Layer-by-Layer-Processed All-Polymer Solar Cells with Enhanced Performance Enabled by Regulating the Microstructure of Upper Layer.

The layer-by-layer (LBL) fabrication method allows for controlled microstructure morphology and vertical component distribution, and also offers a reproducible and efficient technique for fabricating large-scale organic solar cells (OSCs). In this study, the polymers D18 and PYIT-OD are employed to fabricate all-polymer solar cells (all-PSCs) using the LBL method. Morphological studies reveal that the use of additives optimizes the microstructure of the active layer, enhancing the cells' crystallinity and charge transport capability. The optimized device with 2% CN additive significantly reduces bimolecular recombination and trap-assisted recombination. All-PSCs fabricated by the LBL method based on D18/PYIT-OD deliver a power conversion efficiency (PCE) of 15.07%. Our study demonstrates the great potential of additive engineering via the LBL fabrication method in regulating the microstructure of active layers, suppressing charge recombination, and enhancing the photovoltaic performance of devices.

In situ fabrication of Fe3C nanoparticles and porous-carbon composites as high-performance electromagnetic wave absorber.

This study successfully utilized a straightforward approach, choosing liquid-liquid phase separation to build a porous structure and synthesize composite absorbers based on polyimide-based porous carbon/Fe3C (PIC/Fe3C-1, PIC/Fe3C-2) nanoparticles and porous carbon/FeCo alloy nanoparticles (PIC/FeCo). The specially designed network structure pore structures contributed multiple reflection, conduction loss and strong interfacial polarization. After characterization, PIC/Fe3C-2 obtained minimum RL of -35.37 dB at 17.04 GHz with 1.55 mm thickness and effective absorption bandwidth of 4.95 GHz with 1.66 mm thickness. Furthermore, PIC/FeCo, with a thickness of 1.63 mm, exhibits the most robust electromagnetic wave loss ability at 15.6 GHz, with a minimum RL of -56.32 dB and an effective absorption bandwidth of 4.88 GHz. Thus, the design strategy presented in this study could serve as a model for synthesizing other high-performance absorbers, effectively mitigating electromagnetic wave-induced pollution.

In Situ Photogenerated Radicals of Hydroxyl Substituted Pyrene-Based Triphenylamines with Enhanced Transport and Free Doping/Post-Oxidation for Efficient Perovskite Solar Cells.

The high-performance hole transporting material (HTM) is one of the most important components for the perovskite solar cells (PSCs) in promoting power conversion efficiency (PCE). However, the low conductivity of HTMs and their additional requirements for doping and post-oxidation greatly limits the device performance. In this work, three novel pyrene-based derivatives containing methoxy-substituted triphenylamines units (PyTPA, PyTPA-OH and PyTPA-2OH) are designed and synthesized, where different numbers of hydroxyl groups are connected at the 2- or 2,7-positions of the pyrene core. These hydroxyl groups at the 2- or 2,7-positions of pyrene play a significantly role to enhance the intermolecular interactions that are able to generate in situ radicals with the assistance of visible light irradiation, resulting in enhanced hole transferring ability, as well as an enhanced conductivity and suppressed recombination. These pyrene-core based HTMs exhibit excellent performance in PSCs, which possess a higher PCE than those control devices using the traditional spiro-OMeTAD as the HTM. The best performance can be found in the devices with PyTPA-2OH. It has an average PCE of 23.44% (PCEmax = 23.50%), which is the highest PCE among the reported PSCs with the pyrene-core based HTMs up to date. This research offers a novel avenue to design a dopant-free HTM by the combination of the pyrene core, methoxy triphenylamines, and hydroxy groups.

