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
Electrochemical energy storage(EES)systems like batteries and supercapacitors are becoming the key power sources for attempts to change the energy dependency from inadequate fossil fuels to sustainable and renewable r...Electrochemical energy storage(EES)systems like batteries and supercapacitors are becoming the key power sources for attempts to change the energy dependency from inadequate fossil fuels to sustainable and renewable resources.Electrochemical energy storage devices(EESDs)operate efficiently as a result of the construction and assemblage of electrodes and electrolytes with appropriate structures and effective materials.Conventional manufacturing procedures have restrictions on regulating the morphology and architecture of the electrodes,which would influence the performance of the devices.3D printing(3DP)is an advanced manufacturing technology combining computer-aided design and has been recognised as an artistic method of fabricating different fragments of energy storage devices with its ability to precisely control the geometry,porosity,and morphology with improved specific energy and power densities.The capacity to create mathematically challenging shape or configuration designs and high-aspect-ratio 3D architectures makes 3D printing technology unique in its benefits.Nevertheless,the control settings,interactive manufacturing processes,and protracted post-treatments will affect the reproducibility of the printed components.More intelligent software,sophisticated control systems,high-grade industrial equipment,and post-treatment-free methods are necessary to develop.3D printed(3DPd)EESDs necessitate dynamic printable materials and composites that are influenced by performance criteria and fundamental electrochemistry.Herein,we review the recent advances in 3DPd electrodes for EES applications.The emphasis is on printable material synthesis,3DP techniques,and the electrochemical performance of printed electrodes.For the fabrication of electrodes,we concentrate on major 3DP technologies such as direct ink writing(DIW),inkjet printing(IJP),fused deposition modelling(FDM),and stereolithography3DP(SLA).The benefits and drawbacks of each 3DP technology are extensively discussed.We provide an outlook on the integration of synthesis of emerging nanomaterials and fabrication of complex structures from micro to macroscale to construct highly effective electrodes for the EESDs.展开更多
Redox-enzyme‐mediated electrochemical processes such as hydrogen production,nitrogen fixation,and CO_(2) reduction are at the forefront of the green chemistry revolution.To scale up,the inefficient two‐dimensional(2...Redox-enzyme‐mediated electrochemical processes such as hydrogen production,nitrogen fixation,and CO_(2) reduction are at the forefront of the green chemistry revolution.To scale up,the inefficient two‐dimensional(2D)immobilization of redox enzymes on working electrodes must be replaced by an efficient dense 3D system.Fabrication of 3D electrodes was demonstrated by embedding enzymes in polymer matrices.However,several requirements,such as simple immobilization,prolonged stability,and resistance to enzyme leakage,still need to be addressed.The study presented here aims to overcome these gaps by immobilizing enzymes in a supramolecular hydrogel formed by the self‐assembly of the peptide hydrogelator fluorenylmethyloxycarbonyldiphenylalanine.Harnessing the self‐assembly process avoids the need for tedious and potentially harmful chemistry,allowing the rapid loading of enzymes on a 3D electrode under mild conditions.Using the[FeFe]hydrogenase enzyme,high enzyme loads,prolonged resistance against electrophoresis,and highly efficient hydrogen production are demonstrated.Further,this enzyme retention is shown to arise from its interaction with the peptide nanofibrils.Finally,this method is successfully used to retain other redox enzymes,paving the way for a variety of enzyme‐mediated electrochemical applications.展开更多
While transition-metal oxides such as α-MoO_(3)provide high capacity,their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes.Two-dimensional(2D)MXenes,offer meta...While transition-metal oxides such as α-MoO_(3)provide high capacity,their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes.Two-dimensional(2D)MXenes,offer metallic conductivity,but their capacitance is limited in aqueous electrolytes.Insertion of partially solvated cations into Ti_(3)C_(2)MXene from lithium-based water-in-salt(WIS)electrolytes enables charge storage at positive potentials,allowing a wider potential window and higher capacitance.Herein,we demonstrate that α-MoO_(3)/Ti_(3)C_(2)hybrids combine the high capacity of α-MoO_(3)and conductivity of Ti_(3)C_(2)in WIS(19.8 m LiCI)electrolyte in a wide1.8 V voltage window.Cyclic voltammograms reveal multiple redox peaks from α-MoO_(3)in addition to the well-separated peaks of Ti_(3)C_(2)in the hybrid electrode.This leads to a higher specific charge and a higher rate capability compared to a carbon and binder containing α-MoO_(3)electrode.These results demonstrate that the addition of MXene to less conductive oxides eliminates the need for conductive carbon additives and binders,leads to a larger amount of charge stored,and increases redox capacity at higher rates.In addition,MXene encapsulated α-MoO_(3)showed improved electrochemical stability,which was attributed to the suppressed dissolution of α-MoO_(3).The work suggests that oxide/MXene hybrids are promising for energy storage.展开更多
