Effects of particle size on the thermal stability of lithiated graphite anode

The thermal behavior of fully lithiated natural graphite flakes with different particle sizes has been investigated using differential scanning calorimetry (DSC). For DSC measurements, a fully lithiated graphite anode was heated in a hermetically sealed high pressure pan with a poly vinylidene diflouride (PVdF) binder and 1 M LiPF₆ solution in ethylene carbonate (EC)-diethyl carbonate (DEC) mixture. It has been founded that the particle size has a strong influence on the thermal stability of the lithiated graphite anode. The heat generation due to the solid electrolyte interface (SEI) decomposition increases with decreasing the particle size. The onset temperatures for exothermic reactions after initial SEI decomposition appear to be lower for graphite electrodes with smaller particle sizes. This is attributed to a thermal induced delithiation facilitated by reduced diffusion path and higher surface area in smaller graphites. The structural changes in graphites during DSC scan have been investigated by ex situ X-ray diffraction (XRD) and Raman spectrometer.     

Enhanced thermal properties of the solid electrolyte interphase formed on graphite in an electrolyte with fluoroethylene carbonate

The influence of fluoroethylene carbonate (FEC) on the electrochemical and thermal properties of graphite anodes is examined. The dQ/dV graph of graphite/Li cells shows that the electrochemical reduction peak of an electrolyte shifts to higher potential in the presence of FEC. The DSC results for graphite anodes cycled in FEC-containing electrolytes clearly exhibit that an exothermic peak at around 120 °C mostly disappears. It is demonstrated by X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) that SEI formed by the electrochemical reduction of FEC consists of a relatively high proportion of LiF and gives low interfacial resistance for graphite/Li/Li cells.     

Thermal stability of the interface between discharged non-graphitizable carbon and electrolyte for lithium-ion batteries

The thermal stability of a non-graphitizable carbon electrode was studied quantitatively by differential scanning calorimetry (DSC). Charged non-graphitizable carbon electrode powder gave exothermic peaks at around 300 °C and the heat values varied depending on the ratio of the electrode powder to coexisting electrolyte solution. Based on the similarities in the exothermic behaviors of charged graphite and non-graphitizable carbon electrodes, the exothermic reactions at around 300 °C should be assigned to the reductive decomposition of a surface film by charged non-graphitizable carbon. On the other hand, non-graphitizable carbon electrode powder showed exothermic reactions at around 290 °C even at a discharged state, while almost no exothermic heat was seen for a discharged graphite electrode powder at temperatures above 250 °C. The heat values decreased as Li-ions in the non-graphitizable carbon electrode were extracted. Based on the present results and a consideration of the slow diffusion and irreversible trapping of Li-ions in non-graphitizable carbon, Li-ions remaining in non-graphitizable carbon could induce exothermic reactions at around 290 °C, even at a discharged state.     

Study of the formation of a solid electrolyte interphase (SEI) in ionically crosslinked polyampholytic gel electrolytes

An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate with acrylic acid. A novel ionically crosslinked polyampholytic gel electrolyte was prepared through the free radical copolymerization of the ionic complex and acrylamide in a solvent mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (1:1:1, v/v) containing 1 mol/L of LiPF₆. The impedance analysis indicated that the ionic conductivity of the polyampholytic gel electrolyte was rather close to that of solution electrolytes in the absence of a polymer at the same temperature. The temperature dependence of the conductivity was found to be well in accord with the Arrhenius behavior. The formation processes of the solid electrolyte interphase (SEI) formed in both gel and solution electrolytes during the cycles of charge-discharge were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry curves show a strong peak at a potential of 0.68 V and an increase of the interfacial resistance from 17.2 Ω to 35.8 Ω after the first cycle of charge-discharge. The results indicate that the formation process of SEI formed in both gel and solution electrolytes was similar which could effectively prevent the organic electrolyte from further decomposition and inserting into the graphite electrode. The morphologies of SEI formed in both gel and solution electrolytes were analyzed by field emission scanning electron microscopy. The results indicate that the SEI formed in the gel electrolyte showed a rough surface consisting of smaller solid depositions. Moreover, the SEI formed in the gel electrolyte became more compact and thicker as the cycling increased.     

