solar devices. Simultaneously, the stability of perovskites is subjected to a thorough study, exposing the materials to various environmental conditions, highlighting key determinants of their durability. Films of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> demonstrate distinct differences in terms of topography, optical performance, and stability. Research has unveiled that planar perovskite solar cells based on FAPbI<sub>3</sub> offer higher photoelectric conversion efficiency, surpassing their MAPbI<sub>3</sub>-based counterparts in terms of performance. These advancements aim to overcome stability constraints and enhance the long-term durability of perovskites, ultimately aiming for practical application of these materials. This comprehensive comparative analysis provides an enlightened understanding of the optoelectronic performance and stability of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> perovskites, which is critically important to guide future research and development of solar devices that are both more efficient and sustainable.展开更多
Perovskite materials have drawn a lot of interest recently due to their potential to increase solar cell efficiency. This study uses the solar cell capacitance simulator (SCAPS-1D) to develop and simulate a perovskite...Perovskite materials have drawn a lot of interest recently due to their potential to increase solar cell efficiency. This study uses the solar cell capacitance simulator (SCAPS-1D) to develop and simulate a perovskite solar cell made of semiconductor materials. The design that has been suggested is Al:ZnO/ZnO/CdS/CsSnCl<sub>3</sub> and MoS<sub>2</sub>. The analysis focuses on how different characteristics of the material affect the device’s performance. The analysis of the data reveals that the architecture had 26.15% power conversion efficiency (PCE). The solar cell creates an interest in developing a non-toxic solar cell with low manufacturing costs, outstanding conversion efficiency, and stability.展开更多
Perovskite LaMnO3 powders with an average crystallite size of 12.5 nm were rapidly synthesized via a microwave-induced autocombustion reaction using glycine as a fuel and nitrate as an oxidant. After self-propagating ...Perovskite LaMnO3 powders with an average crystallite size of 12.5 nm were rapidly synthesized via a microwave-induced autocombustion reaction using glycine as a fuel and nitrate as an oxidant. After self-propagating combustion, the desired nanocrystalline perovskite LaMnO3 was obtained and no further calcination was carried out. The possible processes of combustion reaction were discussed according to the principle of propellant chemistry. The autocombustion and thermal decomposition of the precursor were investigated using the TG-DTA and FT-IR techniques. The influences of glycine-nitrate molar ratio and heat-treatment temperature on the perovskite phase formation and crystallite size of as-burnt powder were studied by XRD. The morphology and size of the as-burnt powder before and after milling were characterized and compared by TEM.展开更多
Cesium lead iodide(CsPbI_(3)) perovskite has gained great attention in the photovoltaic(PV) community because of its unique optoelectronic properties, good chemical stability and appropriate bandgap for sunlight harve...Cesium lead iodide(CsPbI_(3)) perovskite has gained great attention in the photovoltaic(PV) community because of its unique optoelectronic properties, good chemical stability and appropriate bandgap for sunlight harvesting applications. However, compared to solar cells fabricated from organic-inorganic hybrid perovskites, the commercialization of devices based on all-inorganic CsPbI_(3) perovskites still faces many challenges regarding PV performance and long-term stability. In this work, we discovered that tetrabutylammonium bromide(TBABr) post-treatment to CsPbI_(3) perovskite films could achieve synergistic stabilization with both TBA+cation intercalation and Br-doping. Such TBA^(+) cation intercalation leads to onedimensional capping with TBAPb I3 perovskite formed in situ, while the Br-induced crystal secondary growth helps effectively passivate the defects of CsPbI_(3) perovskite, thus enhancing the stability. In addition, the incorporation of TBABr can improve energy-level alignment and reduce interfacial charge recombination loss for better device performance. Finally, the highly stable TBABr-treated CsPbI_(3)-based perovskite solar cells show reproducible photovoltaic performance with a champion efficiency up to 19.04%, while retaining 90% of the initial efficiency after 500 h storage without encapsulation.展开更多
