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.

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.

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.

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.

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.

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.

Synergistic effect of indium doping and chlorine surface passivation on CsPbI3 perovskite quantum dots for deep-red light-emitting devices.

Deep-red CsPbI3 perovskite quantum dots (PeQDs) are essential for high-efficiency perovskite light-emitting diodes (PeLEDs) because of their high color purity and high photoluminescence quantum yield (PLQY). The synergetic strategy of indium (In) doping and chlorine (Cl) surface passivation not only partially replaced Pb2+ ions with the smaller ionic In3+ but also filled I- vacancies by Cl- on the surface, maintaining the humidity stability for more than 24 days and yielding excellent PLQY. Benefiting from this synergetic strategy, deep-red (approximately at 683 nm) CsPbI3 PeLEDs showed a maximum luminance and external quantum efficiency (EQE) of 311 cd m-2 and 8.32%, respectively.

Re-Stickable Yarn Supercapacitors with Vaper Phase Polymerized Multi-Layered Polypyrrole Electrodes for Smart Garments.

Yarn supercapacitors have attracted significant attention for wearable energy storage due to their ability to be directly integrated with garments. Conducting polymer polypyrrole (PPy) based yarn supercapacitors show limited cycling stability because of the huge volume changes during the charge-discharge processes. In addition, laundering may cause damage to such yarn supercapacitors. Here, the fabrication of PPy-based re-stickable yarn supercapacitors is reported with good cycling stability by employing vapor phase polymerization (VPP) and water-soluble polyethylene oxide (PEO) film as the adhesive layer. VPP duration and cycle are controlled to achieve multi-layered PPy electrodes. The assembled yarn supercapacitors show a good cycling stability with capacitance retention of 79.1% after 5000 charge-discharge cycles. The energy stored in the yarn supercapacitor is sufficient to power a photodetector. After gluing the yarn supercapacitors onto a PEO film, the devices can be stunk on and peeled off the garment to avoid the mechanical stresses during the washing process. Three yarn supercapacitors connected in parallel on PEO film show negative changes in electrochemical performance after 5 sticking-peeling cycles. This work provides a facile way to fabricate PPy-based re-stickable energy storage devices with high cycling stability for smart garments.

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.

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.

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.

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.

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.

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.

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.

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.

Synthesis and Properties Comparison of Low Dielectric Silicon Containing Polyimides.

Recent studies have shown that the introduction of silicon can effectively improve the dielectric properties of polyimide (PI), and the introduction of a silicon-oxygen bond can increase the flexibility of the PI molecular structure, which is conducive to reducing the moisture absorption rate of PI materials. In this experiment, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl disiloxane (DSX) was mixed with 4,4'-diaminodiphenyl ether (ODA) in different proportions. A series of PI films containing silicon was obtained by random polymerization with pyromellitic dianhydride (PMDA), 3,3',4,4'-diphenylketotetrahedral anhydride (BTDA) and biphenyl dianhydride (BPDA), and then tetrad copolymerization with three kinds of dianhydrides. At the same time, the PI structures were put into calculation software to obtain the simulated polarization results, and then the films were characterized by various properties. The results showed that the characterization results were consistent with that of simulation, and the best overall PI formula was when the ratio of diamines was 1:9 and mixed with PMDA. The performance data were as follows: the vitrification temperature was about 320 °C, T5 was 551 °C, water absorption was 1.56%, dielectric constant (Dk) was 2.35, dielectric loss (Df) was 0.007, tensile strength was 70 MPa and elongation at break was 10.2%.

Phase equilibria and conformational behavior of dendrimers in porous media: Towards chromatographic analysis of dendrimers.

HYPOTHESIS: The intricate entropy-enthalpy interplay of dendrimers confined in pores affects their conformation and retention in the porous stationary phase. This work aims at providing important insights into its impacts on partitioning and chromatographic separation in both size-exclusion chromatography (SEC) and interaction chromatography (IC) regimes. SIMULATIONS: Using Monte Carlo (MC) simulations, we investigated the bulk-pore phase equilibria and the conformational behavior of flexible dendrimers differing in generation, in spacer length and in fraction of modified terminal groups interacting differently with pore walls than the majority building units. FINDINGS: With increasing interaction strength, a distinct transition from a roughly spherical shape caused by simultaneous interactions with two walls to an ellipsoidal (or even disklike) conformation tenaciously adhering to only one wall was observed for moderately confined dendrimers. The strongly deformed dendrimers subjected to severe confinement gain high energy and the samples differing in the degree of modification become chromatographically discernable thanks to large energy differences. Consequently, our results suggest that the column fillings with fairly narrow pores which are ineffective in SEC, are highly efficient separation media for dendrimer studies by IC above the critical adsorption point (CAP). Overall, our simulations reveal useful information for advancing and optimizing experimental liquid chromatography studies of dendrimers.

Modeling the Phase Equilibria of Associating Polymers in Porous Media with Respect to Chromatographic Applications.

Associating copolymers self-assemble during their passage through a liquid chromatography (LC) column, and the elution differs from that of common non-associating polymers. This computational study aims at elucidating the mechanism of their unique and intricate chromatographic behavior. We focused on amphiphilic diblock copolymers in selective solvents, performed the Monte Carlo (MC) simulations of their partitioning between a bulk solvent (mobile phase) and a cylindrical pore (stationary phase), and investigated the concentration dependences of the partition coefficient and of other functions describing the phase behavior. The observed abruptly changing concentration dependences of the effective partition coefficient demonstrate the significant impact of the association of copolymers with their partitioning between the two phases. The performed simulations reveal the intricate interplay of the entropy-driven and the enthalpy-driven processes, elucidate at the molecular level how the self-assembly affects the chromatographic behavior, and provide useful hints for the analysis of experimental elution curves of associating polymers.

Multifunctional PCL composite nanofibers reinforced with lignin and ZIF-8 for the treatment of bone defects.

Polycaprolactone (PCL) nanofibers have become an ideal material for bone tissue engineering due to a series of advantages. Considering the clinical treatment of bone defects, in addition to meeting the golden standard, PCL based nanofibers also need to be multifunctional to anti-inflammatory, antibacterial properties, and enhance the bone regeneration and repair. Herein, we successfully developed the multifunctional PCL/LIG/ZIF-8 composite nanofibers by loading ZIF-8 on electrospun PCL/lignin (PCL/LIG) nanofibers. The prepared composite nanofibers exhibit fairly good wettability and acceptable degradation rate, as well as excellent antioxidative stress and antibacterial properties originating from the incorporated LIG and loaded ZIF-8. Moreover, owing to the synergistic effect of LIG and ZIF-8, the composite nanofibers present excellent osteogenic differentiation, which can be verified in biomineralization experiments and real-time quantitative polymerase chain reaction. These results indicate that the PCL/LIG/ZIF-8 composite nanofibers, as potential healthcare candidate, have a promising applied in the treatment of bone defects.