The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spac...The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.展开更多
This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes...This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.展开更多
基金supported by the National Key Research and Development Programs-Intergovernmental International Cooperation in Science and Technology Innovation Project(Grant No.2022YFE0118400)the Natural Science Foundation of Hunan Province(2023JJ50132)+1 种基金Shenzhen Science and Technology Innovation Committee(Grants Nos.JCYJ20220818100211025,and KCXST20221021111616039)Shenzhen Science and Technology Program(No.20231128110928003)。
文摘The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.
基金supported by the National Natural Science Foundation of China(22271075,22171071)。
文摘This study presents a novel polyoxometalate(POM)constructed crystalline inorganic framework,featuring a 2D layered architecture with irregular porosity and inherent proton sources.This unique configuration establishes an intrinsic hydrogen bonding network that facilitates proton hopping(Grotthuss mechanism),achieving a[100]directional proton conductivity of 1.75×10^(-3)S cm^(-1)under a low relative humidity(RH)of 35%at 298 K.Notably,under elevated conditions(338 K,95%RH),it attains a superprotonic conductivity of 1.61 S cm^(-1),representing one of the highest values recorded for framework materials to date.Analysis of the molecular structure,pore geometry characteristics and topological connectivity,and water vapor adsorption experiment(offering proton diffusion coefficient),indicates that the exceptional water-mediated proton dynamics stem from the interlayer S-shaped irregular pore channels,which probably induce a siphon-like effect to significantly enhance the transport of hydrated protons under the vehicle mechanism.This work not only proposes a POM strategy for constructing 2D inorganic frameworks but also reveals the irregular pore channel-enhanced proton dynamics,providing new insights into the optimization of proton conductors.