All-inorganic cesium lead bromide(CsPbBr3)perovskite is attracting growing interest as functional materials in photovoltaics and other optoelectronic devices due to its superb stability.However,the fabrication of high...All-inorganic cesium lead bromide(CsPbBr3)perovskite is attracting growing interest as functional materials in photovoltaics and other optoelectronic devices due to its superb stability.However,the fabrication of high-quality CsPbBr3 films still remains a big challenge by solution-process because of the low solubility of the cesium precursor in common solvents.Herein,we report a facile solution-processed approach to prepare high-quality CsPbBr3 perovskite films via a two-step spin-coating method,in which the Cs Br methanol/H2 O mixed solvent solution is spin-coated onto the lead bromide films,followed by an isopropanol-assisted post-treatment to regulate the crystallization process and to control the film morphology.In this fashion,dense and uniform CsPbBr3 films are obtained consisting of large crystalline domains with sizes up to microns and low defect density.The effectiveness of the resulting CsPbBr3 films is further examined in perovskite solar cells(PSCs)with a simplified planar architecture of fluorine–doped tin oxide/compact Ti O2/CsPbBr3/carbon,which deliver a maximum power conversion efficiency of 8.11%together with excellent thermal and humidity stability.The present work offers a simple and effective strategy in fabrication of high-quality CsPbBr3 films for efficient and stable PSCs as well as other optoelectronic devices.展开更多
Due to the unique structure of perovskite materials,their capacitance can be improved by introducing oxygen vacancy.In this paper,the LaMnO3-δ material containing oxygen vacancy was synthesized by molten salt method ...Due to the unique structure of perovskite materials,their capacitance can be improved by introducing oxygen vacancy.In this paper,the LaMnO3-δ material containing oxygen vacancy was synthesized by molten salt method in KNO3-NaNO3-NaNO2 melt.The La-Mn-O crystal grows gradually in molten salt with the increase of temperature.It was confirmed that LaMnO3-δ with perovskite structure and incomplete oxygen content were synthesized by molten salt method and presented a three-dimensional shape.LaMnO3-δ stores energy by redox reaction and adsorption of OH-in electrolyte simultaneously.In comparison with the stoichiometric LaMnO3 prepared by the sol-gel method,LaMnO3-δ prepared by molten salt method proffered higher capacitance and better performance.The galvanostatic charge-discharge curve showed specific capacitance of 973.5 F/g under current density of 1 A/g in 6 M KOH.The capacitance of LaMn03-δ was 82.7%under condition of 5 A/g compared with the capacitance at the current of 1A/g,and the specific capacitances of 648.0 and 310.0 F/g were obtained after 2000 and 5000 cycles of galvanostatic charging-discharging,respectively.Molten salt synthesis method is relatively simple and suitable for industrial scale,presenting a promising prospect in the synthesis of perovskite oxide materials.展开更多
The structural, electronic, and optical properties of cubic perovskite NaMgF3 are calculated by plane-wave pseudopo- tential density functional theory. The calculated lattice constant a0, bulk modulus B0, and the deri...The structural, electronic, and optical properties of cubic perovskite NaMgF3 are calculated by plane-wave pseudopo- tential density functional theory. The calculated lattice constant a0, bulk modulus B0, and the derivative of bulk modulus B~ are 3.872/~, 78.2 GPa, and 3.97, respectively. The results are in good agreement with the available experimental and theo- retical values. The electronic structure shows that cubic NaMgF3 is an indirect insulator with a wide forbidden band gap of Eg = 5.90 eV. The contribution of the different bands is analyzed by total and partial density of states curves. Population analysis of NaMgF3 indicates that there is strong ionic bonding in the MgF2 unit, and a mixture of ionic and weak covalent bonding in the NaF unit. Calculations of dielectric function, absorption coefficient, refractive index, electronic energy loss spectroscopy, optical reflectivity, and conductivity are also performed in the energy range 0 to 70 eV.展开更多
基金P.G.acknowledges the financial support from the Youth Foundation of Shandong Natural Science Foundation(No.ZR2023OB230)National Natural Science Foundation(No.22309035)Double First-class Discipline Construction Fund Project of Harbin Institute of Technology at Weihai(No.2023SYLHY11).