Dual-Strategy Tailoring Molecular Structures of Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transport materials (HTMs) are ideal materials for highly efficient and stable n-i-p perovskite solar cells (PSCs), but most current design strategies for tailoring the molecular structures of HTMs are limited to single strategy. Herein, four HTMs based on dithienothiophenepyrrole (DTTP) core are devised through dual-strategy methods combining conjugate engineering and side chain engineering. DTTP-ThSO with ester alkyl chain that can form six-membered ring by the S⋅⋅⋅O noncovalent conformation lock with thiophene in the backbone shows good planarity, high-quality film, matching energy level and high hole mobility, as well as strong defect passivation ability. Consequently, a remarkable power conversion efficiency (PCE) of 23.3 % with a nice long-term stability is achieved by dopant-free DTTP-ThSO-based PSCs, representing one of the highest values for un-doped organic HTMs based PSCs. Especially, the fill factor (FF) of 82.3 % is the highest value for dopant-free small molecular HTMs-based n-i-p PSCs to date. Moreover, DTTP-ThSO-based devices have achieved an excellent PCE of 20.9 % in large-area (1.01 cm2) devices. This work clearly elucidates the structure-performance relationships of HTMs and offers a practical dual-strategy approach to designing dopant-free HTMs for high-performance PSCs.

Dependence of Interlayer or Sulfur Host on Hollow Framework of Lithium-Sulfur Battery.

Lithium-sulfur batteries are recognized as the next generation of high-specific energy secondary batteries owing to their satisfactory theoretical specific capacity and energy density. However, their commercial application is greatly limited by a series of problems, including disordered migration behavior, sluggish redox kinetics, and the serious shuttle effect of lithium polysulfides. One of the most efficient approaches to physically limit the shuttle effect is the rational design of a hollow framework as sulfur host. However, the influence of the hollow structure on the interlayers has not been clearly reported. In this study, the Mo2 C/C catalysts with hollow(H-Mo2 C/C) and solid(S-Mo2 C/C) frameworks are rationally designed to explore the dependence of the hollow structure on the interlayer or sulfur host. In contrast to the physical limitations of the hollow framework as host, the hollow structure of the interlayer inhibited lithium-ion diffusion, resulting in poor electrochemical properties at high current densities. Based on the superiority of the various frameworks, the H-Mo2 C/C@S | S-Mo2 C/C@PP | Li cells are assembled and displayed excellent electrochemical performance. This work re-examines the design requirements and principles of catalyst frameworks in different battery units.

Polyimide-based porous carbon and cobalt nanoparticle composites as high-performance electromagnetic wave absorbers.

This study successfully utilized a straightforward approach, choosing liquid-liquid phase separation to build a porous structure and synthesize composite absorbers based on polyimide-based porous carbon and cobalt nanoparticles (designated as PPC/Co-700 and PPC/Co-800). A fine porous structure was achieved as a result of the excellent heat resistance of polyimide resulting in an excellent electromagnetic wave absorption ability of PPC/Co composites. The results obtained clearly indicated that PPC/Co-700 and PPC/Co-800 exhibit a porous structure with coral-like pores, enhancing both impedance matching properties and microwave attenuation abilities. This improvement in impedance matching conditions and dissipation capability is attributed to the synergistic effect of dielectric loss induced by carbon and magnetic loss induced by Co nanoparticles. PPC/Co-700 showed the strongest absorption performance with a minimum reflection loss of -59.85 dB (30 wt% loading, thickness of 3.42 mm) and an effective absorption bandwidth (EABW, RL ≤ -10 dB) of 6.24 GHz (30 wt% loading, thickness of 2.78 mm). Therefore, this work provides a facile strategy for the development of a promising absorbing material with outstanding electromagnetic wave absorption performance.

Pyrene-Based Deep-Blue Fluorophores with Narrow-Band Emission.

