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.

Enhanced thermal and electrical properties of poly (D,L-lactide)/ multi-walled carbon nanotubes composites by in-situ polymerization

Biodegradable poly （D,L-lactide） （PLA）/carboxyl-functionalized multi-walled carbon nanotubes （c-MWCNTs） composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.

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.

Remote plasma enhanced cyclic etching of a cyclosiloxane polymer thin film

The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.

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.

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.

PREPARATION OF POLYSULFONAMIDE AND MODIFIED TITANIUM OXIDE NANOCOMPOSITES BY IN-SITU POLYMERIZATION

A kind of new nano composite with ultraviolet （UV） ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide （PSA） was synthesized with 4, 4＇-diaminodiphenyl sulfone （DDS） and terephthaloyl chloride （TPC） in the common solvent N, N-Dimethyl- -acetamide （DMAc）. Nano filler is a certain nano titanium oxide modified by silicon oxide （TMS）, which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy （AFM）, thermal gravimetric Analysis （TGA） and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.

Morphology and conductivity of in-situ PEO-LiClO_4-TiO_2 composite polymer electrolyte

PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.

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.

STUDIES ON THE PERMEABILITY OF P VC/EBBA OVERLAPPED ULTRATHIN COMPOSITE MEMBRANES MODIFIED BY PLASMA-POLYMERIZATION WITH FLUOROCARBON MONOMERS

The PVC/EBBA ultrathin composite membranes with thickness of about 100 nm were prepared by spreading the solution on water surface. The overlapped composite membrane showed a characteristic aggregation structure in which the polymer matrix exists as a three-dimensional spongy network and the liquid crystal domains werc observed. Tne surface modification for the overlapped membranes was carried out by means of plasma-polymerization with the monomers of fluorocarbon compounds. Both Arrhenius plots of permeability coefficients for oxygen ((?)_O_2) in the membrane samples before and after modification showed significant increase in the vicinity of the T_(KN) of EBBA.

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.

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℃.

In situ polymerization preparation and mechanical properties of nanocomposites based on PA10T/10I-block-PEG copolymer and graphene oxide

Poly(decamethylene terephthalamide/decamethylene isophthalamide)-block-polyvinyl alcoho)(PA10 T/10 IPEG) copolymer/graphene oxide(GO) composites were prepared via in-situ melt polymerization and two different nano-filler addition approaches were compared. The relationship between the micro-structure and performance of the elastomer composites prepared by one-step and two-step methods was explored. The results show that the two-step method significantly promoted the dispersion of the GO in a polymer matrix, and facilitated the grafting of more hard molecular chains. Thus, the elastic modulus and tensile strength of the nanocomposite have been significantly improved by the presence of GO. This was because of the strong interaction between the functional groups on the surface of the GO and the hard molecular chains. This would be also be favorable to load transfer across the interface. Additionally, the elongation at the break of composites increased by 10% with the addition of a small amount of GO(0.2% wt). This is because hard domains tend to be enriched on the surface of GO in composites and act as a lubricating layer at the interface between the GO and matrix, leading to increased deformation ability. This work provides an effective strategy to prepare elastomer composites with high strength and toughness.

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.

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.

Introducing electrolytic electrochemical polymerization for constructing protective layers on Ni-rich cathodes of Li-ion batteries

LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)is the most promising cathode for high-energy Li-ion batteries,despite its poor cycling stability that originates from the reactions that occur with the electrolyte.Herein,to solve this interfacial issue,a facile electrolytic electrochemical polymerization process was introduced in this paper,and a uniform conductive electrolyte interface(polyaniline)was successfully constructed on the surface of the NCM811 porous electrode(PANI-NCM),which facilitated the charge transfer during charge/discharge.The side reactions at the interface between the cathode and the electrolyte are suppressed,and thereby,the cycling performance and rate capability are considerably improved.PANI-NCM delivers an initial capacity of 157.2 mAh·g^(-1)as well as excellent cyclability(capacity retention of 88%after 500 cycles at 2C),whereas the capacity of the bare NCM811 has dropped to 31.3 mAh·g^(-1).In addition,polypyrrole and polythiophene also can be formed through electrolytic electrochemical polymerization process,which provides a practicable tactic to modify the interfacial stability of cathodes for high-energy Li-ion batteries.

SiO_(2) nanofiber composite gel polymer electrolyte by in-situ polymerization for stable Li metal batteries

Gel polymer electrolytes(GPEs) are promising alternatives to liquid electrolytes applied in high-energydensity batteries.Here superior SiO_(2) nanofiber composite gel polymer electrolytes(SNCGPEs) are developed via in-situ ionic ring-opening polymerization of 1,3-dioxolane(DOL) monomers in SiO_(2) nanofiber membrane(PDOL-SiO_(2)) for lithium metal batteries.The oxygen atoms of PDOL together with Si-O of SiO_(2) construct a more efficient channel for Li^(+) migration.Consequently,the lithium ion transference number(t_(Li^(+)) and ionic conductivity(σ) at 30℃ of PDOL-SiO_(2) are 0.80 and 1.68×10^(-4)S/cm separately.PDOL-SiO_(2) manifests the electrochemical decomposition potentials of 4.90 V.At 0.5 mA/cm^(2),Li|PDOL-SiO_(2) |Li cell shows a steady cycling performance for nearly 1400 h.LFP|PDOL-SiO_(2) |Li battery can steadily cycle at 0.5 C with a capacity retention rate of 89% after 200 cycles.While cycling at 2 C,the capacity retention rate can maintain at 78% after 300 cycles.This contribution provides a innovative strategy for accelerating Li^(+)transportation via designing PDOL molecular chains throughout the SiO_(2) nanofiber framework,which is crucial for high-energy-density LMBs.

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.

偶联法SBS聚合工艺控制及质量影响因素分析

介绍偶联法苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的聚合反应特点和工艺流程,分析产品质量影响因素,阐述产品质量调节和控制的要点,如有效控制聚合反应引发温度和压力,在聚合单元对聚合胶液定期多次取样,并通过凝胶渗透色谱分析聚合反应的稳定性和产品质量异常情况,及时对胶液的相对分子质量、偶联剂加料时间、偶联效率等进行相应调整。对SBS实际生产过程中的常见异常情况进行分析,并提出有针对性的解决措施,保证产品质量稳定。