文摘High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unparalleled performance,the relationships between multiple active sites and reaction intermediates are still obscure.Here,enlightened by theoretical screening,we tailor a high-entropy perovskite fluoride(KCoMnNiMgZnF_(3)-HEC)with various active sites to overcome the limitations of conventional catalysts in redox process.The entropy effect modulates the d-band center and d orbital occupancy of active centers,which optimizes the d–p hybridization between catalytic sites and key intermediates,enabling a moderate adsorption of LiO_(2)and thus reinforcing the reaction kinetics.As a result,the Li–O2 battery with KCoMnNiMgZnF_(3)-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability,preceding majority of traditional catalysts reported.These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.
基金support of National Natural Science Foundation of China(22179027)gratefully acknowledged.This work was also supported by the Natural Science Foundation of Guangxi Province(2021GXNSFAA075063,2018GXNSFDA281005)+1 种基金the National Key Research and Development Program of China(2017YFE0105500)Science&Technology Research Project of Guangdong Province(2017A020216009).
文摘Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.
基金supported by the National Natural Science Foundation of China(Nos.U21A20310,22278164,22122805,22308112)the Science and Technology Program of Guangzhou,China(No.2023A04J0665)China Postdoctoral Science Foundation(No.2023M741214)。
文摘Crystallization process determines the quality of perovskite films and the performances of resultant perovskite solar cells(PSCs).Dimethylamine oxalate has been proven as a multifunctional modulator,and is explored as an efficient additive in manipulating the crystallization process of CsPbI_(3) perovskite films.On one hand,oxalate serves as the precipitator that facilitates the nucleation process of intermediate.The larger size of intermediate is conductive to the larger size and smaller grain boundaries of resultant perovskite.On the other hand,in subsequent annealing process,the phase conversion and growth process of transient perovskite can be decelerated due to the strong interactions of oxalate with both dimethylamine cation(DMA^(+))and Pb^(2+).Due to the optimized crystallization kinetics,the morphology and quality of CsPbI_(3) perovskite films are comprehensively improved with lower defect concentrations,and charge recombination loss is effectively suppressed.Benefiting from the optimized crystal quality of perovskite films,the carbon electrode-based CsPbI_(3) PSCs exhibit a champion efficiency of 18.48%.This represents one of the highest levels among all hole transport layer-free inorganic perovskite solar cells.
基金Project supported by the National Key Research and Development Program of China(Grant No.2021YFA1400300)the National Natural Science Foundation of China(Grant Nos.22271309,21805215,11934017,12261131499,and 11921004)+1 种基金the Beijing Natural Science Foundation(Grant No.Z200007)the Fund from the Chinese Academy of Sciences(Grant No.XDB33000000)。
文摘Bi-based perovskite ferroelectric thin films have wide applications in electronic devices due to their excellent ferroelectric properties.New Bi-based perovskite thin films Bi(Cu_(1/2)Ti_(1/2))O_(3)–PbTiO_(3)(BCT–PT) are deposited on Pt(111)/Ti/SiO_(2)/Si substrates in the present study by the traditional sol–gel method.Their structures and related ferroelectric and fatigue characteristics are studied in-depth.The BCT–PT thin films exhibit good crystallization within the phase-pure perovskite structure,besides,they have a predominant(100) orientation together with a dense and homogeneous microstructure.The remnant polarization(2P_(r)) values at 30 μC/cm^(2) and 16 μC/cm^(2) are observed in 0.1BCT–0.9PT and 0.2BCT–0.8PT thin films,respectively.More intriguingly,although the polarization values are not so high,0.2BCT–0.8PT thin films show outstanding polarization fatigue properties,with a high switchable polarization of 93.6% of the starting values after 10^(8) cycles,indicating promising applications in ferroelectric memories.
