Facet-dependent Thermal and Electrochemical Degradation of Lithium-rich Layered Oxides

Lithium-rich layered oxides(LLOs)are promising candidate cathode materials for safe and inexpensive high-energy-density Li-ion batteries.However,oxygen dimers are formed from the cathode material through oxygen redox activity,which can result in morphological changes and structural transitions that cause performance deterioration and safety concerns.Herein,a flake-like LLO is prepared and aberration-corrected scanning transmission electron microscopy(STEM),in situ high-temperature X-ray diffraction(HT-XRD),and soft X-ray absorption spectrum(sXAS)are used to explore its crystal facet degradation behavior in terms of both thermal and electrochemical processes.Void-induced degradation behavior of LLO in different facet reveals significant anisotropy at high voltage.Particle degradation originates from side facets,such as the(010)facet,while the close(003)facet is stable.These results are further understood through ab initio molecular dynamics calculations,which show that oxygen atoms are lost from the{010}facets.Therefore,the facet degradation process is that oxygen molecular formed in the interlayer and accumulated in the ab plane during heating,which result in crevice-voids in the ab plane facets.The study reveals important aspects of the mechanism responsible for oxygen-anionic activity-based degradation of LLO cathode materials used in lithium-ion batteries.In particular,this study provides insight that enables precise and efficient measures to be taken to improve the thermal and electrochemical stability of an LLO.

Thermal characteristic evolution of lithium-ion batteries during the whole lifecycle

This work extensively investigates the thermal characteristic evolution of lithium-ion batteries under different degradation paths,and the evolution mechanism through multi-angle characterization is revealed.Under different degradation paths,the evolution trend of temperature rise rate remains unchanged with respect to depth of discharge during the adiabatic discharge process,albeit to varying degrees of alteration.The temperature rise rate changes significantly with aging during the adiabatic discharge process under low-temperature cycling and high-rate cycling paths.The total heat generation rate,irreversible heat generation rate,and reversible heat generation rate exhibit similar evolution behavior with aging under different degradation paths.The interval range of endothermic process of reversible electrochemical reactions increases and the contribution of irreversible heat to the total heat increases with aging.To further standardize the assessment of different degradation paths on the thermal characteristics,this work introduces the innovative concept of“Ampere-hour temperature rise”.In low-temperature cycling and high-rate cycling paths,the ampere-hour temperature rise increases significantly with aging,particularly accentuated with higher discharge rates.Conversely,in high-temperature cycling and high-temperature storage paths,the ampere-hour temperature rise remains relatively stable during the initial stages of aging,yet undergoes a notable increase in the later stages of aging.The multi-angle characterization reveals distinct thermal evolution behavior under different degradation paths primarily attributed to different behavior changes of severe side reactions,such as lithium plating.The findings provide crucial insights for the safe utilization and management of lithium–ion batteries throughout the whole lifecycle.

Efficient activation of the Co/SBA-15catalyst by high-frequency AC-DBD plasma thermal effects for toluene removal

Dielectric barrier discharge(DBD)plasma excited by a high-frequency alternating-current(AC)power supply is widely employed for the degradation of volatile organic compounds(VOCs).However,the thermal effect generated during the discharge process leads to energy waste and low energy utilization efficiency.In this work,an innovative DBD thermally-conducted catalysis(DBD-TCC)system,integrating high-frequency AC-DBD plasma and its generated thermal effects to activate the Co/SBA-15 catalyst,was employed for toluene removal.Specifically,Co/SBA-15 catalysts are closely positioned to the ground electrode of the plasma zone and can be heated and activated by the thermal effect when the voltage exceeds 10 k V.At12.4 k V,the temperature in the catalyst zone reached 261℃ in the DBD-TCC system,resulting in an increase in toluene degradation efficiency of 17%,CO_(2)selectivity of 21.2%,and energy efficiency of 27%,respectively,compared to the DBD system alone.In contrast,the DBD thermally-unconducted catalysis(DBD-TUC)system fails to enhance toluene degradation due to insufficient heat absorption and catalytic activation,highlighting the crucial role of AC-DBD generated heat in the activation of the catalyst.Furthermore,the degradation pathway and mechanism of toluene in the DBD-TCC system were hypothesized.This work is expected to provide an energy-efficient approach for high-frequency AC-DBD plasma removal of VOCs.