High-efficiency narrow-band luminescent materials have attracted intense interest, resulting in their great colorimetric purity. This has led to a variety of high-tech applications in high-definition displays, spectral analysis, and biomedicine. In this study, a rigid pyrene core was employed as the molecular backbone, and four narrow-band pyrene-based blue emitters were synthesized using various synthetic methods (such as Lewis-acid catalyzed cyclization domino reactions, Pd-catalyzed coupling reactions like Suzuki-Miyaura and Sonogashira). Due to the steric effect of the hydroxy group at the 2-position, the target compounds exhibit deep blue emission (<429 nm, CIEy < 0.08) with full width at half-maximum (FWHM) less than 33 nm both in solution and when solidified. The experimental and theoretical results indicated that the substituents at the 1- and 3-positions afford a large dihedral angle with the pyrene core, and the molecular motion is almost fixed by multiple intra- and intermolecular hydrogen bonding interactions in the crystallized state, leading to a suppression of the vibrational relaxation of the molecular structure. Moreover, we observed that the suppression of the vibrational relaxation in the molecular structures and the construction of rigid conjugated structures can help develop narrow-band organic light-emitting materials.

Tandem pyrolysis-catalytic upgrading of plastic waste towards kerosene-range products using Si-pillared vermiculite with transition metal modification.

The transformation of waste plastics to fuel products is an appealing strategy to address plastic-associated environmental and energy issues. In this study, a tandem pyrolysis-catalytic upgrading approach, using a series of mono-/bitransition-metal-modified Si-pillared vermiculite catalysts, was adopted to transform disposable grocery bags (i.e., a polyethylene-based material) to kerosene-range fuels. The results revealed that the silicon pillars contributed to the catalyst's excellent thermal stability to withstand temperatures of up to 1000 °C, while the transition-metallic species (e.g., Co/Ni/Fe) contributed to the fine-tuning of the catalyst's acidity and porosity. Specifically, Co-Fe/Si-pillared vermiculite (SPV) (5:5) produced the highest yield of oil products (75.7 wt%), with alkane and aromatic selectivities of 57.5% and 27.8%, respectively, resembling the composition of kerosene. The catalyst's high selectivities for the targeted products were attributed to the controllable acidity and porosity, enabling a balance to be achieved between these two properties. Pathways were proposed for the tandem pyrolysis in the presence of Co-Fe/SPV. The vermiculite-based catalysts showed satisfactory reusability following regeneration. Beyond polyethylene-based plastics, these catalysts are also applicable to the pyrolysis of other plastic feedstocks. Because vermiculite is a low-cost material, the developed catalyst has good commercialization potential for a wide spectrum of waste-to-energy conversions.

The Synergistic Effect of Additives for Formamidinium-Based Inverted Dion-Jacobson 2D Perovskite Solar Cells with Enhanced Photovoltaic Performance.

Two-dimensional (2D) perovskite solar cells (PSCs) have attracted rapid growing attention due to their excellent environmental and operational stability. As an important type of 2D perovskite, Dion-Jacobson (DJ) 2D perovskites exhibit better structural integrity and more stable optoelectronic properties than those of Ruddlesden-Popper (RP) ones because of the elimination of weak van der Waals interactions. Random phase distribution, phase impurity, and weak crystallinity, however, can lead to severe nonradiative recombination losses in 2D perovskites and inferior device stability. Herein, formamidinium chloride (FACl) and lead chloride (PbCl2) are selected as additives to fabricate efficient and stable DJ 2D PSCs. The synergistic effect of additives could efficiently induce crystallization and suppress the low-n phase perovskites. The obtained 2D perovskites exhibit extended charge lifetime and enhanced charge transfer. The corresponding PSC device delivers an efficiency of 16.63% with a significantly improved open-circuit voltage (VOC) of 1.18 V and a fill factor (FF) of 81.65% than the control one. This PCE ranks the highest for inverted FA-based 2D DJ PSCs. Moreover, this device has exhibited exceptional long-term stability, which retains more than 95% of the initial efficiencies at about 50% relative humidity for 600 h.

Template free preparation of graphene tubes from polyimide catalyzed by calcium carbonate.

This work reports a new means of preparing graphene tubes (GTs) without relying on chemical vapor deposition (CVD) and it's template-free. Surprisingly, we found that under the action of calcium oxide (CaO) and after 1500 °C heat treatment, a large amount of GTs grew on the surface of polyimide (PI). These nanotubes have a maximum diameter of about 600 nm and a length of up to millimeters, and some nanotubes even have a branching structure. We propose a simple, effective and green method which exhibits prospects for large-scale production of GTs using polymeric materials.

