Exploring the thermal stability of lithium-ion cells via accelerating rate calorimetry:A review

Given the importance of lithium-ion cell safety,a comprehensive review on the thermal stability of lithium-ion cells investigated by accelerating rate calorimetry(ARC),is provided in the present work.The operating mechanism of ARC is discussed first,including the usage and the reaction kinetics.Besides that,the thermal stability of the cathode/anode materials at elevated temperatures is revealed by examining the impacts of some significant factors,i.e.,the lithium content,particle size,material density,lithium salt,solvent,additive,binder and initial heating temperature.A comparison of the common cathode materials indicates that the presence of Mn and polyanion could significantly enhance the thermal stability of cathode materials,while the doping of Al also helps to restrain the reactivity.Except for their high capacity,some alloy materials demonstrate more competitive safety than traditional carbon anode materials.Furthermore,the thermal behaviors of full cells under abusive conditions are reviewed here.Due to the sensitivity of ARC to the kinetic parameters,a reaction kinetic modeling can be built on the basis of ARC profiles,to predict the thermal behaviors of cell components and cells.Herein,a shortcircuit modeling is exampled.

Integrative analysis of indirect calorimetry and metabolomics profiling reveals alterations in energy metabolism between fed and fasted pigs

Background: Fasting is a simple metabolic strategy that is used to estimate the maintenance energy requirement where the energy supply for basic physiological functions is provided by the mobilization of body reserves.However, the underlying metabolic components of maintenance energy expenditure are not clear. This study investigated the differences in heat production(HP), respiratory quotient(RQ) and plasma metabolites in pigs in the fed and fasted state, using the techniques of indirect calorimetry and metabolomics.Methods: Nine barrows(45.2 ± 1.7 kg BW) were fed corn-soybean based meal diets and were kept in metabolism crates for a period of 14 d. After 7 d adaptation, pigs were transferred to respiratory chambers to determine HP and RQ based on indirect calorimetry. Pigs were fed the diet at 2,400 k J ME/(kg BW0.6·d) during d 8 to 12. The last 2 d were divided into 24 h fasting and 48 h fasting treatment, respectively. Plasma samples of each pig were collected from the anterior vena cava during the last 3 d(1 d while pigs were fed and 2 d during which they were fasted).The metabolites of plasma were determined by high-resolution mass spectrometry using a metabolomics approach.Results: Indirect calorimetry analysis revealed that HP and RQ were no significant difference between 24 h fasting and 48 h fasting, which were lower than those of fed state(P < 0.01). The nitrogen concentration of urine tended to decrease with fasting(P = 0.054). Metabolomics analysis between the fed and fasted state revealed differences in15 compounds, most of which were not significantly different between 24 h fasting and 48 h fasting. Identified compounds were enriched in metabolic pathways related to linoleic acid metabolism, amino acid metabolism,sphingolipid metabolism, and pantothenate and Co A biosynthesis.Conclusion: These results suggest that the decreases in HP and RQ of growing pigs under fasting conditions were associated with the alterations of linoleic acid metabolism and amino acid metabolism. The integrative analysis also revealed that growing pigs under a 24-h fasting were more appropriate than a 48-h fasting to investigate the metabolic components of maintenance energy expenditure.

New Developments in the Calorimetry of High-Temperature Materials

1. Introduction Thermodynamics forms the fundamental underpinning of reactivity, transformation, and stability, and controls processes such as synthesis, corrosion and degradation, environmental transport, catalysis, and biological reactivity. In the materials field, the wealth of new compounds, polymorphs, hybrid organic–inorganic hybrid materials and metal organic frameworks, high-entropy alloys, and multiphase and nanophase materials attained by a variety of non-equilibrium synthesis and processing methodologies has outrun the available thermodynamic data, hampering current understanding of synthetic pathways, materials compatibility, and longevity during use, degradation, corrosion, and dissolution, and limiting our understanding of environmental contamination and transport for new materials.