The function of vinylene carbonate as a thermal additive to electrolyte in lithium batteries

The role of vinylene carbonate (VC) as a thermal additive to electrolytes in lithium ion batteries is studied in two aspects: the protection of liquid electrolyte species and the thermal stability of the solid electrolyte interphase (SEI) formed from VC on graphite electrodes at elevated temperatures. The nuclear magnetic resonance (NMR) spectra indicate that VC can not protect LiPF₆ salt from thermal decomposition. However, the function of VC on SEI can be observed via impedance and electron spectroscopy for chemical analysis (ESCA). These results clearly show VC-induced SEI comprises polymeric species and is sufficiently stable to resist thermal damage. It has been confirmed that VC can suppress the formation of resistive LiF, and thus reduce the interfacial resistance.     

Burnout behavior of ceramic coated open cell polyurethane (PU) sponges

Open cell rigid foams made from polyurethane (PU) are frequently used in ceramic processing for preparation of porous ceramics by the so-called replica technique. This work presents data regarding the PU burnout, shrinkage characteristics as well as the morphology of the ceramic coated PU sponges during heating up. Shrinkage of the ceramic coated PU sponges closely follows the mass loss due to PU decomposition. Two temperatures (i) 267 °C and (ii) 380 °C were identified at which PU decomposition reaches local maxima. Shrinkage measurements on ceramic coated PU sponges reveal that both PU decomposition stages lead to similar extends of shrinkage in the ceramic coated PU sponge. Differential thermal analysis (DTA) showed that the two decomposition related temperatures (267 and 380 °C) differ concerning the energy release. While the low-temperature signal is endothermic, an exothermic signal was detected at 380 °C. The morphology of the ceramic coated PU sponges was investigated with scanning electron microscopy (SEM) which gave insight into the formation of hollow ceramic struts—a well known feature of ceramics being prepared by the replica technique.     

The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes

The thermal stability of graphite anodes used in Li-ion batteries has been investigated, with the influence of electrolyte salt under special scrutiny, LiPF₆, LiBF₄, LiCF₃SO₃ and LiN(SO₂CF₃)₂ in an ethylene carbonate (EC)/dimethyl carbonate (DMC) solvent mixture. Differential scanning calorimetry (DSC) showed exothermic reactions in the temperature range 60-200 °C for all electrolyte systems. The reactions were coupled to decomposition of the solid electrolyte interphase (SEI) and reactions involving intercalated lithium. The onset temperature of the exothermic reactions increased with type of salt in the order: LiBF₄<LiPF₆<LiCF₃SO₃<LiN(SO₂CF₃)₂. X-ray photoelectron spectroscopy (XPS) was used to identify surface species formed prior to and after the exothermic reactions, to clarify different thermal behaviour for different salts. The decomposed SEI's in LiCF₃SO₃ and LiN(SO₂CF₃)₂ electrolytes were found to be mainly solvent-based, including lithium alkyl carbonate decomposition to stable Li₂CO₃ and the formation of poly(ethylene oxide) (PEO)-type polymers. In the LiBF₄ and LiPF₆ systems, decomposition was governed by salt reactions, which decomposed the salts and resulted in the main product LiF.     

Surface chemistry of intermetallic AlSb-anodes for Li-ion batteries

The solid electrolyte interphase (SEI) layer on AlSb electrodes has been studied in Li/AlSb cells containing a LiPF₆ EC/DEC electrolyte using X-ray photoelectron spectroscopy (XPS). Data were collected before SEI-formation, during formation, and after formation at 0.01 V versus Li⁰/Li⁺, and at full delithiation in cycled cells at 1.20 V. The thickness of the SEI layer increases during lithiation and decreases during delithiation. This dynamic behaviour occurs continuously on cycling the cells. The growth of the SEI layer can be attributed predominantly to the deposition of carbonaceous species below 0.50 V versus Li⁰/Li⁺; these species disappear almost completely during delithiation. The extra surface-layer formation is a consequence of the additional charge that is needed to lithiate the remaining Sb component of the micrometer-sized AlSb particles at low potentials as seen by synchrotron-based X-ray diffraction. Aluminium is not reactive to lithium alloying in this electrolyte. Relatively small amounts of LiF were detected in the AlSb SEI layers compared to that commonly found in the SEI layers on graphite electrodes.     

