In-situ polymerized PEO-based solid electrolytes contribute better Li metal batteries:Challenges,strategies,and perspectives

Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Crystalline Morphology and Crystallization Characteristics of In-situ Blends of Anionic Polyamide 6 with Noncrystallizable Semiaromatic Polyamide Copolymer

A noncrystallizable semiaromatic polyamide copolymer（NSAP） was dissolved in molten caprolactam, and PA6/ NSAP blends were produced in-situ via the anionic ring-opening polymerization of caprolactam. The presence of a single loss tangent（tanS） peak measured by means of dynamic mechanical analysis（DMA） proves the miscibility between PA6 and NSAP in the blends. It was found that there existed drastic changes in the crystallographic form and crystallization kinetics for the in-situ blends, e.g. , when 20% NSAP was added, nearly all crystallites existed in the ,y form and the crystallization could hardly occur upon cooling even at a rate of 2.5 ℃/min. Moreover, cold crystallization appears during the subsequent heating, and its melting point is 40 ℃ lower than that of the virgin system. On the other hand, the size of the spherulites only decreases modestly. It is suggested that the introduction of irregular stiff segments originated from NSAP into PA6 macromolecule chain, which resulted from transamidation during the polymerization play a dominant role in the drastic change of crystallization kinetics and the resultant morphology of the in-situ blends.

Nanomorphology in A–D–A type small molecular acceptors-based bulk heterojunction polymer solar cells

Recent developments in acceptor–donor–acceptor(A–D–A) type non-fullerene acceptors have led to substantial improvements in bulk-heterojunction polymer solar cells efficiency. The device performance strongly depends on photoactive layer morphology, as the molecular packing, donor–acceptor interface and phase separation significantly affect the charge-transfer states and charge carrier dynamics. In this review, we start with a brief introduction of the techniques most effectively utilized to characterize multiphase morphology. Then, we summarize recent progress in A–D–A type acceptors, with the emphasis on understanding the molecular structure–morphology–performance relationships. Finally, an outlook on correlating morphological characteristics with photovoltage losses is presented for further improving device performance.

SYNTHESIS AND CHARACTERIZATION OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES VIA AN in-situ POLYMERIZATION APPROACH

Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Preparation of Polysulfonamide/ZnO Nanocomposite by In-Situ Polymerization

Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.

A NOVEL EOR POLYMER (Ⅱ)——INVESTIGATION ON IN-SITU GELATION OF SMRF SYSTEM IN BEREA CORE

In-situ gelation of aqueous sulfomethylated resorcinol formaldehyde (SMRF) system inBerea core has been investigated. Two sets of displacement experiments were conducted with thissystem (containing 5% NaCl, 0. 036% CaCl_2. 2H_2O). The brine permeabilities of the coreswere reduced significantly from about 600 to 0.1 md. The in-situ gelation in Berea core occurreda little bit earlier than gelation anticipated from bulk test in the experiments. The gel time waseasier to control at initial pH between 6 and 8. During injection of SMRF system, the apparentviscosity was less than 1 mPa·s at 41℃.

Fabrication and Characterization of Bulk Heterojunction Solar Cells Based on Liquid-Crystal Semiconductive Polymer

Bulk heterojunction solar cells based on poly poly(9,9-dioctylfluorene-co-bithiophene) (F8T2) as liquid crystal semiconductive polymer and C60 as electron acceptor were fabricated and characterized. Thermal treatment of the bulk heterojunction films at annealing in the range of glass temperature and liquid crystal transition was performed for tuning optimization with improving the photovoltaic and optical properties. The photovoltaic performance was depended on morphological behavior in active layer at crystal state below glass temperature. The F8T2 thin film worked for electron-donor layer as p-type semiconductor to support charge transfer in active layer. Mechanisms of the photovoltaic properties were discussed on the basis of experimental results.

CHANGES OF STRUCTURE AND PROPERTIES OF POLY (ETHYLENE TEREPHTHALATE) CAUSED BY IN-SITU POLYMERIZATION OF PYRROLE

Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly （ethylene terephthalate） （PET） film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.

Effect of Crystallinity of Fullerene Derivatives on Doping Density in the Organic Bulk Heterojunction Layer in Polymer Solar Cells

Polymer solar cells （PSCs） based on poly（3-hexylthiophene） （P3HT） and [6,6]-phenyl-C61-butyric acid methyl ester （PCBM） are fabricated by using 1,8-diiodooctane （DIO） as a solvent additive to control the doping density of the PSCs. It is shown that the processing of DIO does not change the doping density of the P3HT phase, while it causes a dramatic reduction of the doping density of the PCBM phase, which decreases the doping density of the whole blend layer from 3.7 × 10^16 cm-3 to 1.2 ×10^16 cm-3. The reduction of the doping density in the PCBM phase originates from the increasing crystallinity of PCBM with DIO addition, and it leads to a decreasing doping density in the blend film and improves the short circuit current of the PSCs.

