Nanostructures and multi-scale aggregation of high ion exchange capacity short-side-chain perfluorosulfonic acid dispersion.

Short-side-chain perfluorosulfonic acid (SSC-PFSA) ionomers with high ion-exchange-capacity are promising candidates for high-temperature proton exchange membranes (PEMs) and catalyst layer (CL) binders. The solution-casting method determines the importance of SSC-PFSA dispersion characteristics in shaping the morphology of PEMs and CLs. Therefore, a thorough understanding of the chain behavior of SSC-PFSA in dispersions is essential for fabricating high-quality PEMs and CLs. In this study, we have employed multiple characterization techniques, including dynamic light scatting (DLS), small-angle X-ray scattering (SAXS), and cryo-transmission electron microscope (Cryo-TEM), to fully study the chain aggregation behaviors of SSC-PFSA in water-ethanol solvents and elucidate the concentration-dependent self-assembly process. In dilute dispersions (2 mg/mL), SSC-PFSA assembles into mono-disperse rod-like aggregates, featuring a twisted fluorocarbon backbone that forms a hydrophobic stem, and the sulfonic acid side chains extending outward to suit the hydrophilic environment. As the concentration increases, the radius of rod particles increases from 1.47 to 1.81 nm, and the mono-disperse rod particles first form a "end-to-end" configuration that doubles length (10 mg/mL), and then transform into a swollen network structure in semi-dilute dispersion (20 mg/mL). This work provides a well-established structure model for SSC-PFSA dispersions, which is the key nanostructure to be inherited by PEMs.

ZIF67-ZIF8@MFC-Derived Co-Zn/NC Interconnected Frameworks Combined with Perfluorosulfonic Acid Polymer as a Highly Efficient and Stable Composite Electrocatalyst for Oxygen Reduction Reactions.

The development of precious metal-free (M-N-C) catalysts for the oxygen reduction reaction (ORR) is considered crucial for reducing fuel cell costs. Herein, Co-Zn/NC interconnected frameworks with uniformly dispersed Co nanoparticles and graphitic carbon are designed and successfully synthesized through the in situ growth of zeolitic imidazolate frameworks (ZIF67 and ZIF8) along with biomass nano-microfibrillar cellulose (MFC), followed by pyrolysis. A Co-Zn/NC composite is prepared by combining Co-Zn/NC with a perfluorosulfonic acid polymer. The Co-Zn/NC composite catalyst exhibits excellent ORR catalytic activity (E0 = 0.974 V vs. RHE, E1/2 = 0.858 V vs. RHE) and good long-term durability, with 90% current retention after 10000s, surpassing that of commercial Pt/C in alkaline media. The hierarchical porous structure, coupled with the uniform distribution of Co nanoparticles and nitrogen doping, contributes to superior electrocatalytic performance, while the interconnected frameworks and graphitic carbon ensure good stability. Additionally, the Co-Zn/NC composite demonstrates promising applications in acidic media. This strategy offers significant guidance to develop advanced non-precious metal carbon-based catalysts for highly efficient and stable ORR.

Rational Materials and Structure Design for Improving the Performance and Durability of High Temperature Proton Exchange Membranes (HT-PEMs).

Hydrogen energy as the next-generation clean energy carrier has attracted the attention of both academic and industrial fields. A key limit in the current stage is the operation temperature of hydrogen fuel cells, which lies in the slow development of high-temperature and high-efficiency proton exchange membranes. Currently, much research effort has been devoted to this field, and very innovative material systems have been developed. The authors think it is the right time to make a short summary of the high-temperature proton exchange membranes (HT-PEMs), the fundamentals, and developments, which can help the researchers to clearly and efficiently gain the key information. In this paper, the development of key materials and optimization strategies, the degradation mechanism and possible solutions, and the most common morphology characterization techniques as well as correlations between morphology and overall properties have been systematically summarized.

Design Rules of the Mixing Phase and Impacts on Device Performance in High-Efficiency Organic Photovoltaics.

