Flame-retardant ammonium polyphosphate/MXene decorated carbon foam materials as polysulfide traps for fire-safe and stable lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries with high loading of flammable sulfur faces the challenges of electrochemical performance degradation owing to the shuttle effect and safety issues related to fire or explosion accidents.In this work,we report a three-dimensional(3D)conductive nitrogen-doped carbon foam supported electrostatic self-assembled MXene-ammonium polyphosphate(NCF-MXene-APP)layer as a heat-resistant,thermally-insulated,flame-retardant,and freestanding host for Li-S batteries with a facile and costeffective synthesis method.Consequently,through the use of NCF-MXene-APP hosts that strongly anchor polysulfides,the Li-S batteries demonstrate outstanding electrochemical properties,including a high initial discharge capacity of 1191.6 mA h g^(-1),excellent rate capacity of 755.0 mA h g^(-1)at 1 C,and long-term cycling stability with an extremely low-capacity decay rate of 0.12%per cycle at 2 C.More importantly,these batteries can continue to operate reliably under high temperature or flame attack conditions.Thus,this study provides valuable insights into the design of safe high-performance Li-S batteries.

Leakage Proof,Flame-Retardant,and Electromagnetic Shield Wood Morphology Genetic Composite Phase Change Materials for Solar Thermal Energy Harvesting

Phase change materials(PCMs)offer a promising solution to address the challenges posed by intermittency and fluctuations in solar thermal utilization.However,for organic solid-liquid PCMs,issues such as leakage,low thermal conductivity,lack of efficient solar-thermal media,and flamma-bility have constrained their broad applications.Herein,we present an innova-tive class of versatile composite phase change materials(CPCMs)developed through a facile and environmentally friendly synthesis approach,leveraging the inherent anisotropy and unidirectional porosity of wood aerogel(nanowood)to support polyethylene glycol(PEG).The wood modification process involves the incorporation of phytic acid(PA)and MXene hybrid structure through an evaporation-induced assembly method,which could impart non-leaking PEG filling while concurrently facilitating thermal conduction,light absorption,and flame-retardant.Consequently,the as-prepared wood-based CPCMs showcase enhanced thermal conductivity(0.82 W m^(-1)K^(-1),about 4.6 times than PEG)as well as high latent heat of 135.5 kJ kg^(-1)(91.5%encapsula-tion)with thermal durability and stability throughout at least 200 heating and cooling cycles,featuring dramatic solar-thermal conversion efficiency up to 98.58%.In addition,with the synergistic effect of phytic acid and MXene,the flame-retardant performance of the CPCMs has been significantly enhanced,showing a self-extinguishing behavior.Moreover,the excellent electromagnetic shielding of 44.45 dB was endowed to the CPCMs,relieving contemporary health hazards associated with electromagnetic waves.Overall,we capitalize on the exquisite wood cell structure with unidirectional transport inherent in the development of multifunctional CPCMs,showcasing the operational principle through a proof-of-concept prototype system.

Flame-retardant oligomeric electrolyte additive for self-extinguishing and highly-stable lithium-ion batteries:Beyond small molecules

Preparing both safe and high-performance lithium-ion batteries(LIBs) based on commonly used commercial electrolytes is highly desirable,yet challenging.To overcome the poor compatibility of conventional small-molecular flame-retardants as electrolyte additives for safe LIBs with graphite anodes,in this study,we propose and design a novel low-cost flame-retardant oligomer that achieves an accurate and complete reconciliation of fire safety and electrochemical performance in LIBs.Owing to the integration of phosphonate units and polyethylene glycol(PEG) chains,this oligomer,which is a phosphonatecontaining PEG-based oligomer(PPO),not only endows commercial electrolytes with excellent flame retardancy but also helps stabilize the electrodes and Li-ion migration.Specifically,adding 15 wt% of PPO can reduce 70% of the self-extinguishing time and 54% of total heat release for commercial electrolytes.Moreover,LiFePO_(4)/lithium and graphite/lithium cells as well as LiFePO_(4)/graphite pouch full cells exhibit good long-term cycling stability.

EFFECT OF CHEMICAL STRUCTURE OF COMONOMERS ON THE PROPERTIES OF COPOLYESTERS

The effect of different kinds of comonomers with or without flexible chain on properties of copolyesters, such as transition temperature, crystallization velocity, crystallinity and size Of crystallites, is studied. The experimental results indicate the obvious difference in properties between comonomers with iso-and ortho-structure of phenyl ring and comonomers with flexible chain. The influence of chemical structure of comonomers on properties of copolyesters is discussed.