Enhancing the Performance of Perovskite Solar Cells by Introducing 4-(Trifluoromethyl)-1H-imidazole Passivation Agents.

Defects in perovskite films are one of the main factors that affect the efficiency and stability of halide perovskite solar cells (PSCs). Uncoordinated ions (such as Pb2+, I-) act as trap states, causing the undesirable non-radiative recombination of photogenerated carriers. The formation of Lewis acid-base adducts in perovskite directly involves the crystallization process, which can effectively passivate defects. In this work, 4-(trifluoromethyl)-1H-imidazole (THI) was introduced into the perovskite precursor solution as a passivation agent. THI is a typical amphoteric compound that exhibits a strong Lewis base property due to its lone pair electrons. It coordinates with Lewis acid Pb2+, leading to the reduction in defect density and increase in crystallinity of perovskite films. Finally, the power conversion efficiency (PCE) of PSC increased from 16.49% to 18.97% due to the simultaneous enhancement of open-circuit voltage (VOC), short circuit current density (JSC) and fill factor (FF). After 30 days of storage, the PCE of the 0.16 THI PSC was maintained at 61.9% of its initial value, which was 44.3% for the control device. The working mechanism of THI was investigated. This work provides an attractive alternative method to passivate the defects in perovskite.

Polyimide aerogel-derived amorphous porous carbon/crystalline carbon composites for high-performance microwave absorption.

High-performance polyimide-based porous carbon/crystalline composite absorbers (PIC/rGO and PIC/CNT) were prepared by vacuum freeze-drying and high-temperature pyrolysis. The excellent heat resistance of polyimides (PIs) ensured the integrity of their pore structure during high-temperature pyrolysis. The complete porous structure improves the interfacial polarization and impedance-matching conditions. Furthermore, adding appropriate rGO or CNT can improve the dielectric losses and obtain good impedance-matching conditions. The stable porous structure and strong dielectric loss enable fast attenuation of electromagnetic waves (EMWs) inside PIC/rGO and PIC/CNT. The minimum reflection loss (RLmin) for PIC/rGO is -57.22 dB at 4.36 mm thickness. The effective absorption bandwidth (EABW, RL below -10 dB) for PIC/rGO is 3.12 GHz at 2.0 mm thickness. The RLmin for PIC/CNT is -51.20 dB at 2.02 mm thickness. The EABW for PIC/CNT is 4.08 GHz at 2.4 mm thickness. The PIC/rGO and PIC/CNT absorbers designed in this work have simple preparations and excellent EMW absorption performances. Therefore, they can be used as candidate materials in EMW absorbing materials.

Synthesis of Furan-Based Diamine and Its Application in the Preparation of Bio-Based Polyimide.

Furan-based compounds are a new class of compounds characteristic of wide abundance, feasible availability, and environmental friendliness. Presently, polyimide (PI) is the best membrane insulation material in the world, which is widely used in the fields of national defense, liquid crystals, lasers, and so on. At present, most polyimides are synthesized using petroleum-based monomers bearing benzene rings, while furan-based compounds bearing furan rings are rarely used as monomers. The production of petroleum-based monomers is always associated with many environmental issues, and their substitution with furan-based compounds seems a solution to addressing these issues. In this paper, t-butoxycarbonylglycine (BOC-glycine) and 2,5-furandimethanol, bearing furan rings, were employed to synthesize BOC-glycine 2,5-furandimethyl ester, which was further applied for the synthesis of furan-based diamine. This diamine is generally used to synthesize bio-based PI. Their structures and properties were thoroughly characterized. The characterization results showed that BOC-glycine could be effectively obtained using different posttreatment methods. And BOC-glycine 2,5-furandimethyl ester could be effectively obtained by optimizing the accelerating agent of 1,3-dicyclohexylcarbodiimide(DCC) with either 1.25 mol/L or 1.875 mol/L as the optimum value. The PIs originated from furan-based compounds were synthesized and their thermal stability and surface morphology were further characterized. Although the obtained membrane was slightly brittle (mostly due to the less rigidity of furan ring as compared with benzene ring), the excellent thermal stability and smooth surface endow it a potential substitution for petroleum-based polymers. And the current research is also expected to shed some insight into the design and the fabrication of eco-friendly polymers.