Tuning desolvation kinetics of in-situ weakly solvating polyacetal electrolytes for dendrite-free lithium metal batteries

The host structure of polymers significantly influences ion transport and interfacial stability of electrolytes,dictating battery cycle life and safety for solid-state lithium metal batteries.Despite promising properties of ethylene oxide-based electrolytes,their typical clamp-like coordination geometry leads to crowd solvation sheath and overly strong interactions between Li^(+)and electrolytes,rendering difficult dissociation of Li+and unfavorable solid electrolyte interface(SEI).Herein,we explore weakly solvating characteristics of polyacetal electrolytes owing to their alternately changing intervals between–O–coordinating sites in the main chain.Such structural asymmetry leads to unique distorted helical solvation sheath,and can effectively reduce Li^(+)-electrolyte binding and tune Li^(+)desolvation kinetics in the insitu formed polymer electrolytes,yielding anion-derived SEI and dendrite-free Li electrodeposition.Combining with photoinitiated cationic ring-opening polymerization,polyacetal electrolytes can be instantly formed within 5 min at the surface of electrode,with high segmental chain motion and well adapted interfaces.Such in-situ polyacetal electrolytes enabled more than 1300-h of stable lithium electrodeposition and prolonged cyclability over 200 cycles in solid-state batteries at ambient temperatures,demonstrating the vital role of molecular structure in changing solvating behavior and Li deposition stability for high-performance electrolytes.

Visualization of adaptive polymer flow and displacement in medium-permeable 3D core-on-a-chip

Polymer flooding has been witnessed an effective technology for enhancing oil recovery from medium-to low-permeability reservoirs;however, direct visualization of polymer solution flow in such reservoir condition is still lacking. In this work, a three-dimensional (3D) core-on-a-chip device with a permeability of around 200 mD was prepared and employed to visualize the pore-scale flow and displacement of a self-adaptive polymer (SAP, 8.7 × 106 g·mol−1)−whose microscopic association structure and macroscopic viscosity can reversibly change in response to shear action−versus partially hydrolyzed polyacrylamide (HPAM), by recording their flow curves, monitoring dynamic transportation process via particle imaging velocimetry, and building 3D structure of remaining oil. The results show that, in single-phase flow, all polymer solutions exhibit flow thinning and then thickening regions as flow rate increases, but the transition between two regimes occurs at a small Weissenberg number (10−3−10−1) in this medium-permeable condition. In contrast to HPAM-1 with close weight-average molecular weight (Mw), the adaptive character not only extends SAP's shear-govern region, allowing SAP to propagate piece by piece and achieve higher accessible pore volume, but it also enhances the elastic resistibility of polymer in the extension-dominated regime, increasing the microscopic displacement efficiency. These two effects result in 1.5–3 times more oil recovery factor for SAP than for HPAM-1. Regarding ultra-high-Mw HPAM-2 (25 × 106 g·mol−1), plugging and chain degradation do occur, thus producing lower oil recovery than SAP. This work provides a direct approach for in-situ assessment of polymer-based displacing system under a more authentic condition of practical reservoirs.

Eutectic Solution Enables Powerful Click Reaction for In-Situ Construction of Advanced Gel Electrolytes

Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.

卧式捏合反应器及其在聚合工业中的研究进展

卧式捏合反应器具有大的反应体积,优异的混合性能、表面更新性能、传热性能和自清洁性能,因而在本体聚合、缩合聚合和聚合物脱挥等领域具有广阔的应用前景。综述了几种捏合反应器及其搅拌特性研究,以及在聚合工业中的应用研究,指出捏合反应器具有非常复杂的几何结构,实验测量技术具有很大的局限性,计算流体力学(CFD)模拟为主要的研究方法;进一步指出具有自清洁特性的捏合反应器是聚合物搅拌设备开发的主要方向,高效、集约化、绿色、环保的先进工艺与装置是促进我国聚合工业发展的关键。

改性PMMA树脂本体聚合反应及拉挤工艺应用

为了实现拉挤工艺成型纤维增强聚甲基丙烯酸甲酯(PMMA)复合材料的生产,采用了不同的助剂来调控PMMA聚合反应过程,改善甲基丙烯酸甲酯(MMA)单体的本体聚合。其中邻苯二甲酸二丁酯(DBP)作为增塑剂,N,N-二甲基苯胺(DMA)和乙酸丁酯(BAC)作为反应调整助剂,将各种助剂以一定比例混入树脂体系中进行聚合。首先将各树脂体系在60℃进行20 min预聚合得到预聚体,再对不同体系的预聚体进行差示扫描量热(DSC)测试和反应动力学分析。结果表明,在不同升温速率(β)下,加入DMA体系的反应起始温度都有所降低,DMA能够加快聚合初期的反应进程,而加入BAC则使得β为25℃/min时的反应温度区间从36.1℃提高到41.3℃。使用Kissinger法和Ozawa法进行拟合分析,得到各体系反应的平均活化能(Ea),其中加入DMA使得体系Ea降低至40.71 kJ/mol,比未添加反应调整助剂的体系下降了16.9%。最终用各体系树脂进行拉挤实验,发现仅有添加了BAC的体系能够生产质量合格的产品。在拉挤工艺生产纤维增强PMMA复合材料过程中,加入一定量BAC助剂能够减缓树脂聚合集中放热,提高产品质量。