B_(2)O_(3)-Zn O-SiO_(2)(BZS)glass containing Cu O with excellent acid resistance,wetting properties,and high-temperature sintering density was prepared by high temperature melting method and then applied in copper ter...B_(2)O_(3)-Zn O-SiO_(2)(BZS)glass containing Cu O with excellent acid resistance,wetting properties,and high-temperature sintering density was prepared by high temperature melting method and then applied in copper terminal electrode for multilayer ceramic capacitors(MLCC)applications.The structure and property characterization of B_(2)O_(3)-Zn O-SiO_(2)glass,including X-ray diffraction,FTIR,scanning electron microscopy,high-temperature microscopy,and differential scanning calorimetry,indicated that the addition of CuO improved the glass’s acid resistance and glass-forming ability.The wettability and acid resistance of this glass were found to be excellent when CuO content was 1.50 wt%.Compared to BZS glass,the CuO-added glass exhibited excellent wettability to copper powder and corrosion resistance to the plating solution.The sintered copper electrode films prepared using the glass with CuO addition had better densification and lower sintering temperature of 750℃.Further analysis of the sintering mechanism reveals that the flowability and wettability of the glass significantly impact the sintering densification of the copper terminal electrodes.展开更多
The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology ...The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology and constitution of Ir film were examined by scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS） and X-ray diffraction （XRD）. It is found that the reduction mechanism of Ir（III） is a three-electron step and electro reaction is a reversible diffusion controlled process; the diffusion coefficients of Ir（III） at 1083, 1113, 1143 and 1183 K are 1.56×10-4, 2.23×10-4, 2.77×10-4 and 4.40×10-4 cm2/s, respectively, while the activation energy of the electrode reaction is 102.95 kJ/mol. The compacted Ir film reveals that the applied potential greatly affects the deposition of Ir, the thickness of Ir film deposited at the potential of reduction peak is the highest, the temperature of the molten salt also exerts an influence on deposition, the film formed at a lower temperature is thinner, but more micropores would occur on film when the temperature went too high.展开更多
LaNiO3 (LNO) thin films were prepared on Pt(111) / Ti / SiO2 / Si substrate by metal-organic decomposition (MOD) method. Pb(Zr,Ti)O3 ferroelectric thin films and their compositionally graded thin films were prepared o...LaNiO3 (LNO) thin films were prepared on Pt(111) / Ti / SiO2 / Si substrate by metal-organic decomposition (MOD) method. Pb(Zr,Ti)O3 ferroelectric thin films and their compositionally graded thin films were prepared on LNO / Pt / Ti / SiO2 /Si substrates by Sol-gel method. The composition depth profile of a typical up-graded film was determined by using a combination of Auger Electron Spectroscopy (ASE) and Ar Ion Etching. The results confirm that the processing method produces graded composition changes. XRD analysis showed that the graded thin films possessed composite structure of tetragonal and rhombohedral. The dielectric constants of Up-graded and Down-graded thin films were higher than that of each thin film unit. The dielectric constants were 277 and 269 at 10 kHz, respectively. The loss tangents were 0.019 and 0.018 at 10 kHz, respectively. The Hysteresis loops showed that the remanent polarizations of graded thin films were higher than that of each thin film unit, but the coercive fields were smaller. The remanent polarizations of Up-graded and Down-graded thin films were 30.06 and 26.96 μC·cm-2, respectively. The coercive fields were 54.14, 54.23 kV·cm-1, respectively. The pyroelectric coefficients of Up-graded and Down-graded thin films were 4.62, 2.51×10-8 C·cm-2·K-1 at room temperature, respectively. They were higher than that of each thin film unit.展开更多
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supported by the National Research Foundation of Korea (NRF)grant funded by the Korea government (MSIT) (No.2021R1A2C2006888)。