Reducing the Permittivity of Polyimides for Better Use in Communication Devices.

Recent studies have shown that introducing fluorinated groups into polyimide (PI) molecules can effectively reduce the dielectric constant (Dk) and dielectric loss (Df) of PIs. In this paper, 2,2'-bis[4-(4-aminophenoxy) phenyl]-1,1',1',1',3,3',3'-hexafluoropropane (HFBAPP), 2,2'-bis(trifluoromethyl)-4,4'-diaminobenzene (TFMB), diaminobenzene ether (ODA), 1,2,4,5-Benzenetetracarboxylic anhydride (PMDA), 3,3',4,4'-diphenyltetracarboxylic anhydride (s-BPDA) and 3,3',4,4'-diphenylketontetracarboxylic anhydride (BTDA) were selected for mixed polymerization to find the relationship between the structure of PIs and dielectric properties. Firstly, different structures of fluorinated PIs were determined, and were put into simulation calculation to learn how structure factors such as fluorine content, the position of fluorine atom and the molecular structure of diamine monomer affect the dielectric properties. Secondly, experiments were carried out to characterize the properties of PI films. The observed change trends of performance were found to be consistent with the simulation results, and the possible basis of the interpretation of other performance was made from the molecular structure. Finally, the formulas with the best comprehensive performance were obtained respectively. Among them, the best dielectric properties were 14.3%TFMB/85.7%ODA//PMDA with dielectric constant of 2.12 and dielectric loss of 0.00698.

Attapulgite Nanorod-Incorporated Polyimide Membrane for Enhanced Gas Separation Performance.

Polyimide (PI) membrane is an ideal gas separation material due to its advantages of high designability, good mechanical properties and easy processing; however, it has equilibrium limitations in gas selectivity and permeability. Introducing nanoparticles into polymers is an effective method to improve the gas separation performance. In this work, nano-attapulgite (ATP) functionalized with KH-550 silane coupling agent was used to prepare polyimide/ATP composite membranes by in-situ polymerization. A series of characterization and performance tests were carried out on the membranes. The obtained results suggested a significant increase in gas permeability upon increasing the ATP content. When the content of ATP was 50%, the gas permeability of H2, He, N2, O2, CH4, and CO2 reached 11.82, 12.44, 0.13, 0.84, 0.10, and 4.64 barrer, which were 126.87%, 119.40%, 160.00%, 140.00%, 150.00% and 152.17% higher than that of pure polyimide, respectively. No significant change in gas selectivity was observed. The gas permeabilities of membranes at different pressures were also investigated. The inefficient polymer chain stacking and the additional void volume at the interface between the polymer and TiO2 clusters leaded to the increase of the free volume, thus improving the permeability of the polyimide membrane. As a promising separation material, the PI/ATP composite membrane can be widely used in gas separation industry.

Polyimide-derived porous carbon/Co particle-based composites for high-performance microwave absorption.

A simple method that combines liquid-liquid phase separation and high-temperature pyrolysis has been developed for the synthesis of polyimide-derived porous carbon/Co particle-based composite absorbers (PIC/Co-800 and PIC/Co-1000). The excellent heat resistance of polyimide allows the composite precursor to maintain its porous structure during pyrolysis. According to the results, PIC/Co-800 and PIC/Co-1000 have a coral-like porous structure, which can enhance the impedance matching property and microwave attenuation ability of the synthesized materials. The impedance matching condition and dissipation ability of PIC/Co-800 and PIC/Co-1000 have been enhanced due to the synergistic effect between the carbon-induced dielectric loss and Co nanoparticle-induced magnetic loss. PIC/Co-1000 shows the highest absorption performance with a minimum reflection loss (RL) of -40.22 dB at a thickness of 5.3 mm and an effective absorption bandwidth (EABW, RL ≤ -10 dB) of 4.10 GHz at a thickness of 1.4 mm. With thicknesses in the range of 1.4 mm to 5.3 mm, the minimum RL value of each thickness is lower than -15 dB. Therefore, this work provides a new strategy for the synthesis of promising absorbing materials with outstanding EMW absorption performance.