基金supported by the National Natural Science Foundation of China (61604131,62025403)the Natural Science Foundation of Zhejiang Province (LY19F040009)+1 种基金the Fundamental Research Funds of Zhejiang SciTech University (23062120-Y)the Open Project of Key Laboratory of Solar Energy Utilization and Energy Saving Technology of Zhejiang Province (ZJS-OP-2020-07)
文摘Formamidine lead triiodide(FAPbI_(3))perovskites have become the most promising photovoltaic materials for perovskite solar cells with record power conversion efficiency(PCE).However,random nucleation,phase transition,and lattice defects are still the key challenges limiting the quality of FAPbI_(3) films.Previous studies show that the introduction or adding of seeds in the precursor is effective to promote the nucleation and crystallization of perovskite films.Nevertheless,the seed-assisted approach focuses on heterogeneous seeds or hetero-composites,which inevitably induce a lattice-mismatch,the genera-tion of strain or defects,and the phase segregation in the perovskite films.Herein,we first demonstrate that high-quality perovskite films are controllably prepared using α-and δ-phases mixed FAPbI_(3) micro-crystal as the homogeneous seeds with the one-step antisolvent method.The partially dissolved seeds with suitable sizes improve the crystallinity of the perovskite flm with preferable orientation,improved carrier lifetime,and increased carrier mobility.More importantly,the α-phase-containing seeds promote the formation of α-phase FAPbI_(3) films,leading to the reduction of residual lattice strain and the suppres-sion of I-ion migration.Besides,the adding of dimethyl 2,6-pyridine dicarboxylate(DPD)into the pre-cursor further suppresses the generation of defects,contributing to the PCE of devices prepared in air ambient being significantly improved to 23.75%,among the highest PCEs for fully air-processed FAPbI_(3) solar cells.The unpackaged target devices possess a high stability,maintaining 80%of the initial PCE under simulated solar illumination exceeding 800 h.
基金financially supported by the National Natural Science Foundation of China (No. 61774169)the Natural Science Foundation of Hunan Province (No. 2022JJ30757)the Guangdong Science and Technology Planning Project (No.2018B030323010)。
文摘Thermal stability of perovskite materials is an issue impairing the long-term operation of inverted perovskite solar cells(PSCs). Herein, the thermal attenuation mechanism of the MAPb I3films that deposited on two different hole transport layers(HTL), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS) and poly(3,4-ethylenedioxythiophene)(PEDOT), is comprehensively studied by applying a heat treatment at 85℃. The thermal stress causes the mutual ions migration of I, Pb and Ag through the device, which leads to the thermal decomposition of perovskite to form Pb I2. Interestingly, we find that I ions tend to migrate more towards electron transport layer(ETL) during heating, which is different with the observation of I ions migration towards HTL when bias pressure is applied. Moreover, the use of electrochemical deposited PEDOT as HTL significantly decreases the defect density of MAPb I3films as compared to PEDOT:PSS supported one. The electrochemical deposition PEDOT has good carrier mobility and low acidity, which avoids the drawbacks of aqueous PEDOT:PSS. Accordingly, the inverted PSCs based on PEDOT show superior durability than that with PEDOT:PSS. Our results reveal detailed degradation routes of a new kind of inverted PSCs which can contribute to the understanding of the failure of thermal-aged inverted PSCs.
基金the National Natural Science Foundation of China(61935017,62175268,21674123,31700507)Fujian Natural Science Foundation for Distinguished Young Scholars(2020J06039)+4 种基金Project of“100 People Planning in Fujian Province,”Fujian Provincial Department of Finance for the research of organic photovoltaic solar cell(Kle20001A)the Science and Technology Development Fund,Macao SAR(File no.FDCT-0044/2020/A1,0082/2021/A2)UM's research fund(File no.MYRG2020-00151-IAPME)Natural Science Foundation of Guangdong Province,China(2019A1515012186)Shenzhen-Hong Kong-Macao Science and Technology Innovation Project(Category C)(SGDX2020110309360100).
