Novel sandwich structured glass fiber Cloth/Poly(ethylene oxide)-MXene composite electrolyte

Recently,poly(ethylene oxide)(PEO)-based solid polymer electrolytes have been attracting great attention,and efforts are currently underway to develop PEO-based composite electrolytes for next generation high performance all-solid-state lithium metal batteries.In this article,a novel sandwich structured solid-state PEO composite electrolyte is developed for high performance all-solid-state lithium metal batteries.The PEO-based composite electrolyte is fabricated by hot-pressing PEO,LiTFSI and Ti_(3)C_(2)T_(x) MXene nanosheets into glass fiber cloth(GFC).The as-prepared GFC@PEO-MXene electrolyte shows high mechanical properties,good electrochemical stability,and high lithium-ion migration number,which indicates an obvious synergistic effect from the microscale GFC and the nanoscale MXene.Such as,the GFC@PEO-1 wt%MXene electrolyte shows a high tensile strength of 43.43 MPa and an impressive Young's modulus of 496 MPa,which are increased by 1205%and 6048%over those of PEO.Meanwhile,the ionic conductivity of GFC@PEO-1 wt%MXene at 60℃ reaches 5.01×10^(-2) S m^(-1),which is increased by around 200%compared with that of GFC@PEO electrolyte.In addition,the Li/Li symmetric battery based on GFC@PEO-1 wt%MXene electrolyte shows an excellent cycling stability over 800 h(0.3 mA cm^(-2),0.3 mAh cm^(-2)),which is obviously longer than that based on PEO and GFC@PEO electrolytes due to the better compatibility of GFC@PEO-1 wt%MXene electrolyte with Li anode.Furthermore,the solid-state Li/LiFePO_(4) battery with GFC@PEO-1 wt%MXene as electrolyte demonstrates a high capacity of 110.2–166.1 mAh g^(-1) in a wide temperature range of 25–60C,and an excellent capacity retention rate.The developed sandwich structured GFC@PEO-1 wt%MXene electrolyte with the excellent overall performance is promising for next generation high performance all-solid-state lithium metal batteries.

POLYMERIZATION OF ETHYLENE METHYL PHOSPHATE IN THE PRESENCE OF SODIUM POLY(ETHYLENE GLYCOL)ATE

Poly(ethylene methyl phosphate)-poly(ethylene glycol)-poly(ethylene methyl phosphate) triblock copolymers carrying hydroxyl group at both chain ends were synthesized with sodium poly(ethylene glycol)ate as initiator. The effects of the factors such as solvent, amount of the initiator and reaction time were investigated. The copolymers were characterized by IR, H-1-NMR, H-1{P-31}-NMR, C-13-NMR, P-31{H-1}-NMR, and DSC. High molecular weight of the copolymer and high yield of the polymerization were achieved within 3 min at 25 degrees C. The polymerization process was studied by P-31{H-1}-NMR and transesterification was found during longer polymerization time.

Structure and Properties of Poly (ethylene terephthalate)/Tin Fluorophosphate Glass Hybrids

Poly(ethylene terephthalate)(PET)/tin fluorophosphate glass(Pglass) hybrids were prepared via melt blending in the present paper,and the phase morphology,dynamic rheology,crystallization behavior,dynamic and static mechanical properties,and thermal stability of the hybrids have been investigated.Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) showed the Pglass particles well dispersed in the PET matrix within a nanoscale.The results showed that the addition of Pglass induced some advantages on the properties of PET matrix,such as the decreasing of melt viscosity,increasing the isothermal crystallization rate and crystallinity,and improving the storage modulus and elasticity modulus.

Synthesis and Properties of Biodegradable Copolymers of 9-Phenyl-2, 4, 8, 10-tetraoxaspiro-[5, 5]undcane-3-one and Ethylene Ethyl Phosphate

Novel biodegradable copolymer poly（CC-co-EEP） was synthesized by ring-opening copolymerization of cyclic carbonate 9-phenyl-2, 4, 8, 10-tetraoxaspiro-[5, 5]undcane-3-one （CC） and ethylene ethyl phosphate （EEP）. The obtained poly （CC-co-EEP）s were characterized by FTIR, ^1H NMR, ^13C NMR and gel permeation chromatography （GPC）. In vitro hydrolytic degradation of the copolymers were investigated in phosphate buffer solution （pH=7.4）. Hydrophilic phosphate units apparently improved the degradability of poly（carbonate-phosphate）.