Hierarchically Multifunctional Polyimide Composite Films with Strongly Enhanced Thermal Conductivity

The development of lightweight and integration for electronics requires flexible films with high thermal conductivity and electromagnetic interference(EMI) shielding to overcome heat accumulation and electromagnetic radiation pollution.Herein,the hierarchical design and assembly strategy was adopted to fabricate hierarchically multifunctional polyimide composite films,with graphene oxide/expanded graphite(GO/EG) as the top thermally conductive and EMI shielding layer,Fe_(3)O_(4)/polyimide(Fe_(3)O_(4)/PI) as the middle EMI shielding enhancement layer and electrospun PI fibers as the substrate layer for mechanical improvement.PI composite films with 61.0 wt% of GO/EG and 23.8 wt% of Fe_(3)O_(4)/PI exhibits high in-plane thermal conductivity coefficient(95.40 W(m K)^(-1)),excellent EMI shielding effectiveness(34.0 dB),good tensile strength(93.6 MPa) and fast electric-heating response(5 s).The test in the central processing unit verifies PI composite films present broad application prospects in electronics fields.

THERMAL DEGRADATION AND FLAME RETARDANCY OF CALCIUM ALGINATE FIBERS

Calcium alginate fibers were prepared by wet spinning of sodium alginate into a coagulating bath containing calcium chloride.The thermal degradation and flame retardancy of calcium alginate fibers were investigated with thermal gravimetry(TG),X-ray diffraction(XRD),limiting oxygen index(LOI) and cone calorimeter(CONE).The results show that calcium alginate fibers are inherently flame retardant with a LOI value of 34,and the heat release rate(HRR),total heat release(THR),CO and CO_2 concentrations during com...

Thermal Degradation Kinetics of N,N'-Di(diethoxythiophosphoryl)-1,4-phenylenediamine

The non-isothermal degradation kinetics of N,N＇-di（diethoxythiophosphoryl）-1,4-phenylenediamine in N2 was studied by TG-DTG techniques.The kinetic parameters,including the activation energy and pre-exponential factor of the degradation process for the title compound were calculated by means of the Kissinger and Flynn-Wall-Ozawa（FWO）method and the thermal degradation mechanism of the title compound was also studied with the Satava-Sestak methods.The results indicate that the activation energy and pre-exponential factor are 152.61 kJ/mol and 9.06×101 4s -1with the Kissinger method and 154.08 kJ/mol with the Flynn-Wall-Ozawa method,respectively.It has been shown that the degradation of the title compound follows a kinetic model of one-dimensional diffusion or parabolic law,the kinetic function is G（α）=α2and the reaction order is n=2.

THERMAL DEGRADATION OF POLY(ARYLENE SULFIDE SULFONE)/NMETHYLPYRROLIDONE CRYSTAL SOLVATE

The thermal degradation of poly（arylene sulfide sulfone）/N-methylpyrrolidone （PASS/NMP） crystal solvate was studied by thermogravimetric analysis （TGA） and was compared with pure PASS in order to determine the way in which the formation of the crystal solvate affected the thermal properties of the polymer. The activation energy of the solid state process was determined using Kissinger＇s method, which does not require knowledge of the reaction mechanism （RM）, to be 174.18 kJ/mol which was lower than that for pure PASS （E = 214 kJ/mol）. The study of master curves together with interpretation of integral methods, allows confirmation that the thermal degradation mechanism for PASS in the crystal solvate system is a decelerated Rn type, which is a solid-state process based on a phase boundary controlled reaction, in the conversion range considered. Whereas, the pure PASS follows a decelerated Dn thermodegradation mechanism in the same conversion range.

Thermal degradation and isothermal crystalline behavior of poly(trimethylene terephthalate)

Poly（trimethylene terephthalate） （PTT） is an excellent fiber material. Its thermal degradation and isothermal crystalline behaviors were in this study investigated using thermogravimetric analysis （TGA）, thermogravimetric analysis-Fourier transform infrared spectroscopy （TGA-FTIR） analysis, differential scanning calorimetry （DSC） and X-ray diffraction （XRD）. The thermal degradation mechanism of PTT follows Mclafferty rearrangement principle. The PTTwithintrinsicviscosity（IV） of 0.74 dL/g has a maximum crystallinity of about 55% at 190 ℃, as demonstrated by DSC and XRD measurements consistently.

Thermal Stability and Degradation of Chitosan Modified by Cinnamic Acid

The reaction of chitosan with cinnamic acid gave the corresponding N-cinnamoyl chitosan (NCC) polymer. The chem-ical structure of the modified polymer was characterized by IR, 1H-NMR and elemental analysis. Thermogravim- etric analysis reveals that the thermal stability of chitosan polymer is greater than NCC polymer. The activation energies of thermal degradation of chitosan and NCC polymers were determined using Arrhenius relationship. Thermal degradation of NCC polymer was studied and the products of degradation were identified by GC-MS technique. It seems that the mechanism of degradation of NCC polymer is characterized by elimination of low-molecular weight radicals. Combination of these radicals and random scission mechanism along the backbone chain are the main source of the degradation products.