Synthesis and Characterization of Polyimides with Naphthalene Ring Structure Introduced in the Main Chain.

In this paper, a new aromatic diamine monomer 4,4'-(2,6-naphthalenediyl)bis[benzenamine]) (NADA) was synthesized and a series of modified PI films containing naphthalene ring structure obtained by controlling the molar ratio of NADA monomer, ternary polymerization with 4,4'-oxydianiline (ODA), and pyromellitic dianhydride (PMDA). The effects of the introduction of the naphthalene ring on the free volume and various properties of PI were investigated by molecular dynamic simulations. The results show that the comprehensive properties of the modified films are all improved to some extent, with 5% thermal weight loss temperature (Td5%) of 569 °C, glass transition temperature (Tg) of 381 °C, tensile strength of 96.41 MPa, and modulus of elasticity of 2.45 GPa. Dielectric property test results show that the dielectric constant (Dk) of the film at 1 MHz is reduced from 3.21 to 2.82 and dielectric loss (Df) reduced from 0.0091 to 0.0065. It is noteworthy that the PI-1 dielectric constant is reduced from 3.26 to 3.01 at 10 GHz with only 5% NADA doping, which is expected to yield the best ratio and provide the possibility of industrial production.

Highly Stable 4.6 V LiCoO2 Cathodes for Rechargeable Li Batteries by Rubidium-Based Surface Modifications.

Among extensively studied Li-ion cathode materials, LiCoO2 (LCO) remains dominant for portable electronic applications. Although its theoretical capacity (274 mAh g-1 ) cannot be achieved in Li cells, high capacity (≤240 mAh g-1 ) can be obtained by raising the charging voltage up to 4.6 V. Unfortunately, charging Li-LCO cells to high potentials induces surface and structural instabilities that result in rapid degradation of cells containing LCO cathodes. Yet, significant stabilization is achieved by surface coatings that promote formation of robust passivation films and prevent parasitic interactions between the electrolyte solutions and the cathodes particles. In the search for effective coatings, the authors propose RbAlF4 modified LCO particles. The coated LCO cathodes demonstrate enhanced capacity (>220 mAh g-1 ) and impressive retention of >80/77% after 500/300 cycles at 30/45 °C. A plausible mechanism that leads to the superior stability is proposed. Finally the authors demonstrate that the main reason for the degradation of 4.6 V cells is the instability of the anode side rather than the failure of the coated cathodes.

Attapulgite Nanorods Incorporated MXene Lamellar Membranes for Enhanced Decontamination of Dye Wastewater.

Due to its unique physical and chemical properties, MXene has recently attracted much attention as a promising candidate for wastewater treatment. However, the low water permeation flux of MXene membrane remains a challenge that has not been fully solved. In this study, attapulgite was used to increase the flux of MXene membrane through a facile one-pot method, during which the MXene nanosheets were self-assembled while being intercalated by the attapulgite nanorods to finally form the composite membranes. Under optimal conditions, an increase of water permeation flux of 97.31% could be observed, which was attributed to the broadened nano-channel upon the adequate intercalation of attapulgite nanorods. Its permeation flux and rejection rate for methylene blue (MB) were further studied for diverse applications. In contrast to bare MXene, the permeation flux increased by 61.72% with a still high rejection rate of 90.67%, owing to the size rejection. Overcoming a key technique barrier, this work successfully improved the water permeability of MXene by inserting attapulgite nanorods, heralding the exciting prospects of MXene-based lamellar membrane in dye wastewater treatment.