Surface Morphology and Thermo-Electrical Energy Analysis of Polyaniline (PANI) Incorporated Cotton Fabric

With the exponential development in wearable electronics,a significant paradigm shift is observed from rigid electronics to flexible wearable devices.Polyaniline(PANI)is considered as a dominant material in this sector,as it is endowed with the optical properties of both metal and semiconductors.However,its widespread application got delineated because of its irregular rigid form,level of conductivity,and precise choice of solvents.Incorporating PANI in textile materials can generate promising functionality for wearable applications.This research work employed a straightforward in-situ chemical oxidative polymerization to synthesize PANI on Cotton fabric surfaces with varying dopant(HCl)concentrations.Pre-treatment using NaOH is implemented to improve the conductivity of the fabric surface by increasing the monomer absorption.This research explores the morphological and structural analysis employing SEM,FTIR and EDX.The surface resistivity was measured using a digital multimeter,and thermal stability is measured using TGA.Upon successful polymerization,a homogenous coating layer is observed.It is revealed that the simple pre-treatment technique significantly reduces the surface resistivity of Cotton fabric to 1.27 kΩ/cm with increasing acid concentration and thermal stability.The electro-thermal energy can also reach up to 38.2°C within 50 s with a deployed voltage of 15 V.The modified fabric is anticipated to be used in thermal regulation,supercapacitor,sensor,UV shielding,antimicrobial and other prospective functional applications.

本体法聚氯乙烯预聚合釜防粘釜技术改进

介绍了本体法聚氯乙烯生产工艺,分析了预聚合釜粘釜的主要原因并提出了相应的改进措施,包括增加预聚合釜自动高压清洗装置和防粘釜剂自动喷涂装置。改进后延长了预聚合釜的清釜周期,提高了装置产能,降低清釜作业带来的安全风险。

Research progress of in-situ gelling ophthalmic drug delivery system

Blindness and vision impairment are the most devastating global health problems resulting in a substantial economic and social burden.Delivery of drug to particular parts of the anterior or posterior segment has been a major challenge due to various protective barriers and elimination mechanisms associated with the unique anatomical and physiological nature of the ocular system.Drug administration to the eye by conventional delivery systems results in poor ocular bioavailability(<5%).The designing of a novel approach for a safe,simple,and effective ocular drug delivery is a major concern and requires innovative strategies to combat the problem.Over the past decades,several novel approaches involving different strategies have been developed to improve the ocular delivery system.Among these,the ophthalmic in-situ gel has attained a great attention over the past few years.This review discussed and summarized the recent and the promising research progress of in-situ gelling in ocular drug delivery system.

Shorter alkyl chain in thieno[3,4-c]pyrrole-4,6-dione(TPD)-based large bandgap polymer donors – Yield efficient non-fullerene polymer solar cells

Typically,conjugated polymers are composed of conjugated backbones and alkyl side chains.In this contribution,a cost-effective strategy of tailoring the length of alkyl side chain is utilized to design highperforming thieno[3,4-c]pyrrole-4,6-dione(TPD)-based large bandgap polymer donors PBDT-BiTPD(Cχ)(χ=48,52,56),in which x represents the alkyl side chain length in term of the total carbon number.A combination of light absorption,device,and morphology examinations make clear that the shorter alkyl side chains yield(i) higher crystallinity and more predominant face-on crystallite orientation in their neat and BHJ blend films,(ii) higher charge mobilities(6.7×10^(-4) cm~2 V^(-1) s^(-1) for C48 vs.3.2×10^(-4) cm~2 V^(-1) s^(-1) for C56),and negligible charge recombination,consequently,(iii) significantly improved fill-factor(FF) and short current(J_(SC)),while almost the same open circuit voltage(V_(OC)) of ca.0.82 V in their corresponding BHJ devices.In parallel,as alkyl side chain lengths decrease from C56 to C48,power conversion efficiencies(PCEs) increased from 7.8% for C56 to 11.1% for C52,and further to14.1% for C48 in their BHJ solar cells made with a narrow bandgap non-fullerene acceptor Y6.This systematic study declares that shortening the side chain,if providing appropriate solubility in device solution processing solvents,is of essential significance for developing high-performing polymer donors and further improving device photovoltaic performance.

In-situ self-templated preparation of porous core-shell Fe_(1-x)S@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.