Thermal Degradation Studies of Some Strongly Acidic Cation Exchange Resins

The thermal degradation of some sulfonic cationites namely Amberlite IR-120, Indion-223 and In-dion-225 was investigated using instrumental techniques like thermal analysis (TG) and Scanning Electron Microscopy (SEM). Fourier Transform Infrared Spectroscopy (FTIR) was used to characterize the resins degradation steps. The sulfonic cationites undergo degradation through dehydration, followed by decomposition of sulfonic acid functional groups liberating SO2. The thermogravimetric analysis of above cationites at higher temperature up to 520oC, show mass loss of 61.61% and 25.43% respectively for Indion-223 and Indion-225, while Amberlite IR-120 cationite get burned off completely.

Microscopic degradation mechanism of polyimide film caused by surface discharge under bipolar continuous square impulse voltage

Polyimide （PI） film is an important type of insulating material used in inverter-fed motors. Partial discharge （PD） under a sequence of high-frequency square impulses is one of the key factors that lead to premature failures in insulation systems of inverter-fed motors. In order to explore the damage mechanism of PI film caused by discharge, an aging system of surface discharge under bipolar continuous square impulse voltage （BCSIV） is designed based on the ASTM 2275 01 standard and the electrical aging tests of PI film samples are performed above the partial discharge inception voltage （PDIV）. The chemical bonds of PI polymer chains are analyzed through Fourier transform infrared spectroscopy （FTIR） and the dielectric properties of unaged and aged PI samples are investigated by LCR testers HIOKI 3532-50. Finally, the micro-morphology and micro-structure changes of PI film samples are observed through scanning electron microscopy （SEM）. The results show that the physical and chemical effects of discharge cut off the chemical bonds of PI polymer chains. The fractures of ether bond （C-O-C） and imide ring （C-N-C） on the backbone of a PI polymer chain leads to the decrease of molecular weight, which results in the degradation of PI polymers and the generation of new chemical groups and materials, like carboxylic acid, ketone, aldehydes, etc. The variation of microscopic structure of PI polymers can change the orientation ability of polarizable units when the samples are under an AC electric field, which would cause the dielectric constant e to increase and dielectric loss tan ~ to decrease. The SEM images show that the degradation path of PI film is initiated from the surface and then gradually extends to the interior with continuous aging. The injection charge could result in the PI macromolecular chain degradation and increase the trap density in the PI oolvmer bulk.

Thermal and Thermo-oxidative Degradation of Flame Retardant High Impact Polystyrene with Triphenyl Phosphate and Novolac Epoxy Resin

Thermal and thermo-oxidative decomposition and decomposition kinetics of flame retardant high impact polystyrene （HIPS） with triphenyl phosphate （TPP） and novolac type epoxy resin （NE） were characterized using thermo-gravimetric experiment. And the flammability was determined by limited oxygen indices （LOI）. The LOI results show that TPP and NE had a good synthetic effect on the flame retardancy of HIPS. Compared with pure HIPS, the LOI values of HIPS/NE and HIPS/TPP only increased by about 5%, and the LOI value of HIPS/TPP/NE reached 42.3%, nearly 23% above that of HIPS. All materials showed one main decomposition step, as radical HIPS scission predominated during anaerobic decomposition. TPP increased the activity energy effectively while NE affected the thermal-oxidative degradation more with the help of the char formation. With both TPP and NE, the materials could have a comparable good result of both thermal and thermal-oxidative degradation, which could contribute to their effect on the flame retardancy.

A 3D graphene/polyimide fiber framework with improved thermal conductivity and mechanical performance

The integration of electronic components and the popularity of flexible devices have come up with higher expectations for the heat dissipation capability and comprehensive mechanical performance of thermal management materials.In this work,after the modification of polyimide(PI)fibers through oxidation and amination,the obtained PDA@OPI fibers(polydopamine(PDA)-modified pre-oxidized PI fibers)with abundant amino groups were mixed into graphene oxide(GO)to form uniform GO-PDA@OPI composites.Followed by evaporation,carbonization,graphitization and mechanical compaction,the G-gPDA@OPI films with a stable three-dimensional(3D)long-range interconnected covalent structure were built.In particular,due to the rich covalent bonds between GO layers and PDI@OPI fibers,the enhanced synergistic graphitization promotes an ordered graphitized structure with less interlayer distance between adjacent graphene sheets in composite film.As a result,the optimized G-gPDA@OPI film displays an improved tensile strength of 78.5 MPa,tensile strain of 19.4%and thermal conductivity of 1028 W/(m·K).Simultaneously,it also shows superior flexibility and high resilience.This work provides an easily-controlled and relatively low-cost route for fabricating multifunctional graphene heat dissipation films.

