Mechanistically Novel Frontal-Inspired In Situ Photopolymerization:An Efficient Electrode|Electrolyte Interface Engineering Method for High Energy Lithium Metal Polymer Batteries

The solvent-free in situ polymerization technique has the potential to tailor-make conformal interfaces that are essential for developing durable and safe lithium metal polymer batteries(LMPBs).Hence,much attention has been given to the eco-friendly and rapid ultraviolet(UV)-induced in situ photopolymerization process to prepare solid-state polymer electrolytes.In this respect,an innovative method is proposed here to overcome the challenges of UV-induced photopolymerization(UV-curing)in the zones where UV-light cannot penetrate,especially in LMPBs where thick electrodes are used.The proposed frontal-inspired photopolymerization(FIPP)process is a diverged frontal-based technique that uses two classes(dual)of initiators to improve the slow reaction kinetics of allyl-based monomers/oligomers by at least 50%compared with the conventional UV-curing process.The possible reaction mechanism occurring in FIPP is demonstrated using density functional theory calculations and spectroscopic investigations.Indeed,the initiation mechanism identified for the FIPP relies on a photochemical pathway rather than an exothermic propagating front forms during the UV-irradiation step as the case with the classical frontal photopolymerization technique.Besides,the FIPP-based in situ cell fabrication using dual initiators is advantageous over both the sandwich cell assembly and conventional in situ photopolymerization in overcoming the limitations of mass transport and active material utilization in high energy and high power LMPBs that use thick electrodes.Furthermore,the LMPB cells fabricated using the in situ-FIPP process with high mass loading LiFePO_(4)electrodes(5.2 mg cm^(-2))demonstrate higher rate capability,and a 50%increase in specific capacity against a sandwich cell encouraging the use of this innovative process in large-scale solid-state battery production.

In Situ Directional Polymerization of Poly(1,3-dioxolane)Solid Electrolyte Induced by Cellulose Paper-Based Composite Separator for Lithium Metal Batteries

In traditional in situ polymerization preparation for solid-state electrolytes,initiators are directly added to the liquid precursor.In this article,a novel cellulose paper-based composite separator is fabricated,which employs alumina as the inorganic reinforcing material and is loaded with polymerization initiator aluminum trifluoromethanesulfonate.Based upon this,a separator-induced in situ directional polymerization technique is demonstrated,and the extra addition of initiators into liquid precursors is no longer required.The polymerization starts from the surface and interior of the separator and extends outward with the gradually dissolving of initiators into the precursor.Compared with its traditional counterpart,the separator-induced poly(1,3-dioxolane)electrolyte shows improved interfacial contact as well as appropriately mitigated polymerization rate,which are conducive to practical applications.Electrochemical measurement results show that the prepared poly(1,3-dioxolane)solid electrolyte possesses an oxidation potential up to 4.4 V and a high Li+transference number of 0.72.After 1000 cycles at 2 C rate(340 mA g^(−1)),the assembled Li||LiFePO_(4)solid battery possesses a 106.8 mAh g^(−1)discharge capacity retention and 83.5%capacity retention ratio,with high average Coulombic efficiency of 99.5%achieved.Our work may provide new ideas for the design and application of in situ polymerization technique for solid electrolytes and solid batteries.

High-Performance Quasi-Solid-State Pouch Cells Enabled by in situ Solidification of a Novel Polymer Electrolyte

Conventional lithium-ion batteries(LIBs)with liquid electrolytes are challenged by their big safety concerns,particularly used in electric vehicles.All-solid-state batteries using solid-state electrolytes have been proposed to significantly improve safety yet are impeded by poor interfacial solid–solid contact and fast interface degradation.As a compromising strategy,in situ solidification has been proposed in recent years to fabricate quasi-solid-state batteries,which have great advantages in constructing intimate interfaces and cost-effective mass manufacturing.In this work,quasi-solid-state pouch cells with high loading electrodes(≥3 m Ah cm^(-2))were fabricated via in situ solidification of poly(ethylene glycol)diacrylate-based polymer electrolytes(PEGDA-PEs).Both single-layer and multilayer quasi-solid-state pouch cells(2.0 Ah)have demonstrated stable electrochemical performance over500 cycles.The superb electrochemical stability is closely related to the formation of robust and compatible interphase,which successfully inhibits interfacial side reactions and prevents interfacial structural degradation.This work demonstrates that in situ solidification is a facile and cost-effective approach to fabricate quasi-solid-state pouch cells with both excellent electrochemical performance and safety.