文摘Electrochemical energy storage(EES)systems like batteries and supercapacitors are becoming the key power sources for attempts to change the energy dependency from inadequate fossil fuels to sustainable and renewable resources.Electrochemical energy storage devices(EESDs)operate efficiently as a result of the construction and assemblage of electrodes and electrolytes with appropriate structures and effective materials.Conventional manufacturing procedures have restrictions on regulating the morphology and architecture of the electrodes,which would influence the performance of the devices.3D printing(3DP)is an advanced manufacturing technology combining computer-aided design and has been recognised as an artistic method of fabricating different fragments of energy storage devices with its ability to precisely control the geometry,porosity,and morphology with improved specific energy and power densities.The capacity to create mathematically challenging shape or configuration designs and high-aspect-ratio 3D architectures makes 3D printing technology unique in its benefits.Nevertheless,the control settings,interactive manufacturing processes,and protracted post-treatments will affect the reproducibility of the printed components.More intelligent software,sophisticated control systems,high-grade industrial equipment,and post-treatment-free methods are necessary to develop.3D printed(3DPd)EESDs necessitate dynamic printable materials and composites that are influenced by performance criteria and fundamental electrochemistry.Herein,we review the recent advances in 3DPd electrodes for EES applications.The emphasis is on printable material synthesis,3DP techniques,and the electrochemical performance of printed electrodes.For the fabrication of electrodes,we concentrate on major 3DP technologies such as direct ink writing(DIW),inkjet printing(IJP),fused deposition modelling(FDM),and stereolithography3DP(SLA).The benefits and drawbacks of each 3DP technology are extensively discussed.We provide an outlook on the integration of synthesis of emerging nanomaterials and fabrication of complex structures from micro to macroscale to construct highly effective electrodes for the EESDs.
基金Ministry of Energy,Israel,Grant/Award Numbers:219‐11‐120,222‐11‐065Israel Science Foundation,Grant/Award Number:GA 2185/17。
文摘Redox-enzyme‐mediated electrochemical processes such as hydrogen production,nitrogen fixation,and CO_(2) reduction are at the forefront of the green chemistry revolution.To scale up,the inefficient two‐dimensional(2D)immobilization of redox enzymes on working electrodes must be replaced by an efficient dense 3D system.Fabrication of 3D electrodes was demonstrated by embedding enzymes in polymer matrices.However,several requirements,such as simple immobilization,prolonged stability,and resistance to enzyme leakage,still need to be addressed.The study presented here aims to overcome these gaps by immobilizing enzymes in a supramolecular hydrogel formed by the self‐assembly of the peptide hydrogelator fluorenylmethyloxycarbonyldiphenylalanine.Harnessing the self‐assembly process avoids the need for tedious and potentially harmful chemistry,allowing the rapid loading of enzymes on a 3D electrode under mild conditions.Using the[FeFe]hydrogenase enzyme,high enzyme loads,prolonged resistance against electrophoresis,and highly efficient hydrogen production are demonstrated.Further,this enzyme retention is shown to arise from its interaction with the peptide nanofibrils.Finally,this method is successfully used to retain other redox enzymes,paving the way for a variety of enzyme‐mediated electrochemical applications.
基金supported by the Fluid Interface Reacions and Transport(FIRST)Centeran Energy Frontier Research Center supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences+1 种基金Synthesis,XRD,and SEM characterization of α-MoO_(3) were supported as a part of the Center for Mesoscale Transport PropertiesEnergy Frontier Research Center supported by the U.S.Department of Energy,Office of Science,Basic Energy Sciences,under award#DE-SC0012673
文摘While transition-metal oxides such as α-MoO_(3)provide high capacity,their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes.Two-dimensional(2D)MXenes,offer metallic conductivity,but their capacitance is limited in aqueous electrolytes.Insertion of partially solvated cations into Ti_(3)C_(2)MXene from lithium-based water-in-salt(WIS)electrolytes enables charge storage at positive potentials,allowing a wider potential window and higher capacitance.Herein,we demonstrate that α-MoO_(3)/Ti_(3)C_(2)hybrids combine the high capacity of α-MoO_(3)and conductivity of Ti_(3)C_(2)in WIS(19.8 m LiCI)electrolyte in a wide1.8 V voltage window.Cyclic voltammograms reveal multiple redox peaks from α-MoO_(3)in addition to the well-separated peaks of Ti_(3)C_(2)in the hybrid electrode.This leads to a higher specific charge and a higher rate capability compared to a carbon and binder containing α-MoO_(3)electrode.These results demonstrate that the addition of MXene to less conductive oxides eliminates the need for conductive carbon additives and binders,leads to a larger amount of charge stored,and increases redox capacity at higher rates.In addition,MXene encapsulated α-MoO_(3)showed improved electrochemical stability,which was attributed to the suppressed dissolution of α-MoO_(3).The work suggests that oxide/MXene hybrids are promising for energy storage.