In nonfullerene acceptor- (NFA-) based solar cells, the exciton splitting takes place at both domain interface and donor/acceptor mixture, which brings in the state of mixing phase into focus. The energetics and morphology are key parameters dictating the charge generation, diffusion, and recombination. It is revealed that tailoringthe electronic properties of the mixing region by doping with larger-bandgap components could reduce the density of state but elevate the filling state level, leading to improved open-circuit voltage (V OC) and reduced recombination. The monomolecular and bimolecular recombinations are shown to be intercorrelated, which show a Gaussian-like relationship with V OC and linear relationship with short-circuit current density (J SC) and fill factor (FF). The kinetics of hole transfer and exciton diffusion scale with J SC similarly, indicating the carrier generation in mixing region and crystalline domain are equally important. From the morphology perspective, the crystalline order could contribute to V OC improvement, and the fibrillar structure strongly affects the FF. These observations highlight the importance of the mixing region and its connection with crystalline domains and point out the design rules to optimize the mixing phase structure, which is an effective approach to further improve device performance.

Capture the high-efficiency non-fullerene ternary organic solar cells formula by machine-learning-assisted energy-level alignment optimization.

Appropriate energy-level alignment in non-fullerene ternary organic solar cells (OSCs) can enhance the power conversion efficiencies (PCEs), due to the simultaneous improvement in charge generation/transportation and reduction in voltage loss. Seven machine-learning (ML) algorithms were used to build the regression and classification models based on energy-level parameters to predict PCE and capture high-performance material combinations, and random forest showed the best predictive capability. Furthermore, two sets of verification experiments were designed to compare the experimental and predicted results. The outcome elucidated that a deep lowest unoccupied molecular orbital (LUMO) of the non-fullerene acceptors can slightly reduce the open-circuit voltage (V OC) but significantly improve short-circuit current density (J SC), and, to a certain extent, the V OC could be optimized by the slightly up-shifted LUMO of the third component in non-fullerene ternary OSCs. Consequently, random forest can provide an effective global optimization scheme and capture multi-component combinations for high-efficiency ternary OSCs.

Interfacial and Permeating Modification Effect of n-type Non-fullerene Acceptors toward High-Performance Perovskite Solar Cells.

Interface passivation in the electron transport layer (ETL) has emerged as a very important and challenging topic for the improvement of stability and efficiency of perovskite solar cells (PSCs). Here, we introduce the n-type small organic molecule Y6 that acts as an effective ETL modifier through surface engineering. As a result, the simple PCBM + Y6 ETL led to significantly stronger light absorption, higher electron extraction ability and transportability, and reduced recombination loss in regular MAPbI3 PSCs. The power conversion efficiency can be significantly increased from 17.39 to 20.02% in inverted p-i-n MAPbI3 PSCs without additional alternation, with an increment of over 15%, along with higher open-circuit voltage and short-circuit current. What is more, the devices with the Y6-modified ETL also exhibited better long-term stability compared to the control devices. This indicates the feasibility of enhancing absorption over a wider light spectrum in a single-junction cell and gaining a comprehensive understanding of interface engineering between the ETL and perovskite layer.

Unraveling the Crystallization Kinetics of 2D Perovskites with Sandwich-Type Structure for High-Performance Photovoltaics.

2D perovskite solar cells with high stability and high efficiency have attracted significant attention. A systematical static and dynamic structure investigation is carried out to show the details of 2D morphology evolution. A dual additive approach is used, where the synergy between an alkali metal cation and a polar solvent leads to high-quality 2D perovskite films with sandwich-type structures and vertical phase segregation. Such novel structure can induce high-quality 2D slab growth and reduce internal and surface defects, resulting in a high device efficiency of 16.48% with enhanced continuous illumination stability and improved moisture (55-60%) and thermal (85 °C) tolerances. Transient absorption spectra reveal the carrier migration from low n to high n species with different kinetics. An [PbI6 ]4- octagon coalescence transformation mechanism coupled with metal and organic cations wrapped is proposed. By solvent vapor annealing, a recrystallization and reorientation of the 2D perovskite slabs occurs to form an ideal structure with improved device performance and stability.

Interfacial and structural modifications in perovskite solar cells.

The rapid and continuous progress made in perovskite solar cell (PSC) technology has drawn considerable attention from the photovoltaic research community, and the application of perovskites in other electronic devices (such as photodetectors, light-emitting diodes, and batteries) has become imminent. Because of the diversity in device configurations, optimization of film deposition, and exploration of material systems, the power conversion efficiency (PCE) of PSCs has been certified to be as high as 25.2%, making this type of solar cells the fastest advancing technology until now. As demonstrated by researchers worldwide, controlling the morphology and defects in perovskite films is essential for attaining high-performance PSCs. In this regard, interface engineering has proven to be a very efficient way to address these issues, obtaining better charge collection efficiency, and reducing recombination losses. In this review, the interfacial modification between perovskite films and charge-transport layers (CTLs) as well as CTLs and electrodes of PSCs has been widely summarized. Grain boundary (GB) engineering and stress engineering are also included since they are closely related to the improvement in device performance and stability.