Flame retardant polyamide 6 by in situ polymerization of ε-caprolactam in the presence of melamine derivatives

An improved method for preparing melamine cyanurate （MCA） based flame retardant polyamide 6 （FRPA6） materials has been proposed. This processing method, i.e., improved in situ polymerization, was used to synthesize flame retardant PA6. In situ formed MCA nanoparticles were supposed to be linked to PA6 chains in the ε-caprolactam hydrolytic polymerization system to obtain startype polymers for the first time. Through TEM photographs, it can be found that the in situ formed MCA nanoparticles with diametric size of less than 50 nm, are nanoscaled, highly uniformly dispersed in the PA6 matrix. Synthesized flame retardant PA6 have good fire performance which can achieve UL-94 V-0 rating at 1.6 mm thickness with the presence of 7.34 wt.% MCA in the matrix.

In situ polymerization coating and characteristics of coated NPK compound fertilizer

Controlled release NPK compound fertilizers were prepared by means of in situ polymerization of monomers on the surface of fertilizer granules at room temperature. Methacrylate, α-methyl acrylic acid, and ethylene dimethylacrylate were used as monomers, Dibenzoyl peroxide as initiator, and cobalt naphthenate, and triethyl amine as promoters. The structures of coating materials were characterized by IR spectra. The thermogravimetric analysis result indicated that the coating materials were of good thermal stability. The mean thickness of single coating measured with screw gauge was ca. 140 μm. The morphologies of uncoated and coated fertilizer granules analyzed by using scanning electron microscopy were changed from porosities and gullies to hills and plain. The release rate of coated compound fertilizers in water could be controlled by the hydrophicity and thickness of coating. The increase in coating hydrophicity caused the increase in release rate of fertilizer. The increase in thickness of coating slowed the release rate.

In-situ Polymerization-modification Process and Foaming of Poly（ethylene terephthalate）

Most of traditional linear poly(ethylene terephthalate)(PET)resins of relatively low molecular mass and narrow molecular mass distribution have low melt strength at foaming temperatures,which are not enough to support and keep cells.An in-situ polymerization-modification process with esterification and polycondensation stages was performed in a 2 L batch stirred reactor using pyromellitic dianhydride(PMDA)or pentaerythritol(PENTA)as modifying monomers to obtain PETs with high melt strength.The influence of amounts of modifying monomers on the properties of modified PET was investigated.It was found that the selected modifying monomers could effectively introduce branched structures into the modified PETs and improve their melt strength.With increasing the amount of the modifying monomer,the melt strength of the modified PET increased.But when the amount of PENTA reached 0.35%or PMDA reached 0.9%,crosslinking phenomenon was observed in the modified PET.Supercritical carbon dioxide(ScCO2)was employed as physical foaming agent to evaluate the foaming ability of modified PETs.The modified PETs had good foaming properties at 14 MPa of CO2pressure with foaming temperature ranging from 265°C to 280°C.SEM micrographs demonstrated that both modified PET foams had homogeneous cellular structures,with cell diameter ranging from 35μm to 49μm for PENTA modified PETs and38μm to 57μm for PMDA modified ones.Correspondingly,the cell density had a range of 3.5×107cells·cm 3to 7×106cells·cm 3for the former and 2.8×107cells·cm 3to 5.8×106cells·cm 3for the latter.

Synthesis of PMA/Eu_2O_3 porous-layered nanocomposite by in situ polymerization and its morphology

The PMA/Eu2O3 porous and layered nanocomposite was prepared by in situ polymerization and characterized by means of X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscope （SEM）, and inflared ray （IR）. Microscopic investigation of the nanocomposite was carded out by atomic force microscopy （AFM）. The results showed that the shape of the composite was layered and porous. Eu2O3 was grafted when methyl acrylate （MA） polymerized; thus Eu2O3 particles appeared on both sides of the chains of polymeric methyl acrylate （PMA）.