文摘Perovskite solar cells(PSCs)have been demonstrated to be one of the most promising technologies in the field of renewable energy.However,the presence of the defects in the perovskite films greatly limits the efficiency and the stability of the PSCs.The additive engineering is one of the most effective approaches to overcome this problem.Most of the successful additives are extracted from the petroleum-based materials,while the research on the biomass-based additives is still lagging behind.In this paper,two ecofriendly hydroxyalkyl cellulose additives,i.e.,hydroxyethyl cellulose(HEC)and hydroxylpropyl cellulose(HPC),are investigated on the performance of the MAPbl_(3)-based inverted PSCs.Due to the strong interaction between the hydroxyl groups of the cellulose and the divalent cations of the perovskite,these additives enhance the crystal grain orientation and significantly repair the defects of the perovskite films.Working as the additives,these two cellulose derivatives show a strong passivation ability,which significantly reduces the trap density and improves the optoelectronic feature of the PSCs.Compared with the average power conversion efficiency(PCE)of the control device(19.19%),an enhancement of~10%is achieved after the addition of HEC.The optimized device(PCE=21.25%)with a long-term stability(10:80 h,PCE=20.93%)is achieved by the incorporation of the HEC additives into the precursor solution.It is the best performance among the PSCs with the cellulose additives up to now.This research provides a novel choice to develop a cost-effective and renewable additive for the PSCs with high efficiency and excellent long-term stability.
基金financially supported by the National Key Research and Development Program of China (No. 2021YFB3800101 and 2022YFE0110300)National Natural Science Foundation of China (No. U19A2089, 52261145696, 52073198, 92163114, and 22161142003)+3 种基金Natural Science Foundation of Jiangsu Province (BK20211598)“111” projectthe Young Elite Scientist Sponsorship Program by CASTCollaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University。
文摘All-inorganic CsPbI_3 quantum dots(QDs) have demonstrated promising potential in photovoltaic(PV) applications. However, these colloidal perovskites are vulnerable to the deterioration of surface trap states, leading to a degradation in efficiency and stability. To address these issues, a facile yet effective strategy of introducing hydroiodic acid(HI) into the synthesis procedure is established to achieve high-quality QDs and devices. Through an in-depth experimental analysis, the introduction of HI was found to convert PbI_2 into highly coordinated [PbI_m]~(2-m), enabling control of the nucleation numbers and growth kinetics. Combined optical and structural investigations illustrate that such a synthesis technique is beneficial for achieving enhanced crystallinity and a reduced density of crystallographic defects. Finally, the effect of HI is further reflected on the PV performance. The optimal device demonstrated a significantly improved power conversion efficiency of 15.72% along with enhanced storage stability. This technique illuminates a novel and simple methodology to regulate the formed species during synthesis, shedding light on ofurther understanding solar cell performance, and aiding the design of future novel synthesis protocols for high-performance optoelectronic devices.
基金Project supported by the Regional Joint Fund of the National Science Foundation of China (Grant No. U21A20492)the Sichuan Science and Technology Program (Grant Nos. 2022YFH0081, 2022YFG0012, and 2022YFG0013)+1 种基金sponsored by the Sichuan Province Key Laboratory of Display Science and TechnologyQiantang Science & Technology Innovation Center。
文摘In the past period of time, perovskite solar cells have gained tremendous developments in improving photovoltaic performance, but they still face severe challenges. Defects in perovskite layers, especially at grain boundaries, severely limit the stabilization and efficiency of solar cells. In this work, we adopt 3-carboxyphenylboronic acid(CPBA) for modifying defects in perovskite thin films. Through the interaction among the carboxyl group, boronic acid and lead ions in the perovskite film, the crystallization effect of the perovskite molecular is greatly optimized. Moreover, the film defects are spontaneously passivated and the band gap is reduced, increasing the open circuit voltage and fill factor. Therefore,power conversion efficiency has been increased from 17.25% to 20.20%. This discovery provides a potential strategy for passivating the trap states in perovskite and enhancing the properties of devices.