Thermal Oxidative Degradation and Ageing Performance of Silicone Rubber Filled with Attapulgite

The natural attapulgite(NAPT)was disaggregated by high-pressure homogenization technology combined with extrusion process to prepare the attapulgite with disaggregated rod crystal bundles(DAPT)and large specific surface area of 133.7 m^(2)/g.NAPT and DAPT were incorporated into the silicone rubber to obtain the composite NAPTSR and DAPT-SR by mechanical blending method,respectively.After thermal oxidative ageing at 300℃ for 0.5 h,temperature for the 5%weight loss increased greatly from 385℃ of the neat silicone rubber to 396-399℃ with addition of NAPT and DAPT.NAPT and DAPT enhanced the interaction between the filler nanoparticles and rubber matrix thus inhibited the nanoparticle agglomeration.The conservation rate of the side methyl group in NAPT-SR and DAPT-SR was greatly improved after ageing.Therefore,the thermal oxidative degradation and ageing performance of the silicone rubber composites was significantly reinforced.Moreover,DAPT could greatly restrain the growth of nanoparticles after ageing.Therefore,DAPT-SR showed the better retention of tensile strength(40.6%),elongation at break(34.9%)and tear strength(30.1%)compared with the corresponding mechanical properties of the neat silicone rubber(10.6%,7.4%,and 5.0%)after ageing.

SYNTHESIS,CHARACTERIZATION AND THERMAL DEGRADATION KINETICS OF POLY(IMINO ISOPHTHALOYL IMINO (2,4,8,10-TETRAOKSOASPIRO [5,5] UNDEKAN-3,9-DIPROPYLENE))

A new polymer,poly(imino isophthaloyl imino(2,4,8,10-tetraoksoaspiro[5,5]undekan-3,9-dipropylene)) [poly(IPIT)]was synthesized by an interfacial polycondensation reaction.The characterization of poly(IPIT)was conducted by using FT-IR,^(13)C-NMR,TG and DTA techniques.The kinetics of the thermal degradation of poly(IPIT)was investigated by thermogravimetric analysis at different heating rates.TG curves showed that the thermal decomposition of poly(IPIT) occurred in three stages.The apparent activation energie...

Fast inactivation of microbes and degradation of organic compounds dissolved in water by thermal plasma

The multifunctionality and the advantages of thermal plasma for the fast inactivation of viable cells and degradation of organic compounds dissolved in waste water are presented.A complete bacterial inactivation process was observed and studied using a thermal plasma treatment source with very short application times,in particular for Staphylococcus aureus bundle spore survival.The survival curves and analyses of the experimental data of the initial and final densities of S.aureus bacteria show a dramatic inhibitory effect of the plasma discharge on the residual bacteria survival ratio.As the exposure time increased,the inactivation process rate increased for direct exposure more than it did for indirect exposure.The evaluation of direct and indirect exposure was based on the analysis of the ultraviolet spectrum from the absorbance spectra of the organic compound dye called benzene sulfonate（C（16）H（11）N2Na O4S）and of viable cells called S.aureus.Organic compounds were degraded and viable cells were killed in a short time by thermal plasma.Moreover,analyses of total carbon,total organic carbon,and total inorganic carbon showed a fast decrease in organically bound carbon,however,this was not as fast as the absorbance spectra revealed by the exposure time increasing more for direct exposure than indirect exposure.After 100 s of exposure to the organic compound dye the removal had a maximun of 40%for samples with indirect exposure to the plasma and a maximum of 90%for samples with the direct exposure.For both samples,where some organic contaminants still remained in treated water,four electrolytes（KCl,Na Cl,Na2SO4,and CH3COONa）were added to be effective for complete sterilization,reaching a purity of 100%.A proposal is made for an optimized thermal plasma water purification system（TPWPS）to improve fast inactivation of microbes and the degradation of organic compounds dissolved in water（especially for direct exposure rather than indirect exposure）using a hybrid plasma torch with an electrical power of 125 kW（500 V–250 A）producing a high-temperature（10 000 K–19 000 K）plasma jet with a maximum gas consumption of 28 mg s^-1.