Flame-retardant Mechanism of Magnesium Oxychloride in Epoxy Resin

Flame-retardant mechanism of magnesium oxychloride （M OC） in EP was in-vestigated by limiting oxygen index （LOI）, XRD, SEM, TG-DTG and DSC. The results show that MOC performed well as an inorganic flame-retardant in EP. When the content of MOC is 50%, the LOI of EP reaches 29.6% and mass of residual char reaches 9.6%. The flame retarde mechanism of MOC is due to the synergies of diluting, cooling, catalyzing char forming and obstructing effects.

Preparation and characterization of biodegradable aliphatic-aromatic copolyesters/nano-SiO_2 hybrids via in situ melt polycondensation

In situ melt polycondensation was proposed to prepare biodegradable aliphatic-aromatic copolyesters/nano-SiO2 hybrids based on terephthalic acid （TPA）, poly（L-lactic acid） oligomer （OLLA）, 1,4-butanediol （BDO） and nano-SiO2. TEM and FT-IR characterizations confirmed that TPA, OLLA and BDO copolymerized to obtain biodegradable copolyesters, poly（butylene terepbthalate-co-lactate） （PBTL）, and the abundant hydroxyl groups on the surface of nano-SiO2 provided potential sites for in situ grafting with the simultaneous resulted PBTL. The nano-SiO2 particles were chemically wrapped with PBTL to form PBTL/nano- SiO2 hybrids. Due to the good dispersion and interfacial adhesion of nano-SiO2 particles with the copolyester matrix, the tensile strength and the Young＇s modulus increased from 5.4 and 5.6 MPa for neat PBTL to 16 and 390 MPa for PBTL/nano-SiO2 hybrids with 5 wt.% nano-SiO2, respectively. The mechanical properties of PBTL/nano-SiO2 hybrids were substantially improved.

SYNTHESIS AND AVERAGE SEQUENCE LENGTH DETERMINATION OF AROMATIC-ALIPHATIC COPOLYESTERS CONTAINING POLY(ALKYLENE OXALATE)UNITS

Two series of aromatic-aliphatic random copolyesters(PEBTOXS)with diverse diol ratios have been synthesized by direct melting polycondensation.Two kinds of diols(glycol(EG)and 1,4-butanediol(BD))are used in combination in order to adjust crystallization and tensile properties,and three kinds of diacids(dimethyl terephthalate(DMT),diethyl oxalate(DEOX),and sebacic acid(SA))are involved.~1H-NMR spectra quantify both composition and structure,and show that the final contents in copolyesters appropriate to the ...

A mechanistic study of flame retardance of novel copolyester phosphorus containing linked pendant groups by TG/XPS/direct Py-MS

The flame retardant mechanism of the copolyester phosphorus containing linked pendant groups was investigated by thermogravimetric （TG）, X-ray photoelectron spectroscopy （XPS） and direct insertion probe pyrolysis mass spectrometry （DP-MS） technique. TG results show that the incorporation of phosphorus containing unit linked pendant groups can destabilize the copolyester due to the cleavage of P-CH2 bond, and phosphorus containing units cannot promote the char-formation of the copolyester during the thermal degradation of the copolyester. XPS spectra indicate that with the increase of the temperature, the P-CH2 bonds of the copolyester break down gradually, the concentration of phosphorus in the condensed phase products decrease gradually and the chemical state of phosphorus does not change in the temperature of 250-380 ℃. Direct pyrolysis MS suggests that the P-CH2 bonds cleavage occurs at pendant groups and species containing phosphorus can volatilize into the gas phase. A flame retardant mechanism is proposed for the gas phase mode of action of the halogen-free copolyester phosphorus containing linked pendant groups.

Synthesis and Structure of Butylene Terephthalate-ε-Caprolactone Copolyesters

A series of butylene terephthalate-E-caprolactone copolyesters (BCL) with different hard segment content were successfully synthesized and characterized by 1H-NMR. DSC. PLM and U viscometer, The sequence structure and crystallization characteristics of BCL copolyesters were carefully investigated.