In situ polymerization preparation and characterization of Li_4Ti_5O_(12)-polyaniline anode material

Li4Ti5O12 powders were prepared by so-gel method using tetrabutyl titanate,lithium acetate and absolute alcohol as starting materials.Li4Ti5O12-polyaniline(Li4Ti5O12-PAn)composite was prepared by in situ polymerization method using aniline, ammonium persulfate and hydrochloricarried as starting materials.Li4Ti5O12-PAn composite was characterized by X-ray diffractometry(XRD),infrared spectrum(IR)combined with electrochemical tests.The results show that the electrical conductivity is enhanced obviously due to the introduction of PAn to Li4Ti5O12.Li4Ti5O12-PAn composite exhibits better high-rate capability and cyclability than Li4Ti5O12.The composite can deliver a specific capacity of 191.3 and 148.9 mA·h/g,only 0.13%and 0.61%of the capacity is lose after being discharged 80 times at 0.1C and 2.0C,respectively.

STUDY ON NYLON 6/SUPERFINE RUBBER PARTICLES COMPOSITES VIA IN SITU POLYMERIZATION

Two highly cross-linked superfine styrene-butadiene rubber particles, one with 1 wt% of carboxyl groups and theother without such groups having particle sizes of 130-150 nm and 80-100 nm respectively, were used to prepare nylon6/rubber composites via in situ polymerization. It was found that carboxylic styrene-butadiene dispersed uniformly in nylonmatrix and there was strong interfacial interaction because of the graft polymer formed by the reaction of nylon with carboxylgroup of the rubber, resulting in considerably improved impact strength with almost unchanged tensile strength. However,the addition of styrene-butadiene without carboxyl groups showed intensive agglomeration of the rubber particles and weakinterfacial interactions, and the toughness of the materials was improved slightly. The crystallization and rheological behavior of the composites were also discussed.

Thermoelectric properties of Bi_(0.5)Sb_(1.5)Te_3/polyaniline composites prepared by mechanical blending and in-situ polymerization

Bi 0.5 Sb 1.5 Te 3/polyaniline composites were prepared by mechanical blending and in situ polymerization, and their transport properties were measured. It was found that for the composites with 1%, 3%, 5% and 7% polyaniline (mass fraction) respectively, which were prepared by mechanical blending, the power factors decrease by about 30%, 50%, 55% and 65% compared with the Bi 0.5 Sb 1.5 Te 3 samples, which is mainly due to the remarkable decreases of the electrical conductivity. The electrical conductivity and power factor of the composites samples with 7% polyaniline prepared by in situ polymerization are higher by about 65% and 60%, respectively, than that of the corresponding samples prepared by mechanical blending.

Thermal Stability and Crystallinity Study of Polystyrene/SiO2 Nano-Composites Synthesis via Microwave-Assisted In Situ Polymerization

Serials of polystyrene/SiO2 Nano composites (PS/SiO2) with different content of inorganic fillers were successfully prepared by the in situ bulk radical polymerization of styrene under microwave irradiation. The effect of the amount of Nano SiO2 on the properties of the PS/SiO2 Nanocomposites along with the average relative molecular masses (Mn, Mz and Mw) was investigated by thermal analysis and X-Ray Diffraction (XRD). Their structural model was proposed on the basis of the Optical Microscopy, FTIR (Fourier Transform Infrared) analysis, differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and X-Ray Diffraction (XRD). The dispersion of nanoparticles in Polystyrene is observed in the magnified image. The effect of microwave irradiation power on molecular weight of polystyrene was also studied. It was found that, the microwave assisted reaction needs less time as compare to conventional polymerization and found to be in between 10 to 15 min.

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.

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO_(2) separation

Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.