Study of Thermal,Phase Morphological and Mechanical Properties of Poly(L-lactide)-b-Poly(ethylene glycol)-b-Poly(L-lactide)/Poly(ethylene glycol)Blend Bioplastics

A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.

Three-in-one fire-retardant poly(phosphate)-based fast ion-conductor for all-solid-state lithium batteries

The development of flame retardant or nonflammable electrolytes is the key to improve the safety of lithium batteries,owing to inflammable organic solvents and polymer matrix in common liquid and polymer electrolytes regarded as the main cause of battery fire.Herein,a series of solid-state polyphosphate oligomers(SPPO)as a three-in-one electrolyte that integrated the roles of lithium salt,dissociation matrix,and flame retardant were synthesized.The well-designed SPPO electrolytes showed an optimal ionic conductivity of 5.5×10^(-4)S cm-1at 30℃,an acceptable electrochemical window up to 4.0 V vs.Li/Li+,and lithium ion transference number of 0.547.Stable Li-ion stripping/plating behavior for 500 h of charge-discharge cycles without internal short-circuit in a Li|SPPO|Li cell was confirmed,together with outstanding interface compatibility between the SPPO electrolyte and lithium foil.The optimal Li|SPPO|LiFePO4cell presented good reversible discharge capacity of 149.4 mA h g-1at 0.1 C and Coulombic efficiency of 96.4%after 120 cycles.More importantly,the prepared SPPO cannot be ignited by the lighter fire and show a limited-oxygen-index value as high as 35.5%,indicating splendid nonflammable nature.The SPPO could be a promising candidate as a three-in-one solid-state electrolyte for the improved safety of rechargeable lithium batteries.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

Preparation and Thermo-Responsive Properties of Poly(Oligo(Ethylene Glycol)Methacrylate)Copolymers with Hydroxy-Terminated Side Chain

Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.

Influence of Ethylene Glycol on the Formation of Calcium Phosphate Nanocrystals

A synthesis route of using calcium hydroxide Ca(OH)2 with ethylene glycol solvent and orthophosphoric acid (H3PO4) as reagents is described. Three ratios of ethylene glycol to distilled water 1:0, 1:1 and 0:1 are used as diluting media for Ca(OH)2. Crystals of different morphology and composition are formed under weak alkaline circumstance at pH 7.0-8.0. Acicular calcium phosphate nanocrystals are prepared in pure ethylene glycol while rod-like calcium phosphate nanocrystals form in pure distilled water. The nanograde size of the former is smaller than that of the latter. Calcium-deficient apatite (CDAP) is obtained with a Ca/P molar ratio of 1.66. Therefore, it was deduced that the usage of ethylene glycol solvent could influence the formation of calcium phosphate crystal lattice.

Studies on the Simultaneous Synthesis of Dimethyl Carbonate and Poly(ethylene terephthalate): I. Catalytic Activity of Metal Acetate in Transesterification of Ethylene Carbonate with Dimethyl Terephthalate

A novel direct method for preparation of dimethyl carbonate and poly（ethylene terephthalate） from ethylene carbonate and dimethyl terephthalate has been demonstrated in the presence of metal acetate catalysts, lithium acetate dihydrate showed highest catalytic activity with 47.9% yield of dimethyl carbonate. This method was a green chemical process.

SURFACE MODIFICATION OF BLEND FILMS COMPOSED OF SILK FIBROIN AND POLY(ETHYLENE GLYCOL) MACROMER AND THEIR IN VITRO ANTITHROMBOGENICITY

In order to improve the blood compatibility of silk fibroin (SF), poly(ethylene glycol) macromer (PEGM) in different amounts was added to the SF film to incorporate C=C group into the surface of blend films which were then modified by SO2 gas plasma treatment. ATR-FITR and XPS were used to analyze the chemical change which had occurred on the film's surface. When the content of sulfur on the surface of blend films surpasses 1.59%, the antithrombogenicity of plasma treated films increases remarkably due to surface sulfonation. This result implies that SF with blend of PEGM after SO2 plasma treatment have potential use for making blood-contacting biomaterials.

Controlled delivery of ibuprofen from poly(vinyl alcohol)-poly(ethylene glycol) interpenetrating polymeric network hydrogels

Hydrogels composed of poly(vinyl alcohol)(PVA) and poly(ethylene glycol)(PEG) were synthesized using glutaraldehyde as crosslinker and investigated for controlled delivery of the common anti-inflammatory drug, ibuprofen(IBF). To regulate the drug delivery, solid inclusion complexes(ICs) of IBF in β–cyclodextrin(β–CD) were prepared and added to the hydrogels. The ICs were prepared by the microwave irradiation method, which is more environmentally benign. The formation of IC was confirmed by various analytical techniques and the synthesized hydrogels were also characterized. Controlled release of drug was achieved from the hydrogels containing the ICs in comparison to the rapid release from hydrogels containing free IBF.The preliminary kinetic analysis emphasized the crucial role of β–CD in the drug release process that influences the polymer relaxation, thereby leading to prolonged release. The cytotoxicity assay validated the hydrogels as non-toxic in nature and hence can be utilized for controlled delivery of IBF.