DIFFERENTIAL SCANNING CALORIMETRY AND X-RAY DIFFRACTION STUDIES ON AGING BEHAVIOR OF Zn-Al ALLOYS

Decomposition processes of the quenched Zn-Al alloys were studied by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the stabilities of supersaturated solid solution (SSS) of Zn-Al alloy and α' phase formed by quenching would reduce with the increase of Zn content and the precipitation of η-Zn phases even when aging at ambient temperature, so that the exothermic precipitation peak in DSC curve would disappear. The activation energy of the η-Zn precipitation and the reaction enthalpy were calculated and measured. The kinetics of α' decomposition or η-Zn formation was determined by XRD. The microstructure change during aging was observed by TEM.

Assessment of parameters for precipitation simulation of heat treatable aluminum alloys using differential scanning calorimetry

Differential scanning calorimetry （DSC） has been used extensively to study different solid state reactions. The signals measured in DSC are associated with the growth and dissolution of different precipitates during a specific heat cycle. The time-temperature dependence of heat cycles and the corresponding heat flow evolution measured in the sample by DSC provide valuable experimental information about the phase evolution and the precipitation kinetics in the material. The thermo-kinetic computer simulation was used to predict the DSC signals of samples taken from 6xxx and 2xxx alloys. In the model, the evolution of different metastable and stable phases and the role and influence of excess quenched-in vacancies in the early stage of precipitation were taken into account. Transmission electron microscopy （TEM） and high-resolution TEM were used to verify the existence of precipitates, their size and number density at specific points of the DSC curves.

Indirect calorimetry to estimate energy requirements for growing and finishing Nellore bulls

Determination of nutritional requirements is the basis for diet formulation. The objectives of this study were to determine the net energy requirements for maintenance （NEro） and weight gain （NEg） in Nellore bulls during the growing and finishing phases, and to estimate efficiency of metabolizable energy （ME） utilization for maintenance and gain （km, kg）. Five Nellore bulls were housed in individual pens at the Universidade Federal de Minas Gerais （Belo Horizonte, Brazil） and evaluated over four experimental periods at 210, 315,378 and 454 kg shrunk body weight （SBW）, approximately. During each period, heat production （HP） was quantified by open circuit indirect calorimetry for three feeding levels： ad libitum, restricted and fasting. The NEm requirement was determined by linear regression between the Log of HP andthe ME intake （MEI） for the ad libitum and restricted levels. This requirement was also determined by quantifying fasting heat production （FHP）. The NEQ requirement was calculated by the difference between MEI and HP during ad libitum feeding. The k and kg were calculated by the relationship between net energy （NE） and ME requirements for maintenance and weight gain （MEm, MEp）, respectively. The NEm requirements per kg of metabolic empty body weight （EBW0.75） fluctuated between 348 and 517 kJ d-1, showing a decreasing trend with age, and were higher than the values reported in the literature. The NEg requirements ranged between 48.3 and 164 kJ kg-1 EBW0.75 d-1, and varied according to age and weight gain. The k values varied between 58.6 and 69.7%, while kg varied between 23.4 and 40.2%. We concluded that NEm and NEg requirements were influenced by age and possibly by the level of stress, nervousness and activity of animals into the respirometry chamber. Further studies should quantify HP with records of positional changes （time spent standing vs. lying down）. Additionally, HP quantification should be repeatedly performed in the same experimental period to obtain a representative value of NEg requirements.

Indirect calorimetry in obese female subjects: Factors influencing the resting metabolic rate