Kinetic Parameters of Thermal Degradation of Polymers

The derivative expressions between activation energy (E) and the temperature at the maximum mass loss rate(Tmax) and between activation energy (E) and exponent (N) were deduced in the light of Arrhenius theory. It was found that the increase of activation energy results in the decrease of exponent and the increase of Tmax. The kinetic parameters were involved in the analysis of the thermal degradation of several polymers. The degradation kinetics of these polymers well complied with the prediction of the derivative expressions for the polymer degradation with single mechanism dominated.

Evalution of Thermal Oxidative Degradation of Trimethylol-propane Trioleate by TG/DTA/DSC

In order to evaluate the thermal oxidation degradation behavior of lubricant with different antioxidants,the thermal kinetics equation based on the anlyses of thermogravimetry(TG),differential thermal analysis(DTA),and differential scanning calorimetry(DSC)was established,respectively,to calculate the activation energy of lubricant thermal-oxidative reaction.The thermal analyses of TG and DTA were employed to determine the thermal decomposition properties of ester oils trimethylolpropane trioleate(TMPTO)with butyl-octyl-diphenylamine/octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate/amine-phenol combination antioxidant.The activation energy of the lubricating oil adding antioxidant is increased relative to the TMPTO base oil,and the order of activation energy are Ec(93.732 kJ·mol^(-1))>Ed(88.71 kJ·mol^(-1))>Eb(58.41 kJ·mol^(-1))>Ea(46.32 kJ·mol^(-1)).The experimental results show that octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate in TMPTO has favorable resistance to thermal oxidation and decomposition.The thermal analysis method of DSC accurately reflects the heat exchange of lubricant thermal-oxidative reaction.The order of activation energy is calculated to ED(144.385 kJ·mol^(-1))>EC(110.05 kJ·mol^(-1))>EB(97.187 kJ·mol^(-1))>EA(66.02 kJ·mol^(-1)).It is illustrated that the amine-phenol combination antioxidant has the best thermal oxidation resistance,which is the same as what the oxidation onset temperature effected.

Thermal Degradation and Decomposition Kinetics of Freeze Dried Cow and Camel Milk as well as Their Constituents

A study was conducted to evaluate thermal properties and degradation kinetic parameters of FD cow milk and camel milk powder. FT-IR was used to confirm the fat removal from the whole milk powder. Differential Scanning Calorimetry （DSC） was used to study the thermal transitions. DSC thermograms of WMP showed a two-step endotherm, the former at lower temperatures （cow milk 16-35 ℃, camel milk 25-60 ℃） and the later at higher temperatures （cow milk 75-125 ℃, camel milk 90-160 ℃）. The main difference observed between cow and camel milk was peak maximum temperature for fat melting, AH and other decomposition temperatures. The enthalpy of fat melting was 2.314 J/g and 3.397 J/g for cow and camel milk respectively. Thermogravimetric Analysis （TGA）/derivative thermogravimetric analysis （DTG） also showed two steps degradation. The first step involves lactose degradation and second step corresponds to combined degradation of protein and fat. Hence logβ vs 1000/T was plotted separately for individual components to determine cumulative value of activation energy using Flynn-Wall-Osawa method.

Synthesis and characterization of high strength polyimide/silicon nitride nanocomposites with enhanced thermal and hydrophobic properties

Polyimide(PI)composite films were synthesized incorporating amino modified silicon nitride(Si_(3)N_(4))nanoparticles into PI matrix via in situ polymerization technique.The mechanical and thermal performances as well as the hydrophobic properties of the as prepared composite films were investigated with respect to the dosage of the filler in the PI matrix.According to Thermogravimetric(TGA)analysis,meaningful improvements were achieved in T5(5%weight loss temperature)and T10(10%weight loss temperature)up to 54.1℃ and 52.4℃,respectively when amino functionalized nano Si_(3)N_(4) particles were introduced into the PI matrix.The differential scanning calorimetry(DSC)results revealed that the glass transition temperature(Tg)of the composites was considerably enhanced up to 49.7℃ when amino functionalized Si_(3)N_(4) nanoparticles were incorporated in the PI matrix.Compared to the neat PI,the PI/Si_(3)N_(4) nanocomposites exhibited very high improvement in the tensile strength as well as Young’s modulus up to 105.4%and 138.3%,respectively.Compared to the neat PI,the composites demonstrated highly decreased water absorption behavior which showed about 68.1%enhancement as the content of the nanoparticles was increased to 10 wt%.The SEM(Scanning electron microscope)images confirmed that the enhanced thermal,mechanical and water proof properties are essentially attributed to the improved compatibility of the filler with the matrix and hence,enhanced distribution inside the matrix because of the amino groups on the surface of Si_(3)N_(4) nanoparticles obtained from surface functionalization.