Aggregation-Induced Multilength Scaled Morphology Enabling 11.76% Efficiency in All-Polymer Solar Cells Using Printing Fabrication.

All-polymer solar cells (all-PSCs) exhibit excellent stability and readily tunable ink viscosity, and are therefore especially suitable for printing preparation of large-scale devices. At present, the efficiency of state-of-the-art all-PSCs fabricated by the spin-coating method has exceeded 11%, laying the foundation for the preparation and practical utilization of printed devices. A high power conversion efficiency (PCE) of 11.76% is achieved based on PTzBI-Si:N2200 all-PSCs processing with 2-methyltetrahydrofuran (MTHF, an environmentally friendly solvent) and preparation of active layers by slot die printing, which is the top efficient for all-PSCs. Conversely, the PCE of devices processed by high-boiling point chlorobenzene is less than 2%. Through the study of film formation kinetics, volatile solvents can freeze the morphology in a short time, and a more rigid conformation with strong intermolecular interaction combined with the solubility limit of PTzBI-Si and N2200 in MTHF results in the formation of a fibril network in the bulk heterojunction. The multilength scaled morphology ensures fast transfer of carriers and facilitates exciton separation, which boosts carrier mobility and current density, thus improving the device performance. These results are of great significance for large-scale printing fabrication of high-efficiency all-PSCs in the future.

A one-step method to fabricate novel three-dimensional GaP nanopore arrays for enhanced photoelectrochemical hydrogen production.

Gallium phosphide nanopore arrays with unique three-dimensional interior architectures (3D GaP NPs) are fabricated by electrochemical etching in a neutral solution. As the photoanodes for photoelectrochemical (PEC) hydrogen production, the 3D GaP NPs exhibited a larger photocurrent density (5.65 mA cm-2 at 0 V vs. RHE, which is 58.3 and 2.3 times as large as that of the planar wafer and the NPs reported by our group in our previous work respectively) and a lower onset potential (-0.58 V vs. RHE, shifting negatively nearly 300 mV compared with its counterparts in the previous work). Besides the excellent light-trapping characteristics of the nanostructures, electrochemical impedance spectroscopy (EIS) further confirmed that the enhanced PEC performance was ascribed to the more efficient charge separation and transfer, and the increased surface area with the unique 3D NP arrays. Furthermore, the efficient charge separation may be attributed to the passivated surface states by the neutral solution.

Nickel skeleton three-dimensional nitrogen doped graphene nanosheets/nanoscrolls as promising supercapacitor electrodes.

A novel nickel skeleton 3D nitrogen doped graphene (N-GR/NF) superstructure with interconnected graphene nanosheets and nanoscrolls was synthesized using a facile two-step method. By varying the precursor concentration, the assembly of a graphene aerogel can be easily regulated, yielding different micro-structures and morphologies which accelerate the fast electron/ion transportation. The N-GR/NF composites demonstrate enhanced capacitance of 250 F g-1 at 5 A g-1, good rate performance (237 F g-1 at the current density of 12 A g-1) and cycle stability (90.9% retention after 5000 cycles) in 1 M KOH electrolyte. This study provides a new strategy for the microporous engineering of graphene gel, promising for further exploitation in various other applications.

Galvanic displacement assembly of ultrathin Co3O4 nanosheet arrays on nickel foam for a high-performance supercapacitor.

High-performance supercapacitors are very desirable for many portable electronic devices, electric vehicles and high-power electronic devices. Herein, a facile and binder-free synthesis method, galvanic displacement of the precursor followed by heat treatment, is used to fabricate ultrathin Co3O4 nanosheet arrays on nickel foam substrate. When used as a supercapacitor electrode the prepared Co3O4 on nickel foam exhibits a maximum specific capacitance of 1095 F g-1 at a current density of 1 A g-1 and good cycling stability of 71% retention after 2000 cycling tests. This excellent electrochemical performance can be ascribed to the high specific surface area of each Co3O4 nanosheet that comprises numerous nanoparticles.

Fast Growth of Highly Ordered TiO2 Nanotube Arrays on Si Substrate under High-Field Anodization.