Electrolyte additives for enhanced thermal stability of the graphite anode interface in a Li-ion battery

The influence of electrolyte additives on the thermal stability of graphite anodes in a Li-ion battery has been investigated. The selected additives are: ethyltriacetoxysilane, 1,3-benzoldioxole, tetra(ethylene glycol)dimethylether and vinylene carbonate. These compounds were added in 4% to an electrolyte consisting of 1M LiBF₄ ethylene carbonate (EC)/diethyl carbonate (DEC) solvent mixture. Differential scanning calorimetry (DSC) was used to investigate the thermal stability. The electrochemical performance was investigated by galvanostatic cycling and the formed solid electrolyte interphase (SEI) was characterised by photoelectron spectroscopy (PES) using Al Kα and synchrotron radiation (SR). The onset temperature for the thermally activated reactions was found to increase for all electrodes cycled with additives compared to electrodes cycled without additives. The onset temperature increased in the order: no additive < tetra(ethylene glycol)dimethyl ether < 1,3-benzoldioxole < ethyl-triacetoxysilane < vinylene carbonate. Features in the PES spectra found to be associated with high onset temperatures for thermally activated reactions are: (i) no discernible graphite peak, (ii) small amount of salt species of the type LiF and Li_xBF_yO_z and (iii) larger amounts of organic compounds preferably with a high oxygen content.     

Thermal Decomposition of Potassium Titanium Hexacyanoferrate（Ⅱ） Loaded with Cesium in a Fixed Bed Calciner

The thermal decomposition of potassium titanium hexacyanoferrate（ Ⅱ ） （KTiFC） loaded with cesium （referred to as Used Exchanger,or UE） was-studied at different flow rate of air in a fixed bed calciner. The calcina t ign processconsisted of four stages：ambient temperature- 180℃ （stageⅠ ）, 180-250℃（stage Ⅱ）, 250-400℃ （stage Ⅲ）, and constant 400℃ （stage Ⅳ）.The most intense reaction occurred in stage .Ⅱ. The rate of thermal decomposition was controlled, depending on the O2 flux, by O2 or CN concentration in ditterent stages. Results from differential thermal analysis （DTA） showed that the calcination reaction of the anhydrous UE was exothermic, with an approximate heat output of 4.6kJ·g^-1, which was so large to cause the possible agglomeration of calcined residues. The agglomeration could be avoided by enhancing heat transfer and controlling the O2 flux. It was found that there was no cyanides in the calcined residues and no CN-bearing gases such as HCN and （CN）2 in the off-gas. It seemed that the catalytic oxidation furnace behind the fixed bed calciner could be cancelled.     

High temperature lithium cells using conversion oxide electrodes

Oxidized stainless steel electrodes containing chromium oxides without any conducting additives or binder have been successfully cycled at high temperatures (up to 100 °C) in organic solvent-based electrolytes with high reversibility. Cycling at high temperature results in an enhancement of the capacity at lower voltages, which is maintained upon cycling. After studying different electrolyte candidates, the best results were obtained using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) dissolved in ethylene carbonate.     

Mechanism of self-discharge in graphite-lithium anode

In order to evaluate the anode contribution to the lithium-ion battery self-discharge, three electrode coin cells composed of metallic lithium as reference and counter electrode, organic liquid electrolyte and graphite composite working electrode were constructed as test cells. They were first cycled for a dozen cycles and then stored in the full lithiated state of graphite, at 70 °C for periods from 1 to 8 days. The capacity loss was determined during the first delithiation following storage. The latter was found composed of two terms, a reversible and an irreversible one, where the relative amounts are storage time dependants. Electrochemical impedance spectroscopy (EIS) was used to investigate the changes in the cell interfacial characteristics. A model involving the formation of an absorbed electron-ion-electrolyte complex on the graphite surface is proposed as the mechanism of the reversible and irreversible capacity losses. It is also suggested that precipitation/dissolution reactions are taking place at the solid electrolyte interphase (SEI). Precipitation occurs with insoluble inorganic species such as, LiF and Li₂CO₃, whereas dissolution may concern the organic and/or polymer part of the SEI. The continuous growth of the inorganic (and most resistive) part of the SEI with the subsequent electrode isolation is proposed as the major mechanism of the electrode end of life.     