基金This work was financially supported by National Natural Science Foundation of China(52002121,62004064,21873027,and 21905219)the Key Program for Inter-governmental S&T Innovation Cooperation Projects of National Key R&D Pro-gram of China(2019YFE0107100)+1 种基金Natural Science Foundation of Hubei Province(2020CFA091)Overseas Expertise Introduction Center for Discipline Innova-tion(D18025).
文摘Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by grain boundaries,which seriously hinder the further improvement of power conversion efficiency and stability.Herein,a novel carbon nitride C_(3)N_(3) incorporated into the perovskite precursor solution is a multifunctional strategy,which not only increases the light absorption strength,grain size,and hydrophobicity of the perovskite film,but also effectively passivates the bulk and interfacial defects of perovskite and verified by the first-principles density functional theory calculations.As a result,the efficiency and stability of perovskite solar cells are improved.The device with 0.075 mg mL^(-1) C_(3)N_(3) additive delivers a champion power conversion efficiency of 19.91%with suppressed hysteresis,which is significantly higher than the 18.16% of the control device.In addition,the open-circuit voltage of the modified device with the maximum addition as high as 1.137 V is 90.96% of the Shockley–Queisser limit(1.25 V).Moreover,the power conversion efficiency of the modified device without encapsulation can maintain nearly 90% of its initial value after being stored at 25℃ and 60% relative humidity for 500 h.This work provides a new idea for developing additives to improve the power conversion efficiency and stability of perovskite solar cells.
基金National Natural Science Foundation of China,Grant No.21875013,H.N.ChenBeijing Natural Science Foundation,Grant No.2182031,H.N.Chen.
文摘All-inorganic CsPbI_(3) perovskite has attracted wide attention due to its desirable optical bandgap(Eg:∼1.7 eV)as well as high chemical stability.Nevertheless,the photovoltaic performance of CsPbI_(3) perovskite solar cells(PSCs)was limited by severe nonradiative charge recombination due to high defect density at the grain boundary and surface of perovskitefilms.To address this issue,a pyrrolidinium iodide(PyI)molecule was introduced to modify the surface and grain boundary of CsPbI_(3) perovskitefilms to passivate defects,which improves the quality of CsPbI_(3) perovskitefilms as well as induces the generation of a quasi-2D Py_(2)CsPb_(2)I_(7) capping layer between per-ovskite layer and hole transport layer.Such quasi-2D Py_(2)CsPb_(2)I_(7) capping layer optimizes interface contact between CsPbI_(3) perovskite layer and hole transport layer and blocks the electron transfer from CsPbI_(3) perovskite photoactive layer to the hole transport layer.As a result,the performance of CsPbI_(3) PSCs is well improved to 17.87%for power conversion efficiency(PCE)with an ultra-high fill factor(FF)of 0.84.In addition,the PyI mole-cule modified CsPbI_(3) perovskite devices exhibit excellent stability,which remains its initial PCE almost unchanged after aging for 35 days under the dry air atmosphere(temperature:20℃–30℃,control relative humid-ity(RH):<10%).
文摘The exploitation of fossil resources to meet humanity’s energy needs is the root cause of the climate warming phenomenon facing the planet. In this context, non-carbon-based energies, such as photovoltaic energy, are identified as crucial solutions. Organic perovskites MAPbI<sub>3</sub> and FAPbI<sub>3</sub>, characterized by their abundance, low cost, and ease of synthesis, are emerging as candidates for study to enhance their competitiveness. It is within this framework that this article presents a comparative analysis of the performances of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> perovskites in the context of photovoltaic devices. The analysis focuses on the optoelectronic characteristics and stability of these high-potential materials. The optical properties of perovskites are rigorously evaluated, including band gaps, photoluminescence, and light absorption, using UV-Vis spectroscopy and photoluminescence techniques. The crystal structure is characterized by X-ray diffraction, while film morphology is examined through scanning electron microscopy. The results reveal significant variations between the two types of perovskites, directly impacting the performance of resulting solar devices. Simultaneously, the stability of perovskites is subjected to a thorough study, exposing the materials to various environmental conditions, highlighting key determinants of their durability. Films of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> demonstrate distinct differences in terms of topography, optical performance, and stability. Research has unveiled that planar perovskite solar cells based on FAPbI<sub>3</sub> offer higher photoelectric conversion efficiency, surpassing their MAPbI<sub>3</sub>-based counterparts in terms of performance. These advancements aim to overcome stability constraints and enhance the long-term durability of perovskites, ultimately aiming for practical application of these materials. This comprehensive comparative analysis provides an enlightened understanding of the optoelectronic performance and stability of MAPbI<sub>3</sub> and FAPbI<sub>3</sub> perovskites, which is critically important to guide future research and development of solar devices that are both more efficient and sustainable.