AIM: To evaluate selected factors influencing resting energy expenditure(REE) in obese female subjects.METHODS: Seventy seven 61 obese Caucasian women [mean age of 52.93 ± 13.45 years, and mean body mass index(BMI) of 41.78 ± 11.54 kg/m2] were enrolled; measurements of resting metabolic rate(RMR) by a ventilated, open-circuit system, indirect calorimeter were performed after an overnight fast. Body composition as well as medications, physical parameters, blood samples, disease pattern, and smoking were considered. RESULTS: RMR was significantly associated with body weight(r = 0.732, P < 0.001), body height(r = 0.401,P = 0.008), BMI(r = 0.504, P < 0.001), waist circumference(r = 0.602, P < 0.001), mid-upper arm circumference(r = 0.417, P = 0.006), mid-upper arm muscle circumference(r = 0.344, P = 0.028), total body water(r = 0.339, P = 0.035), body temperature(r = 0.409, P = 0.007), smoking(P = 0.031), serum T4 levels(r = 0.331, P = 0.036), obstructive sleep apnoea syndrome(OSAS; P = 0.023), impaired glucose tolerance(IGT; P = 0.017) and impaired glycaemic status, including hyperinsulinism, IGT and diabetes mellitus(P = 0.003).CONCLUSION: Future research should be prompted to optimize the procedure of indirect calorimetry to achieve clinical benefits in obese subjects.

Research on thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane based on differential scanning calorimetry

In order to test the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane(RDX),the linear temperature rise experiment of RDX was carried out by differential scanning calorimeter under different heating rate conditions.The kinetic calculation of RDX thermal decomposition curve was carried out by Kissinger and Ozawa methods,respectively,and the thermal analysis software was used to calculate the parameters such as self-accelerating decomposition temperature.The results show that the initial decomposition temperature range,decomposition peak temperature range,and decomposition completion temperature range of RDX are 208.4-214.2,225.7-239.3 and 234.0-252.4℃,respectively,and the average decomposition enthalpy is 362.9 J·g^-1.Kissinger method was used to calculate the DSC experimental data of RDX,the apparent activation energy obtained is 190.8 kJ·mol^-1,which is coincident with the results calculated by Ozawa method at the end of the reaction,indicating that the apparent activation energy calculated by the two methods is relatively accurate.When the packaging mass values are 1.0,2.0 and 5.0 kg,respectively,the self-accelerating decomposition temperatures are 97.0,93.0 and 87.0℃,respectively,indicating that with the increase of packaging mass,the self-accelerating decomposition temperature gradually decreases,and the risk increases accordingly.

CALORIMETRY DETERMINATION OF ^(210)Po IN TARGETS

The polonium-210 activity in raw material targets which was used to make the start neutron source rods of Qinshan Nuclear Power Station was determined in calorimetry. The calorimeter used is a twin-cup isothermal one. It works at room temperature and does not need any device of constant temperature. The instruments used for calorimetry are simple and have good properties. The background is from -1μV to + 2 μ V when the room temperature changs between 16℃ and 28 ℃. The data gotten in calorimetry are in correspondence within ±3.4 % with those from liquid scintillation method after the targets were dissolved, additionally in correspondence within ±1.7% with the data given by Amersham Laboratories for 241Am determination.

Interaction between Heparin and Fibronectin: Using Quartz Crystal Microbalance with Dissipation, Immunochemistry and Isothermal Titration Calorimetry

The adsorption behavior of heparin and fibronectin was studied by quartz crystal microbalance with dissipation(QCM-D), and the interaction between heparin and fibronectin was evaluated using immunochemistry and isothermal titration calorimetry(ITC) measurement. The results showed that there was competitive adsorption between heparin and fibronectin, and the preadsorption of fibronectin could prevent subsequent heparin adsorption to some extent, and the adsorbed Hep/Fn complex on the surface was in a rigid form. The bioactivity of heparin and fibronectin could be affected by the bulk concentration of each, and both heparin and fibronectin in Hep/Fn complex formed under p H 4 condition displayed larger bioactivity than that formed under p H 7 condition. Moreover, the fibronectin showed more exposed cell-binding sites at the p H value lower than physiological condition. The results of ITC further suggested that the interaction between heparin and fibronectin under p H 4 was stronger than under p H 7, and the complex was also more stable. The study brings forth the detailed interaction between heparin and fibronectin, which will be helpful for better understanding the interaction mechanism of the two biomolecules. The results may be potentially useful for the development of new generation of cardiovascular biomaterials.