Characterization and Properties of Electroless Nickel Plated Poly (ethylene terephthalate) Nonwoven Fabric Enhanced by Dielectric Barrier Discharge Plasma Pretreatment

In order to develop a more economical pretreatment method for electroless nickel plating, a dielectric barrier discharge （DBD） plasma at atmospheric pressure was used to improve the hydrophilicity and adhesion of poly （ethylene terephthalate） （PET） nonwoven fabric. The properties of the PET nonwoven fabric including its liquid absorptive capacity （WA）, aging behavior, surface chemical composition, morphology of the surface, adhesion strength, surface electrical resistivity and electromagnetic interference （EMI）- shielding effectiveness （SE） were studied. The liquid absorptive capacity （WA） increased due to the incorporation of oxygen-containing and nitrogen-containing functional groups on the surface of PET nonwoven fabric after DBD airplasma treatment. The surface morphology of the nonwoven fibers became rougher after plasma treatment. Therefore, the surface was more prone to absorb tin sensitizer and palladium catalyst to form an active layer for the deposition of electroless nickel. SEM and X-ray diffraction （XRD） measurements indicated that a uniform coating of nickel was formed on the PET nonwoven fabric. The average EMI-SE of Ni-plating of PET nonwoven fabric maintained a relatively stable value （38.2 dB to 37.3 dB） in a frequency range of 50 MHz to 1500 MHz. It is concluded that DBD is feasible for pretreatment of nonwoven fabric for electroless nickel plating to prepare functional material with good EMI-SE properties.

Poly(L-lactide)-Poly(ethylene glycol) Multiblock Copolymers: Synthesis and Properties

Poly (L-lactide)-poly(ethylene glycol) multiblock copolymers with predetermined block lengths were synthesized by polycondensation of PLA diols and PEG diacids. These copolymers presented special properties, such as better miscibility between the two components, low crystallinity and better hydrophilicity, which can be modulated by adjusting the block lengths of the two components.

THE STRUCTURE AND PROPERTIES OF CHITOSAN/POLYETHYLENE GLYCOL/SILICA TERNARY HYBRID ORGANIC-INORGANIC FILMS

The ternary hybrid films consisting of chitosan(CS),polyethylene glycol(PEG)and nano-sized silica which was surface-modified by amino groups(RNSA)were prepared.The structures of the blend membranes were characterized by attenuation total reflection-infrared spectroscopy(ATR-IR),X-ray diffraction(XRD),optical microscopy(OM)and differential scanning calorimetry(DSC).The results showed that the addition of silica affected not only the distribution and crystallinity of PEG on the sample surface,but also the pha...

Y-shaped block copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) synthesized by ATRP

Novel Y-shaped block copolymers of poly（ethylene glycol） and poly（N-isopropylacrylamide）, PEG-b-（PNIPAM）2, were successfully synthesized through atom transfer radical polymerization （ATRP）. A difunctional macroinitiator was prepared by esterification of 2,2-dichloroacetyl chloride with poly（ethylene glycol） monomethyl ether （PEG）. The copolymers were obtained via the ATRP ofN-isopropylacrylamide （NIPAM） at 30℃ with CuCl/Me6TREN as a catalyst system and DMF/H2O （v/v = 3：1） mixture as solvent. The resulting copolymers were characterized by gel permeation chromatography （GPC） and ^1H NMR. These block copolymers show controllable molecular weights and narrow molecular weight distributions （PDI 〈 1.15）. Their phase transition temperatures and the corresponding enthalpy changes in aqueous solution were measured by differential scanning calorimetry （DSC）. As a result, the phase transition temperature of PEG45-b-（PNIPAM55）2 is higher than that of PNIPAM, however, the corresponding enthalpy change is much lower, indicating the significant influence of the macromolecular composition and architecture on the phase transition.