Minimising heat losses during batch ohmic heating of solid food

The influence of cell design on the uniformity of batch ohmic heating of a solid foodstuff was examined. Various ways of minimising heat loss from the cell surface including insulation or providing supplementary heat via a heating belt or panel were assessed but discarded in favour of housing the cell in a hot air cabinet maintained at 80 °C and eliminating the surrounding cell body. Various electrode materials and designs were evaluated prior to opting in favour of platinised titanium electrodes of minimal practicable thickness (1 mm). The final system developed involved the use of a combined ohmic/convection heating with the food stuff contained in a plastic casing pressurised between two spring-loaded electrodes. Under optimised conditions a maximum overall temperature variation of 12.1 °C within the product was achieved after 150 s which was reduced to 8.6 °C after 3 min standing time.     

On the role of the thermal treatment of sulfided Rh/CNT catalysts applied in the oxygen reduction reaction

Low loading sulfided rhodium catalysts supported on carbon nanotubes (CNTs) were prepared from RhCl₃ by deposition–precipitation using hydrogen peroxide, followed by an exposure to hydrogen sulfide and an additional thermal treatment in the range from 400 °C to 900 °C. Hydrogen sulfide was generated online from hydrogen and sulfur vapor over molybdenum disulfide as catalyst. By elemental analysis, the Rh loading of the prepared catalysts was found to be 1.4–1.8 wt%. Morphology and composition of the resulting catalysts were characterized by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and X-ray photoelectron spectroscopy (XPS). Nanoparticles were found to be highly dispersed on the CNTs with an average diameter as small as 1.0 nm determined by TEM. Sintering occurred during heat treatments at 650 °C and 900 °C in helium, as evidenced by XRD, TEM, and XPS. The treatment with hydrogen sulfide significantly enhanced the activity of the supported rhodium catalysts for the oxygen reduction reaction (ORR) in hydrochloric acid, as determined by rotating disc electrode measurements. The sulfided catalyst annealed at 650 °C with a particle size of about 2.5 ± 1.0 nm showed the best performance for the ORR, which is discussed based on the presence of a more stable rhodium sulfide layer on the metallic rhodium particles.     

Thermal stability of mercury captured by ash

The thermal stability of mercury captured by ash was studied by sampling ash throughout the collection train of two Kentucky power plants. Sampling occurred over multiple years and involved both fresh and archived samples. During one ash collection episode, sampling was from the combustion of a single pulverized coal feed. The other collections involved ash from blended feeds. Ash was collected from economizer, mechanical and electrostatic precipitator hoppers. Feed coals, rejects and bottom ash were also sampled. Fractions of all the samples were heated in a thermal analyzer to maximum temperatures increased sequentially from 100 to 500 °C in 100 °C increments. The mercury content of the spent material was then determined by analysis of the solids for Hg. From this data the thermal decomposition temperature of the captured mercury was determined. The total mercury captured by each sample, thermal stability of the mercury in relation to collection site, and correlations between mercury capture and chemical composition of the sample were also determined. The data showed that mercury was released between 300–400 °C for all ash samples. The thermal release of Hg between 300–400 °C was studied in greater detail by following the Hg release in several samples at 25 °C intervals from 300–400 °C. The concentration of mercury captured in the ESPs hoppers was greater than in the ash collected from the economizer or mechanical separators.     

Thermal transformations of sonicated pyrophyllite

The differences on the thermal behaviour (DTG–DTA) of three pyrophyllite samples measured before and after sonication have been studied. Sonication treatment produces substantial textural modifications but negligible changes in the structure of the material. These modifications produce important changes in the thermal behaviour of pyrophyllite samples. Thus, it produces a decrease of more than 100 °C in the dehydroxylation temperature as measured by DTG and DTA effects. In addition, the exothermic effect of mullite formation shifts to lower temperature (about 30 °C) in sonicated pyrophyllite. These modification in the thermal behaviour are related to the pronounced decrease in particle size. The dehydroxylation effect of kaolinite that accompanies two of the studied samples, overlaps with that of sonicated pyrophyllite; however, the exothermic effect at 975 °C of kaolinite remain unchanged with the treatment.     