A comparative study on the reactivity of charged Ni-rich and Ni-poor positive electrodes with electrolyte at elevated temperatures using accelerating rate calorimetry

The reactivity between charged Li(Li_(0.115)Mn_(0.529)Ni_(0.339)Al_(0.017))O_(2)(Li-rich),single crystal Li(Ni_(0.8)Mn_(0.1)Co_(0.1))O_(2)(SC-NMC811),LiFePO_(4)(LFP) and LiMn_(0.8)Fe_(0.2)PO_(4)(LMFP) positive electrodes at different states of charge(SOCs) and traditional carbonate-based electrolyte at elevated temperatures is systematically studied using accelerating rate calorimetry(ARC).The results show that the SOC greatly affects the thermal stability of the Li-rich and SC-NMC811 when traditional carbonate-based electrolyte is used.Although an increase in the SOC increases the energy density of lithium-ion cells,it also increases the reactivity between charged Li-rich and SC-NMC811 samples with electrolyte at elevated temperatures.In comparison with SC-NMC811,the Li-rich samples are much more stable at elevated temperatures,and the latter have higher specific capacity.SC-NMC811 samples are less reactive than traditional polycrystalline NMC811.Both LFP and LMFP samples show excellent thermal stability at elevated temperatures.The substitution of Fe by Mn in the olivine series positive materials does not impact the reactivity with electrolyte.

Determination of Standard Molar Enthalpies of Formation for "White Powdery Tungstic Acid" and for Dodecatungstophosphoric Acid by Solution Calorimetry

'White powdery tungstic acid' has been used for preparing various types of tungsten-containing compounds due to its high reactivity. The present paper covers the standard molar enthalpies of formation, △H0/f of three tungsten- containing acids. The values found for 'white powdery tungstic acid' WO3·1. 68H2O, 'yellow tungstic acid' WO3·1. 20H2O and dodecatungstophosphoric acid H3(PW12O40)·25H2O at 298. 15 K were-(1312±1), - (1192±1) and -(18150±13) kJ mol-1, respectively.

Studies of the Energy Release of Mitochondria from Sporophyte Cytoplasmic Male Sterile Rice by Differential Scanning Calorimetry

The differential scanning calorimetric (DSC)curves of the mitochondria isolated from two varieties of sporophyte cytoplasmic male sterile and their fertile lines of Yie Bai and Ma Xie type rice have been determined. The curves show that the energy is released continuously as temperature rise to 70℃. Some thermodynamic and kinetic parameters of the energy release of the mitochondria have been obtained. The presented results showed that the mitochondria from cytoplasmic male sterile rice released more heat and they had higher energy barrier, less rate, and more complicated mechanism than that of their fertile lines in the energy release process.

Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn(C_4H_7O_5)_2(s) by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.

Measurement of Crystallinity of Acrylic Copolymer by Swelling Differential Scanning Calorimetry

In this paper the measurement of crystallinity(C)ofacrylic copolymer(PAC),by Swelling Differential Scan-ning Calorimetry(SDSC)is discussed.Common DSC isonly used for measuring the crystallinity of polymers withmelting point,(T_m),below their decomposition temper-ature,(T_d).As temperature rises,polymers with swell-ing agent added become swollen and dissolved,goingthrough whole process of breaking solid structures.Thus,SDSC makes it possible to measure the crystallini-ty of polymers even with T_d below T_m.But the C mea-sured by WAXD and the total endothermal melting(swelling)heat in SDSC thermograms,(△H_l),are notlinearly correlated.It has been found that,instead of the△H_l,△H_l’obtained from the △H_l by subtracting the en-dothermal heat,△H_l,and the C measured by WAXDare linearly correlated.On the basis of this linear rela-tion,the unknown C of another PAC sample is measuredby SDSC.The result is in good accordance with thatmeasured by WAXD.