基金the National Natural Science Foundation of China(Nos.51372179,51772224)the Open Project Foundation of Guangdong Fenghua Advanced Technology(No.FHR-JS-202011024)。
文摘B_(2)O_(3)-Zn O-SiO_(2)(BZS)glass containing Cu O with excellent acid resistance,wetting properties,and high-temperature sintering density was prepared by high temperature melting method and then applied in copper terminal electrode for multilayer ceramic capacitors(MLCC)applications.The structure and property characterization of B_(2)O_(3)-Zn O-SiO_(2)glass,including X-ray diffraction,FTIR,scanning electron microscopy,high-temperature microscopy,and differential scanning calorimetry,indicated that the addition of CuO improved the glass’s acid resistance and glass-forming ability.The wettability and acid resistance of this glass were found to be excellent when CuO content was 1.50 wt%.Compared to BZS glass,the CuO-added glass exhibited excellent wettability to copper powder and corrosion resistance to the plating solution.The sintered copper electrode films prepared using the glass with CuO addition had better densification and lower sintering temperature of 750℃.Further analysis of the sintering mechanism reveals that the flowability and wettability of the glass significantly impact the sintering densification of the copper terminal electrodes.
文摘The reduction mechanism of Ir in the NaCl-KCl-IrCl3 molten salt was investigated by cyclic voltammetry and chronopotentiometry, and Ir film was deposited effectively on platinum in potentiostatic mode. The morphology and constitution of Ir film were examined by scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS） and X-ray diffraction （XRD）. It is found that the reduction mechanism of Ir（III） is a three-electron step and electro reaction is a reversible diffusion controlled process; the diffusion coefficients of Ir（III） at 1083, 1113, 1143 and 1183 K are 1.56×10-4, 2.23×10-4, 2.77×10-4 and 4.40×10-4 cm2/s, respectively, while the activation energy of the electrode reaction is 102.95 kJ/mol. The compacted Ir film reveals that the applied potential greatly affects the deposition of Ir, the thickness of Ir film deposited at the potential of reduction peak is the highest, the temperature of the molten salt also exerts an influence on deposition, the film formed at a lower temperature is thinner, but more micropores would occur on film when the temperature went too high.
文摘LaNiO3 (LNO) thin films were prepared on Pt(111) / Ti / SiO2 / Si substrate by metal-organic decomposition (MOD) method. Pb(Zr,Ti)O3 ferroelectric thin films and their compositionally graded thin films were prepared on LNO / Pt / Ti / SiO2 /Si substrates by Sol-gel method. The composition depth profile of a typical up-graded film was determined by using a combination of Auger Electron Spectroscopy (ASE) and Ar Ion Etching. The results confirm that the processing method produces graded composition changes. XRD analysis showed that the graded thin films possessed composite structure of tetragonal and rhombohedral. The dielectric constants of Up-graded and Down-graded thin films were higher than that of each thin film unit. The dielectric constants were 277 and 269 at 10 kHz, respectively. The loss tangents were 0.019 and 0.018 at 10 kHz, respectively. The Hysteresis loops showed that the remanent polarizations of graded thin films were higher than that of each thin film unit, but the coercive fields were smaller. The remanent polarizations of Up-graded and Down-graded thin films were 30.06 and 26.96 μC·cm-2, respectively. The coercive fields were 54.14, 54.23 kV·cm-1, respectively. The pyroelectric coefficients of Up-graded and Down-graded thin films were 4.62, 2.51×10-8 C·cm-2·K-1 at room temperature, respectively. They were higher than that of each thin film unit.