Structural regulation chemistry of lithium-ion solvation in nonflammable phosphate-based electrolytes for high interfacial compatibility with graphite anode

With the booming development of lithium-ion batteries,safety has become one of the most primary focuses of current researches.Although there are various approaches to enhance the safety of lithiumion batteries,phosphate-based electrolyte holds the greatest potential for practical application due to their non-flammability.Nonetheless,its compatibility issue with the graphite anode remains a significant obstacle to its widespread use.Herein,an effective method is proposed to improve the compatibility of electrolyte with graphite(Gr)anode by rationally adjusting the proportion of lithium salt and solvent components to optimize the Li^(+)solvation structure.By slightly increasing the Li^(+)/triethyl phosphate(TEP)ratio,TEP alone cannot fully occupy the inner solvation sheath and therefore less polar ethylene carbonate(EC)has to be recruited,and the solvation structure gradually changes from Li^(+)–[TEP]_(4)to Li^(+)–[TEP]_(3)[EC]with the coexistence of EC and TEP.Simultaneously,EC molecules in the Li^(+)–[TEP]_(3)[EC]could be preferentially reduced on graphite compared to the TEP molecules,resulting in the formation of a uniform and durable solid-electrolyte interphase(SEI)layer.Benefiting from the optimized phosphate-based electrolyte,the Gr|Li battery exhibits a capacity retention rate of 96.8%after stable cycling at 0.5 C for 470 cycles which shows a longer cycle life than the battery with carbonate electrolyte(cycling at 0.5 C for 450 cycles).Therefore,this work provides the guidance for designing a non-flammable phosphate-based electrolyte for high-safety and long cycling-life lithium-ion batteries.

Flame Retardancy and Thermal Property of Poly (ethylene terephthalate)/Modified Cyclotriphosphazene Composites

In this study,hexachlorocyclotriphosphazene( HCCP)modified by boric acid and 3-aminopropyltriethoxysilane( KH-550)in solvent diglyme( FR-HCCP) was used as the flame retardant for poly( ethylene terephthalate)( PET) composites. The flame retardancy and thermal property of pure PET and flame-retarded PET composites were mainly investigated. The flame retardancy was investigated by limited oxygen index( LOI) and UL-94 vertical burning test. The results showed that the composites could achieved an increased UL-94 V-0 rating and LOI value 30. 2, when the content of FR-HCCP was just 1%. The pyrolysis-gas chromatography-mass spectrometry( Py-GC / MS) study demonstrated that introducing FR-HCCP into PET would prevent the polymer pyrolysis during heating. TGA analysis showed that the addition of FR-HCCP could improve the char formation of the system. Roman spectra showed the order degree of residue was increasing by adding the additive. The morphology and the chemical structure of the charred residue were detected by SEMand FTIR,respectively. Results demonstrated that a good barrier was formed by the char of the composite,which protected the inside of the composite during burning.

PHASE SEPARATION BEHAVIOR OF SURLYN IN POLY (ETHYLENE TEREPHTHALTE)

The phase separation behavior of blend of Surlyn and poly(ethylene terephthalate) (PET) has been studied by scanning electron microscopy and IR. It is shown that particles of Surlyn are dispersed in PET matrix, and this phase separation is controlled by heat-treated conditions of the blend.

FOURIER TRANSFORM INFRARED STUDIES OF POLY (ETHYLENE TEREPHTHALATE) FILM IN THE GLASS TRANSITION REGION

Three specimens from a solution-cast poly (ethylene terephthalate) (PET) film, one being liquid-N_2 quenched from 92℃(Q), one being slowly cooled from 92℃(SC) and one being quenched and sub-T_g annealed at 67℃(AN), have been studied by specimen difference spectra Q-SC and AN-Q and temperature difference spectra T-70 and T_2-T_1 for every 2℃ steps on heating to 90℃ at 2℃ /min. SC and AN showed more gauche conformers than Q. That means that the PET chain has more trans conformers at higher temperatures and some of these are frozen during quenching through T_g. A band at 1340 cm^(-1) has been found to be complex containing overlapping bands reflecting trans in crystalline regions and trans in amorphous regions. The temperature difference spectra on heating through T_g showed that the spectral changes in Q are gradual while a rather abrupt change occurs in AN at 80—82℃ for the bands at 1340, 1042 and 1020 cm^(-1). No new conformational structure or new vibrational mode is involved. A kind of locking mechanism is suggested which hinders the molecular vibrational changes in AN below T_g until a sudden release occurs at T_g. These locking sites can be nothing else than sites of tighter local packing of chain segments. Consequently it is believed that inter-chain van der Waals attraction energy plays a dominating role in the volume relaxation and sub-T_g annealing of quenched amorphous polymers.