Lithium Salt Combining Fluoroethylene Carbonate Initiates Methyl Methacrylate Polymerization Enabling Dendrite-Free Solid-State Lithium Metal Battery

This work demonstrates a novel polymerization-derived polymer electrolyte consisting of methyl methacrylate,lithium bis(trifluoromethanesulfonyl)imide and fluoroethylene carbonate.The polymerization of MMA was initiated by the amino compounds following an anionic catalytic mechanism.LiTFSI plays both roles including the initiator and Li ion source in the polymer electrolyte.Normally,lithium bis(trifluoromethanesulfonyl)imide has difficulty in initiating the polymerization reaction of methyl methacrylate monomer,a very high concentration of lithium bis(trifluoromethanesulfonyl)imide is needed for initiating the polymerization.However,the fluoroethylene carbonate additive can work as a supporter to facilitate the degree of dissociation of lithium bis(trifluoromethanesulfonyl)imide and increase its initiator capacity due to the high dielectric constant.The as-prepared poly-methyl methacrylate-based polymer electrolyte has a high ionic conductivity(1.19×10^(−3)S cm^(−1)),a wide electrochemical stability window(5 V vs Li^(+)/Li),and a high Li ion transference number(t_(Li^(+)))of 0.74 at room temperature(RT).Moreover,this polymerization-derived polymer electrolyte can effectively work as an artificial protective layer on Li metal anode,which enabled the Li symmetric cell to achieve a long-term cycling performance at 0.2 mAh cm^(−2)for 2800 h.The LiFePO_(4)battery with polymerization-derived polymer electrolyte-modified Li metal anode shows a capacity retention of 91.17%after 800 cycles at 0.5 C.This work provides a facile and accessible approach to manufacturing poly-methyl methacrylate-based polymerization-derived polymer electrolyte and shows great potential as an interphase in Li metal batteries.

In Situ High-performance Gel Polymer Electrolyte with Dual-reactive Cross-linking for Lithium Metal Batteries

Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.

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 polymerized quasi-solid polymer electrolytes enabling void-free interfaces for room-temperature sodium-sulfur batteries

Rechargeable room-temperature(RT)sodium–sulfur(Na–S)batteries hold great potential for large-scale energy storage owing to their high energy density and low cost.However,their practical application is hindered by challenges such as polysulfide shuttling and Na dendrite formation.In this study,a dual salt-based quasi-solid polymer electrolyte(DS–QSPE)was developed via in situ polymerization,achieving high ionic conductivity(4.8×10-4 S·cm-1 at 25°C),a high sodium-ion transference number(0.73),and effective polysulfide confinement.Theoretical calculations and experimental results indicate that the enhanced Na-ion transport is attributed to the strengthened coordination of anions with the polydioxolane chain and the increased dissociation of sodium salts.Importantly,the DS–QSPE forms an interconnected network structure in the sulfurized polyacrylonitrile(SPAN)cathode.This provides abundant and seamless electrochemical reaction interfaces that facilitate efficient and uniform ion transport pathways.As a result,the Na||SPAN battery with DS–QSPE delivers a high capacity of approximately 327.4 mAh·g-1(based on the mass of SPAN)after 200 cycles at 0.2 A·g-1,retaining 81.4%of its initial capacity.This performance considerably surpasses that of batteries using liquid electrolytes.This study offers a straightforward approach to addressing the inter-facial challenges in solid-state Na–S batteries.

In-situ polymerization for PPy/g-C_3N_4 composites with enhanced visible light photocatalytic performance

Polypyrrole‐modified graphitic carbon nitride composites(PPy/g‐C3N4)are fabricated using an in‐situ polymerization method to improve the visible light photocatalytic activity of g‐C3N4.The PPy/g‐C3N4 is applied to the photocatalytic degradation of methylene blue(MB)under visible light irradiation.Various characterization techniques are employed to investigate the relationship between the structural properties and photoactivities of the as‐prepared composites.Results show that the specific surface area of the PPy/g‐C3N4 composites increases upon assembly of the amorphous PPy nanoparticles on the g‐C3N4 surface.Owing to the strong conductivity,the PPy can be used as a transition channel for electrons to move onto the g‐C3N4 surface,thus inhibiting the recombination of photogenerated carriers of g‐C3N4 and improving the photocatalytic performance.The elevated light adsorption of PPy/g‐C3N4 composites is attributed to the strong absorption coefficient of PPy.The composite containing 0.75 wt%PPy exhibits a photocatalytic efficiency that is 3 times higher than that of g‐C3N4 in 2 h.Moreover,the degradation kinetics follow a pseudo‐first‐order model.A detailed photocatalytic mechanism is proposed with·OH and·O2-radicals as the main reactive species.The present work provides new insights into the mechanistic understanding of PPy in PPy/g‐C3N4 composites for environmental applications.