文摘Perovskite materials have drawn a lot of interest recently due to their potential to increase solar cell efficiency. This study uses the solar cell capacitance simulator (SCAPS-1D) to develop and simulate a perovskite solar cell made of semiconductor materials. The design that has been suggested is Al:ZnO/ZnO/CdS/CsSnCl<sub>3</sub> and MoS<sub>2</sub>. The analysis focuses on how different characteristics of the material affect the device’s performance. The analysis of the data reveals that the architecture had 26.15% power conversion efficiency (PCE). The solar cell creates an interest in developing a non-toxic solar cell with low manufacturing costs, outstanding conversion efficiency, and stability.
基金Project supported bythe National Natural Science Foundation of China (50306008) and the Fund fromthe Preli minary Research Project of General Equipment Ministry (41328030507)
文摘Perovskite LaMnO3 powders with an average crystallite size of 12.5 nm were rapidly synthesized via a microwave-induced autocombustion reaction using glycine as a fuel and nitrate as an oxidant. After self-propagating combustion, the desired nanocrystalline perovskite LaMnO3 was obtained and no further calcination was carried out. The possible processes of combustion reaction were discussed according to the principle of propellant chemistry. The autocombustion and thermal decomposition of the precursor were investigated using the TG-DTA and FT-IR techniques. The influences of glycine-nitrate molar ratio and heat-treatment temperature on the perovskite phase formation and crystallite size of as-burnt powder were studied by XRD. The morphology and size of the as-burnt powder before and after milling were characterized and compared by TEM.
基金support from the National Natural Science Foundation of China (Grant Nos. 22025505, 51861145101,21777096)the Program of Shanghai Academic/Technology Research Leader (Grant No. 20XD1422200)+1 种基金the Key Laboratory of Resource Chemistry,Ministry of Education (Grant No.KLRC_ME2003)support from the Energy Materials and Surface Sciences Unit of the Okinawa Institute of Science and Technology Graduate University。
文摘Cesium lead iodide(CsPbI_(3)) perovskite has gained great attention in the photovoltaic(PV) community because of its unique optoelectronic properties, good chemical stability and appropriate bandgap for sunlight harvesting applications. However, compared to solar cells fabricated from organic-inorganic hybrid perovskites, the commercialization of devices based on all-inorganic CsPbI_(3) perovskites still faces many challenges regarding PV performance and long-term stability. In this work, we discovered that tetrabutylammonium bromide(TBABr) post-treatment to CsPbI_(3) perovskite films could achieve synergistic stabilization with both TBA+cation intercalation and Br-doping. Such TBA^(+) cation intercalation leads to onedimensional capping with TBAPb I3 perovskite formed in situ, while the Br-induced crystal secondary growth helps effectively passivate the defects of CsPbI_(3) perovskite, thus enhancing the stability. In addition, the incorporation of TBABr can improve energy-level alignment and reduce interfacial charge recombination loss for better device performance. Finally, the highly stable TBABr-treated CsPbI_(3)-based perovskite solar cells show reproducible photovoltaic performance with a champion efficiency up to 19.04%, while retaining 90% of the initial efficiency after 500 h storage without encapsulation.