Impedance spectroscopy on porous materials: A general model and application to graphite electrodes of lithium-ion batteries

Electrochemical impedance spectroscopy (EIS) was applied to porous negative graphite electrodes for lithium-ion batteries in the EC:DMC, 1 M LiPF₆ electrolyte. The effect of porosity on the electrode response time was studied and a theoretical model was developed, based on free path of the current lines between subsequent reaction sites. The effect of porosity on the electrode response is evidenced by the impedance spectra in which the high frequency capacitive semicircle is distorted. Fresh electrodes (before the formation of the solid electrolyte interphase, SEI) and cycled electrodes have different shapes of the impedance spectra indicating a change of processes at the surface. In particular, the shape of the spectrum for a fresh electrode can be related to an adsorption process. Impedance spectra of fresh electrodes were fitted using a simple model that considers porosity and the assumed electrochemical processes, giving good agreement between model and data. A correlation was found between adsorption sites and irreversible charge capacity in the first cycle.     

Preparation of cobalt ferrite from the thermolysis of cobalt tris(malonato)ferrate(III)trihydrate precursor

Thermal decomposition of cobalt tris(malonato)ferrate(III)trihydrate precursor, Co₃[Fe(CH₂C₂O₄)₃]·3H₂O has been investigated from ambient temperature to 600 °C in static air atmosphere using various physico-chemical techniques, i.e. TG–DTG–DSC, XRD, Mössbauer and IR spectroscopic techniques. The precursor undergoes dehydration and decomposition simultaneously to yield cobalt malonate and iron(II) malonate intermediates at 205 °C. At higher temperature (325 °C) these intermediate species undergo exothermic decomposition to yield CoO and α-Fe₂O₃, respectively. Finally cobalt ferrite, CoFe₂O₄, has been obtained as a result of solid–solid reaction between Fe₂O₃ and CoO at a temperature (380 °C) much lower than that of ceramic method. SEM analysis of the final thermolysis product reveals the formation of monodisperse cobalt ferrite nano-particles with an average particle size of 45 nm. Magnetic studies show that these particles have a saturation magnetization of 3095 G and Curie temperature of 504 °C. Lower magnitude of these parameters as compared to the bulk values is attributed to the smaller particle size.     

Storage behavior of LiNi1/3Co1/3Mn1/3O2/artificial graphite Li-ion cells

A series of Li-ion cells containing LiNi_1/3Co_1/3Mn_1/3O₂ and artificial graphite as the active materials, have been stored at various temperatures from 0 to 70 °C. The 3-electrode impedance study shows that both the solid electrolyte interphase (SEI) film resistance and charge-transfer resistance of the negative electrode first decrease and then increase during storage at 70 °C, while both resistances for the positive electrode increase under this condition. The reversible capacity loss of the 3-electrode cell, which is possibly attributed to dissolution of SEI film, accounts for over half of the total capacity loss after 5 weeks of storage. Gases generated from the swelling aged cell at 60 °C are mainly attributed to the reduction of the electrolyte on the negative electrode. A further study on the side-reaction has been done on graphite electrodes and separators, indicating that SEI films may be rearranged and reformed on negative electrodes, and that some pores on the positive electrode side of separator are blocked due to the oxidation of electrolyte, resulting in poor Li-ion transfer and rise of the ohmic resistance during storage at elevated temperature. However, at 0 °C, this side-reaction is impeded.     

Magnetoresistance of two-phase carbons

The transverse magnetoresistance was studied at liquid nitrogen temperature for carbons with two phases, the turbostratic and the graphitic. Samples investigated were carbons prepared by heat treatment at temperatures between 1320 and 1780°C under pressure of 5 kbar. The starting materials were a coke obtained from polyvinyl chloride carbonized up to 680°C, and an equi-weight mixture of the same coke with a thermal black. Samples obtained from the coke alone by the heat treatment above 1470°C consist of two phases. When the fractionof the graphitic phase ranges 0.5–6%, two new types of field dependence of the transverse magnetoresistance, types 1 and 2, are observed. The field dependence of the magnetoresistance were reproduced by using a model composed of a 2900°C-treated pyrolytic graphite and of a 1900°C-treated extruded petroleum coke carbon, when the resistance ratio between the two components was properly adjusted. This seems to show that the new types of field dependence found in this work are due to the presence of a mixture of graphitic and turbostratic grains in our samples.