Hydrothermal in situ Ligand Synthesis from 1,10-Phenanthroline-5,6-dione and Characterization of 1D Coordination Polymers [Co(bpdc)(H_2O)_3]·H_2O and [Cu(bpy)V_2O_6]

Hydrothermal treatment of MCl2 （ M = Co or Cu ） , NH4 VO3, and 1,10-phenanthroline-5,6-dione （pdon） resulted in the formation of a duplex coordination polymer [ Co （ bpdc ） （ H2O ） 3 ] · H2O （ bpdc = 2,2＇-bipyridine-3,3＇-dicarboxylate） and a chain-like coordination polymer [ Cu （bpy） V2O6 ] （ bpy = 2,2＇-bipyridine ）. X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.

In Situ Synthesis, Structural Characterization and Catalytic Properties of a 2D Cu(Ⅰ)-cyanide Coordination Polymer

A new Cu(Ⅰ) coordination polymer(CP) formulated as [Cu2(L)(CN)2]n(1, L =1,1′-bis(5,6-dimethylbenzimidazole)methane) was synthesized, in which the cyanide anions were generated in situ by the cleavage of C–C bond of acetonitrile under hydrothermal conditions. CP 1 was characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, Pccn space group, with a = 10.314(3), b = 20.966(7), c =9.432(3)?, V = 2039.5(11)?3, Z = 4, C21 H20 Cu2 N6, Mr = 483.51, Dc = 1.575 g×cm^-3,μ= 2.105 mm-1 and F(000)= 984, the final R = 0.0608 and wR = 0.1942 for 1226 observed reflections with Ⅰ> 2s(Ⅰ)for the CP 1. The CP 1 possesses a 2D {63} layer structure which is composed of Cu(Ⅰ) centers bridged by L and CN– ligands. The thermal stability and luminescence properties of CP 1 are discussed in detail. The complex also displays a remarkable activity for the degradation of methyl orange by hydrogen peroxide in a Fenton-like process.

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.

NEW INITIATION SYSTEMS FOR ATOM TRANSFER RADICAL POLYMERIZATION

This review summarizes our achievements in designing new initiation systems for atom transfer radical polymerization (ATRP). First-order kinetics and extension experiments revealed the living nature of these reactions. Tailor- made vinyl polymers with functional end groups were characterized by 1H-NMR and UV-vis spectroscopic analyses. Replacing traditional radical initiators AIBN and BPO, carbon-carbon bond compounds, 1,1,2,2-tetraphenyl-1,2-ethanediol, diethyl 2,3-dicyano-2,3-diphenylsuccinate and diethyl 2,3-dicyano-2,3-di(p-tolyl)succinate, were utilized in reverse ATRP to produce the initiating radical. Sulfur-sulfur bond iniferter, tetraethylthiuram disulfide (TD), in conjunction with CuBr/bpy or NiCl2/PPh3 complex could control the styrene polymerization via redox reaction. Pseudo-halogen transfer reaction was demonstrated to maintain the dormant-active species equilibrium in normal and reverse ATRP with Cu(S2CNEt2), Cu(S2CNEt2)Cl and Fe(S2CNEt2)3 as catalysts. The organic halide initiator and reduced transition metal compound that started the living polymerization were produced in situ from the components of TD/FeCl3/PPh3, TD/CuBr2/bpy and Fe(S2CNEt2)3/FeCl3/PPh3 systems. Accurate control of UV irradiation time favored the radical generation process in photo ATRP with the 2,2-dimethoxy-2-phenylacetophenone/Fe(S2CNEt2)3 initiation system.

DISPERSION AND IN SITU FORMED FIBER OF LOW MELTING POINT METALS IN POLYMER

The dispersion mechanism of low melting point metal (LMPM) particles in polymers was studied using Cox dilute emulsion model. The critical destruction shear stress sigma of LMPM droplets is sigma greater than 2 v/d. When sigma is small, LMPM droplets were dispersed and deformed ellipsoidal or bar droplets whose orientation direction is always at an angle of 45 degree with the direction of shear rate. When sigma is very big and droplets are very fine, polymer melt elasticity behavior and big boundary tension between a polymer melt and LMPM droplets make further fining LMPM droplets become more difficult. Therefore, LMPM droplets produce tensile flow and form LMPM microfibrils in situ in polymer melt. SEM photographs have shown the results predicted using dilute emulsion model. (Author abstract) 7 Refs.