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.

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.

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.

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.

–C≡N functionalizing polycarbonate-based solid-state polymer electrolyte compatible to high-voltage cathodes

Solid-state polymer electrolytes(SPEs) capable of withstanding high voltage are considered to be key for next-generation energy storage devices with inherent safety as well as high energy density.This study involves the rational design of solid-state-C≡N functionalized P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs and its synthesis by in-situ free radical polymerization of vinyl ethylene carbonate(VEC) and 2-cyanoethyl acrylate(CEA).In situ polymerization yields electrode/electrolyte interfaces with low interfacial resistance,forming a stable SEI layer enriched with LiF,Li_(3)N,and RCOOLi,ensuring stable Li plating/stripping for over 1400 h.The-C≡N moiety renders the αH on the adjacent αC positively charged,thereby endowing it with the capability to anchor TFSI^(-).Simultaneously,the incorporation of-C≡N moiety diminishes the electron-donating ability of the C=O,C-O-C,and-C≡N functional groups,facilitating not only the ion conductivity enhancement but also a more rapid Li^(+)migration proved by DFT theoretical calculations and Raman spectroscopy.At room temperature,t_(Li+) of 0.60 for P(VEC_1-CEA_(0.3))/LiTFSI@CE SPEs is achieved when the ionic conductivity σ_(Li+)is 2.63×10^(-4) S cm^(-1) and the electrochemical window is expanded to5.0 V.Both coin cells with high-areal-loading cathodes and the 6.5-mAh pouch cell,exhibit stable charge/discharge cycling.At 25℃,the 4.45-V Li|P(VEC_1-CEA_(0.3))/LiTFSI@CE|LiCoO_(2) battery performs stable cycling over 200 cycles at 0.2 C,with a capacity retention of 82.1%.

High-temperature resistant polymer nanocomposites with exfoliated organic-modified montmorillonite nanosheets strongly adsorbed on polymer chains

It has been demonstrated that almost all polymer-clay nanocomposites show higher temperature stability than that of pure polymer, which is attributed to the active exfoliated clay nanosheet firmly adsorbed onto the polymer chains, due to polerization and nucleation effect, the clay nanosheets could protect the polymer chains from destroying. To prove such mechanism, the water-soluble polymer nanocomposites(AAA/SLS-MMT) were synthesized by the in-situ polymerization of 2-acrylamide-2-methyl-propane sulfonic acid, acrylamide, 4-acryloylmorpholine, and organically modified montmorillonite. The techniques of nuclear magnetic resonance, atomic force microscopy and scanning electron microscopy etc., clearly characterized the successful synthesized of sample's structure, the exfoliated MMT nanosheet adsorbed polymer chain's scale, and well-dispersed morphology, espectively. The adsorption model, X-ray photoelectron spectroscopy presented the existence of strong adsorption, while molecular simulation calculations first concluded that the strong adsorption energy was-13032.06 kcal/mol. Thermo-gravimetric-analysis proved the temperature of maximum thermal degradation of powder sample(AAA/1.0 wt% SLS-MMT) was over 298℃. After ageing at 180℃ for 4 h, the apparent viscosity of 5 g/L AAA/1.0 wt% SLS-MMT aqueous solution was 326.7 mPa,s, while that of pure polymer(AAA) was only 8.3 mPa,s. This optimized sample has the smallest FLAPIvalue at all test temperatures from 180 to 220℃ in both fresh and salt water based drilling fluid. All the evidences of high temperature resistance indicate that the strong adsorption can enhance the thickness of hydrated shell and adsorption of clay particles in drilling fluid at high temperature. Such mechanism supplied the better way to design high-temperature resistant fluid loss additives for deep and ultra-deep oil and gas formation engineering.

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.

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.

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.