基金financial support by the National Natural Science Foundation of China(21975038,21606039,and 51661135021)the Swiss National Science Foundation(IZLCZ2_170177)+3 种基金the Fundamental Research Funds for the Central Universities(DUT17JC39)the Swedish Foundation for Strategic Research(SSF)the Swedish Energy Agencythe Knut and Alice Wallenberg Foundation。
文摘All-inorganic cesium lead bromide(CsPbBr3)perovskite is attracting growing interest as functional materials in photovoltaics and other optoelectronic devices due to its superb stability.However,the fabrication of high-quality CsPbBr3 films still remains a big challenge by solution-process because of the low solubility of the cesium precursor in common solvents.Herein,we report a facile solution-processed approach to prepare high-quality CsPbBr3 perovskite films via a two-step spin-coating method,in which the Cs Br methanol/H2 O mixed solvent solution is spin-coated onto the lead bromide films,followed by an isopropanol-assisted post-treatment to regulate the crystallization process and to control the film morphology.In this fashion,dense and uniform CsPbBr3 films are obtained consisting of large crystalline domains with sizes up to microns and low defect density.The effectiveness of the resulting CsPbBr3 films is further examined in perovskite solar cells(PSCs)with a simplified planar architecture of fluorine–doped tin oxide/compact Ti O2/CsPbBr3/carbon,which deliver a maximum power conversion efficiency of 8.11%together with excellent thermal and humidity stability.The present work offers a simple and effective strategy in fabrication of high-quality CsPbBr3 films for efficient and stable PSCs as well as other optoelectronic devices.
基金financially supported by the China Scholarship Council,the National Natural Science Foundation of China(21976047,21790373 and 51774104)the Fundamental Research funds for the Central Universities(3072019CF1005)+1 种基金the Scientific Research and Special Foundation Heilongjiang Postdoctoral Science Foundation(LBH-Q15019,LBH-Q15020 and LBH-TZ0411)Ph.D.Student Research and Innovation Fund of the Fundamental Research Funds for the Central Universities(3072019GIP1011)。
文摘Due to the unique structure of perovskite materials,their capacitance can be improved by introducing oxygen vacancy.In this paper,the LaMnO3-δ material containing oxygen vacancy was synthesized by molten salt method in KNO3-NaNO3-NaNO2 melt.The La-Mn-O crystal grows gradually in molten salt with the increase of temperature.It was confirmed that LaMnO3-δ with perovskite structure and incomplete oxygen content were synthesized by molten salt method and presented a three-dimensional shape.LaMnO3-δ stores energy by redox reaction and adsorption of OH-in electrolyte simultaneously.In comparison with the stoichiometric LaMnO3 prepared by the sol-gel method,LaMnO3-δ prepared by molten salt method proffered higher capacitance and better performance.The galvanostatic charge-discharge curve showed specific capacitance of 973.5 F/g under current density of 1 A/g in 6 M KOH.The capacitance of LaMn03-δ was 82.7%under condition of 5 A/g compared with the capacitance at the current of 1A/g,and the specific capacitances of 648.0 and 310.0 F/g were obtained after 2000 and 5000 cycles of galvanostatic charging-discharging,respectively.Molten salt synthesis method is relatively simple and suitable for industrial scale,presenting a promising prospect in the synthesis of perovskite oxide materials.
基金Project supported by the National Natural Science Foundation of China(Grant No.11176020)
文摘The structural, electronic, and optical properties of cubic perovskite NaMgF3 are calculated by plane-wave pseudopo- tential density functional theory. The calculated lattice constant a0, bulk modulus B0, and the derivative of bulk modulus B~ are 3.872/~, 78.2 GPa, and 3.97, respectively. The results are in good agreement with the available experimental and theo- retical values. The electronic structure shows that cubic NaMgF3 is an indirect insulator with a wide forbidden band gap of Eg = 5.90 eV. The contribution of the different bands is analyzed by total and partial density of states curves. Population analysis of NaMgF3 indicates that there is strong ionic bonding in the MgF2 unit, and a mixture of ionic and weak covalent bonding in the NaF unit. Calculations of dielectric function, absorption coefficient, refractive index, electronic energy loss spectroscopy, optical reflectivity, and conductivity are also performed in the energy range 0 to 70 eV.