ABSTRACT: Highly ordered TiO2 nanotube arrays (NTAs) on Si substrate possess broad applications due to its high surface-to-volume ratio and novel functionalities, however, there are still some challenges on facile synthesis. Here, we report a simple and cost-effective high-field (90-180 V) anodization method to grow highly ordered TiO2 NTAs on Si substrate, and investigate the effect of anodization time, voltage, and fluoride content on the formation of TiO2 NTAs. The current density-time curves, recorded during anodization processes, can be used to determine the optimum anodization time. It is found that the growth rate of TiO2 NTAs is improved significantly under high field, which is nearly 8 times faster than that under low fields (40-60 V). The length and growth rate of the nanotubes are further increased with the increase of fluoride content in the electrolyte. GRAPHICAL ABSTRACT: Highly ordered TiO2 nanotube arrays (NTAs) on Si substrate have been fabricated by high-field anodization method. A high voltage (90-180 V) leads to a high growth rate of TiO2 NTAs (35-47 nm s-1), which is nearly 8 times faster than the growth rate under low fields (40-60 V). Furthermore, the current density-time curves recorded during the anodization provide a facial method to determine the optimal anodization parameters, leading to an easy obtaining of the desired nanotubes.

Unique Three-Dimensional InP Nanopore Arrays for Improved Photoelectrochemical Hydrogen Production.

Ordered three-dimensional (3D) nanostructure arrays hold promise for high-performance energy harvesting and storage devices. Here, we report the fabrication of InP nanopore arrays (NPs) in unique 3D architectures with excellent light trapping characteristic and large surface areas for use as highly active photoelectrodes in photoelectrochemical (PEC) hydrogen evolution devices. The ordered 3D NPs were scalably synthesized by a facile two-step etching process of (1) anodic etching of InP in neutral 3 M NaCl electrolytes to realize nanoporous structures and (2) wet chemical etching in HCl/H3PO4 (volume ratio of 1:3) solutions for removing the remaining top irregular layer. Importantly, we demonstrated that the use of neutral electrolyte of NaCl instead of other solutions, such as HCl, in anodic etching of InP can significantly passivate the surface states of 3D NPs. As a result, the maximum photoconversion efficiency obtained with ∼15.7 µm thick 3D NPs was 0.95%, which was 7.3 and 1.4 times higher than that of planar and 2D NPs. Electrochemical impedance spectroscopy and photoluminescence analyses further clarified that the improved PEC performance was attributed to the enhanced charge transfer across 3D NPs/electrolyte interfaces, the improved charge separation at 3D NPs/electrolyte junction, and the increased PEC active surface areas with our unique 3D NP arrays.

InP nanopore arrays for photoelectrochemical hydrogen generation.

We report a facile and large-scale fabrication of highly ordered one-dimensional (1D) indium phosphide (InP) nanopore arrays (NPs) and their application as photoelectrodes for photoelectrochemical (PEC) hydrogen production. These InP NPs exhibit superior PEC performance due to their excellent light-trapping characteristics, high-quality 1D conducting channels and large surface areas. The photocurrent density of optimized InP NPs is 8.9 times higher than that of planar counterpart at an applied potential of +0.3 V versus RHE under AM 1.5G illumination (100 mW cm(-2)). In addition, the onset potential of InP NPs exhibits 105 mV of cathodic shift relative to planar control. The superior performance of the nanoporous samples is further explained by Mott-Schottky and electrochemical impedance spectroscopy ananlysis.

A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties.

Here, large-scale and uniform hexagonal zinc oxide (ZnO) nanosheet films were deposited onto indium tin oxide (ITO)-coated transparent conducting glass substrates via a facile galvanic displacement deposition process. Compared with other commonly used solution methods, this process avoids high temperature and electric power as well as supporting agents to make it simple and cost-effective. The as-fabricated ZnO nanosheet films have uniform hexagonal wurtzite structure. The photoelectrochemical (PEC) cell based on ZnO nanosheet film/ITO photoelectrode was also fabricated and its performance was improved by optimizing the solution concentration. A higher photocurrent density of ~500 µA cm-2 under AM 1.5 G simulated illumination of 100 mW cm-2 with zero bias potential (vs. Ag/AgCl electrode) was obtained, which may ascribe to the increased surface-to-volume ratio of disordered ZnO nanosheet arrays. Our developed method may be used to deposit other oxide semiconductors, and the ZnO nanosheet film/ITO PEC cell can be used to design low-cost optoelectronic and photoelectrochemical devices.

Erratum to: A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties.

[This corrects the article DOI: 10.1007/s40820-015-0068-y.].