Research in the Degradation and Antifouling Performance of Copolyesters of L-Lactide and ε-Caprolactonen

Block copolyesters of L-lactide and ε-caprolactone were synthesized by melt copolymerization of ε-caprolactone and L-lactide.The degradation performance of copolyesters was investigated by quartz crystal microbalance with dissipation(QCM-D).Diisocyanate terminated copolyesters could obtain via the reaction of copolyesters and diisocyanate.Diisocyanate terminated copolyesters could react with polyol resin to prepare degradable polyurethane which can be used in antifouling coatings.In this paper,we also discussed the degradation products release action and antifouling performance of the copolyesters film.

Comparison of Flame-retardancy Property and Mechanism between a Phosphate Ester and a Phosphoramine Flame-retardants

A halogen-free flame-retardant (hydroquinone bis (N,N’-diarylphosphoramidate),4N-HDP) containing phosphorus-nitrogen was synthesized.Its structure was characterized by infrared spectroscopy (IR),nuclear magnetic resonance (^(1)H-NMR and^(31)P-NMR).Thermogravimetric analysis (TG),limiting oxygen index (LOI),UL-94 vertical burning test (UL-94),thermogravimetric-infrared instrument (TG-IR) and scanning electron microscopy (SEM) were used to compare the flame-retarding performance and mechanism of hydroquinone bis (diphenyl phosphate) (HDP) and 4N-HDP.TG,IR and TG-IR were used for comparative analysis,indicating that both HDP and 4N-HDP are flame-retardants,and the gas phase and condensed phase act synergistically.In the pyrolysis process,it is divided into two steps:the first step is the breakage of large molecules to small molecules;the second step is the gasification and carbonization of small molecules,and eventually produces phosphate ester and non-flammable gases.Through the comparison of various results,it could be found that 4N-HDP has better flame-retarding performance compared to HDP in the composite with polycarbonate (PC).

Synthesis and Characterization of Poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) Copolyester

Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.

3D flame-retardant skeleton reinforced polymer electrolyte for solid-state dendrite-free lithium metal batteries

For solid polymer electrolytes(SPEs),improving their mechanical and electrochemical properties is the key to obtaining batteries with higher safety and higher energy density.Herein,a novel synergistic strategy proposed is preparing a 3D flame-retardant skeleton(3DPA)and adding nano-multifunctional fillers(Li-ILs@ZIF-8).In addition to providing mechanical support for the polyethylene oxide(PEO)matrix,3DPA also has further contributed to the system’s flame retardancy and further improved the safety.Simultaneously,the electrochemical performance is fully guaranteed by rigid Li-ILs@ZIF-8,which provides fast migration channels forLi^(+),reduces the crystallinity of PEO and effectively inhibits lithium dendrites.The limiting oxygen index of the optimal sample(PL3Z/PA)is as high as 20.5%,and the ionic conductivity reaches 2.89×10^(-4) and 0.91×10^(-3) S cm^(-1) at 25 and 55°C,respectively.The assembled Li|PL3Z/PA|Li battery can be cycled stably for more than 1000 h at a current density of 0.1 m A cm^(-2) without short circuit being pierced by lithium dendrites.The specific capacity of the LFP|PL3Z/PA|Li battery was 160.5 m Ah g^(-1) under a current density of 0.5 C,and the capacity retention rate was 90.0%after 300 cycles.

PROPERTIES AND MICROSTRUCTURE OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS

The properties and structures of thermotropical liquid crystalline copolyesters based on p-hydroxybenzoic acid (PHBA), terephthalic acid (TPR) and bisphenol A (BPA) were studied by DSC, WAXD, hot stage polarized microscopy and NMR. It was found that most of the copolyesters were soluble in many common organic solvents. The copolyesters had low T-m/T-f values and a broad range of liquid crystal phase, making the polymers readily melt-processable. The effects of annealing at different temperatures on the copolyester containing 33% PHBA were also discussed. It was noted that annealing at ca. 200 degrees C (below Tc - n) could lead to the increasing of the crystallinity of the copolyester while the microstructure and sequence structure had not changed. Annealing at ca. 280 degrees C (near Tc - n) could bring a change of crystal and sequence structure and simultaneously made the microdomains be ordered more perfectly.

PRIMARY STUDY ON BLENDS BASED ON THERMOTROPIC LIQUID CRYSTAL COPOLYESTER AND PET

The blend system composed of PET and thermotropic liquid crystal copolyester based on hydroxy benzoic acid, terephthalic acid, diacetylnaphthalene and PET was studied. The results indicated that LCP could play the role of crystal nuclei. The introduction of LCP decreased the melt viscosity of the system and fibrillous structure could be formed in favor conditions.