Analysis of the Pipe Heat Loss of the Water Flow Calorimetry System in EAST Neutral Beam Injector

Neutral beam injection heating is one of the main auxiliary heating methods in controllable nuclear fusion research. In the EAST neutral beam injector, a water flow calorimetry （WFC） system is applied to measure the heat load on the electrode system of the ion source and the heat loading components of the beamline. Due to the heat loss in the return water pipe, there are some measuring errors for the current WFC system. In this paper, the errors were measured experimentally and analyzed theoretically, which lay a basis for the exact calculation of beam power deposition distribution and neutralization efficiency.

Thermodynamics of clayedrug complex dispersions: Isothermal titration calorimetry and high-performance liquid chromatography

An understanding of the thermodynamics of the complexation process utilized in sustaining drug release in clay matrices is of great importance.Several characterisation techniques as well as isothermal calorimetry were utilized in investigating the adsorption process of a model cationic drug(diltiazem hydrochloride,DIL)onto a pharmaceutical clay system(magnesium aluminium silicate,MAS).X-ray powder diffraction(XRPD),attenuated total reflectance Fourier transform infrared spectroscopy(ATRFTIR)and optical microscopy confirmed the successful formation of the DIL-MAS complexes.Drug quantification from the complexes demonstrated variable behaviour in the differing media used with DIL degrading to desacetyl diltiazem hydrochloride(DC-DIL)in the 2 M HCl media.Here also,the authors report for the first time two binding processes that occurred for DIL and MAS.A competitor binding model was thus proposed and the thermodynamics obtained suggested their binding processes to be enthalpy driven and entropically unfavourable.This information is of great importance for a formulator as care and consideration should be given with appropriate media selection as well as the nature of binding in complexes.

NEW METHOD IN CALORIMETRY FOR SUPERHIGH ENERGY HADRONS

A new method in calorimetry for superhigh energy hadrons is proposed.The main feature of the method is the effective detection of soft neutrons,abundantly present in the superhigh energy hadron showers,by using neutron detectors insensitive to minimum ionizing particles.Such a calorimeter allows us to selectively detect the hadrons in the environment of high backgrounds of electrons,photons and muons.

Standard Molar Enthalpy of Formation of Morin Studied by Rotating-Bomb Combustion Calorimetry

Flavonols are plant nature. Morin and other related pigments that are ubiquitous in plant flavonols have come into recent prominence because of their usefulness as anticancer, antitumor, anti-AIDS, and other important therapeutic activities of significant potency and low systemic toxicity. The heat of combustion of morin （molecular formula, C15H10O7·H2O） in oxygen was measured by a rotating-bomb type combustion calorimeter, the standard molar enthalpy of combustion of morin at T = 298.15 K was determined to be △cH^ m （C15H10O7·H2O, s） = - （5 937.99±2.99） kJ·mol^-1. The derived standard molar enthalpy of the formation of morin in solid powder state at T = 298.15 K, △fH^ m（C15H10O7·H2O, s）, was -（1 682.12 ± 3.58） kJ·mol^1, which provide an accurate data of the stability of morin to the pharmacy and pharmacology.

Comparison between Glass and Stainless-Steel Vessels in Differential Scanning Calorimetry Estimation

Differential scanning calorimetry (DSC) provides easy screening for thermal hazard evaluation. Here, we investigate the difference between using glass and stainless-steel vessels on the DSC measurement of exothermic decomposition energy (QDSC) for 41 chemical substances (containing nitro, halogen, peroxide, and sulfur groups, and hydrazine bonds). Two borosilicate glass vessels (capillary and ampule) and one stainless-steel vessel were used. All QDSC values obtained were investigated with reference to the permissible fluctuation range specified by the ASTM (American Society for Testing and Materials) international Both glass vessels produced very similar QDSC values, despite different sample scales. The QDSC values obtained with the glass vessels were generally roughly within the variation tolerance range of the stainless-steel vessel. Notable exceptions were halogen- or sulfur-containing compounds;these exhibited smaller QDSC values with glass vessels in almost all cases. We will investigate whether certain structures in compounds react with stainless steel. The vessel material choice is crucial in evaluating the true reactivity of a substance.