THE NON—ISOTHERMAL CRYSTALLIZATION KINETICS OF A LIQUID CRYSTALLINE RANDOM COPOLYESTER WITH DIFFERENT COMPOSITIONS

The non-isothermal crystallization kinetics analysis of liquid crystalline random copolyestercomposed of p-oxybenzoate (B) and 2, 6-oxynaphthoate (N) monomers was carried out by meansof differential scanning calorimetry basing on Ziabicki and Jeziorny method. Although the compo-sition of 58/42 B-N copolyester had poorer thermodynamic crystallizability comparing with thoseof 30/70 and 75/25, its kinetic crystallizability Go was slightly larger. This fact was due to thepoorer match of sequences of 58/42 B-N in domains of nematic melt,and therefore better mobilityof chains during crystallization. The Avrami exponents of three composition species were allabout 2. 5, implying two dimensional growth in so-called non-periodic layer crystallites and a mixture of homogeneous and heterogeneous nucleation.

DYNAMIC RHEOLOGICAL AND THERMAL PROPERTY OF Q-RESIN CONTAINING THERMOTROPIC LIQUID CRYSTALLINE COPOLYESTER AND ITS BLEND WITH PET

A thermotropic liquid crystalline copolyester (LCP) based on p-acetoxy-benzoic acid (49.9mol%), 2,7-diacetoxynaphthalene (22.3 mol%), terephthalic acid (22.3%) and Q-resin (polyethylene 2,6-naphthalene, 5.5%) was prepared via melt transesterification, and then a blend was prepared by physically mixing 40% therm0tropic liquid crystallline copolyester and 60% polyethlene terephthalate (PET). The thermal properties of both-4he LCP and the blend were studied by DSC and the result showed that the various transition temperatures for the blend were rather close to those for pure PET. The thermal stability of LCP, blend and PET was characterized by TGA. The dynamic theological properties of LCP and thc blend were studied by the oscillation test on a rheometric mechanical spectrometer( Instron RM3250) with parallel plate disk. The results showed that the theological behavious of the blend melt exhibit as conventional polymeric melt in the whole experimental frequency range (0.02—12 Hz). However, for the melt

CRYSTALLIZATION BEHAVIOR OF A THERMOTROPIC LIQUID CRYSTAL COPOLYESTER

A thermotropic liquid crystal copolyester resin based on p-hydroxybenzoic acid, 2, 6-naphthoic acid, hydroxyquinone and PET was synthesized by melt condensation and studied. The results based on DSC and X-ray diffraction indicated that there were a rapid and a slow crystallization processes for the copolyester at certain conditions. A critical temperature was suggested, below which the slow crystallization could hardly happen. Above the critical temperature the extent of the slow crystallization process depended not only on annealing temperature but also on the annealing time. A fine crystal structure with high melting point and narrow diffraction peak was formed under favorable conditions.

Nonisothermal Crystallization Kinetics of Poly(butylene adipate-co-terephthalate) Copolyester

Nonisothermal crystallization behavior of poly(butylene adipate-co-terephthalate)(PBAT) synthesized via direct esterification and polycondensation reactions was investigated by the differential scanning calorimetry(DSC).The Avrami equation modified by Jeziorny and the Z.S.Mo equation were employed to describe the non-isothermal crystallization kinetics of copolyester samples.The test results showed that the Avrami equation was successful in describing nonisothermal crystallization process of PBAT copolyesters.PBAT copolyester could give birth to secondary crystallization.The crystallization parameter(Zc) increased with an increasing cooling rate and the Avrami exponent(n) was around 2.3.For a given cooling rate,the value of Zc demonstrated a sagging trend with an increase in adipic acid(AA) content.The equation proposed by Z.S.Mo was successful in describing the nonisothermal crystallization kinetics of PBAT copolyesters.

SYNTHESIS AND CHARACTERIZATION OF AROMATIC LIQUID CRYSTALLINE COPOLYESTERS WITH REGULAR SEQUENCE STRUCTURE

Several novel aromatic liquid crystalline copolyesters with regular sequence structure were prepared by melt Sehotten-Baumann polycondensation via complex monomer. Polarizing microscope with hot stage, thermal analysis and X-ray diffraction were used to investigate the structure and properties of the copolyesters. The effects of structural units, such as flexible spacer, noncolinear meta-linked phenylene unit, crankshaft unit, kink with flexible bridging unit and various substituted benzene rings on melting temperature of aromatic copolyesters were studied and discussed on the basis of crystalline structure of the polymers.