Temperature Dependence Of Activation Energy Research Articles

A modification to the Friedman and Ortega isoconversional methods for evaluation of the activation energy as a function of conversion and temperature

The Friedman and Ortega isoconversional methods typically apply linear regression to the isoconversional kinetic data for calculation of activation energy solely as a function of extent of conversion. However, in complex reactions, activation energy depends on both conversion and temperature. Our modification involves quadratic curve fitting instead of linear regression, resulting in the determination of activation energy as a function of conversion and temperature. The new technique enables the calculation of the temperature dependence of activation energy for different heating rates, making it a valuable addition to isoconversional analysis. The conventional and modified approaches were utilized on the isoconversional kinetic data concerning polyethylene thermal degradation. The results provided a more detailed representation of the variations in activation energy when nonlinear regression was used.

Admittance Spectroscopy Study of Defects in β-Ga2O3

We present a comprehensive investigation of electrically active defects and transport properties in commercial (2¯01) edge-defined film-fed growth β-Ga2O3 using admittance spectroscopy measurements from 14 K up to 450 K. Isothermal capacitance-frequency measurements were conducted from 410 to 450 K to resolve a defect ∼0.8 eV below the conduction band edge and compared with deep-level transient spectroscopy and isothermal capacitance transient spectroscopy measurements. We report significant non-Arrhenius behavior of a defect ∼100 meV below the conduction band and apply the Arrhenius transformation matching method to extract its temperature-dependent activation energy and capture cross-section in the temperature range of 75 to 195 K. At low temperatures (<50 K), we use bias-dependent admittance spectroscopy to extract the electron mobility in β-Ga2O3 from the modified dielectric relaxation frequency. Finally, we discuss the potential of admittance spectroscopy for defect characterization in wide bandgap semiconductors in terms of the defect detection range, instrument requirements, and the frequency-temperature experiment space.

Synthesis, Structural and Fluorescence Investigations of Novel Li2Ba5W3O15:Sm3+ Phosphors for Photonic Device Applications.

In the current study, Sm3+ ions doped Lithium Barium Tungstate (Li2Ba5W3O15) (LBW) phosphors with the ability to emit orange-red light were made using the traditional high-temperature solid-state reaction technique. The structure and phase of the as-synthesized phosphor samples were examined via X-ray diffraction (XRD) patterns. The diffraction peaks of the undoped LBW and Sm3+ ions doped LBW phosphors closely resemble those of the Joint Committee on Powder Diffraction Standards (JCPDS) pattern with card number 01-072-1717. Scanning electron microscopy (SEM) was employed for the analysis of the morphological characteristics of the synthesized phosphor material. Fourier Transform Infrared (FT-IR) spectroscopy was used to study several vibrational and molecular bands present in the host matrix. Using diffuse reflectance spectra (DRS), the optical band gap values (Eg) were evaluated by applying Tauc's method. The photoluminescence (PL) spectra characteristics at λex = 336nm indicate the emission of dopant ions (Sm3+) in the deep orange-red region corresponding to 4G5/2 → 6H5/2 transition (at 581nm) with concentration quenching after 2mol % of Sm3+ ions. Using the PL spectra, the CIE chromaticity coordinates of LBWS2.0 phosphor were estimated and found in the deep visible orange-redarea, indicating the potential use of the prepared phosphor material for phosphor-converted white light emitting diodes (w-LEDs) applications. Double exponential behaviour can be seen in the PL decay spectralprofiles obtained under λem = 581nm and λex = 336nm. The experimental lifetimes (τexp) decrease as the concentration of Sm3+ ions rise. The temperature-dependent PL (TDPL) and activation energy results show that the as-synthesized phosphor has considerably superior thermal stability. The results of the current research contemplate us the applicability of Sm3+ ions doped LBW phosphor for photonic devices such as w-LEDs.

Investigation of the structural and electrical conductivity properties in pure and cation exchanged rectorite

Clay minerals, as biofriendly and low-cost materials, are highly essential for the modern industrial applications including the production of clean energy, its storage and conversion. Here, the capabilities of pure and cation exchanged rectorite, a regularly interstratified phyllosilicate from Beatrix Mine (South Africa) were explored and discussed. A comprehensive characterization was performed by means of high resolution solid-state NMR, electrochemical impedance spectroscopy and powder X-ray diffraction. 23Na MAS and 3QMAS NMR spectroscopy was used to characterize accessibility of interlayer space in rectorite for exchangeable cations. Three Na sites attributed to easily exchangeable Na+ on the surface or in large pores, Na+ in dehydrated micaceous interlayers and Na+ in hydrated smectite interlayers were identified. Differences in hydration states in smectitic interlayers depending on the type of intercalation were detected using 1H MAS NMR. A higher amount of hydrating water molecules in pure and Mg-exchanged rectorites was attributed to the higher hydration energy of Ca2+ and Mg2+. The temperature dependences of electrical conductivity in this work were best described using the empirical Vogel-Tammann-Fulcher equation with the temperature-dependent effective activation energy parameter. Significantly stronger change of activation energy in Mg2+ exchanged rectorite in the temperature range of 10 °C to 50 °C as compared to pure rectorite and its Na+, Li+ and NH4+ modifications was related to an extensive H-bond network in the interlayers, which facilitated an effective proton transfer responsible for electric conductivity. The obtained resutls suggested a greater potential for the use of Mg-exchanged rectorite as ionic conductor at enhanced temperatures.

Electrical and optical properties of a lead-free complex double perovskite BaNaFeMoO6: Photovoltaic and thermistor applications

In this communication, synthesis (solid-state reaction) and characterizations of a complex double perovskite BaNaFeMoO6 are reported. X-ray diffraction analysis (structure and lattice parameters) adopts a monoclinic structure while Raman spectroscopy provides information about the vibrational characteristics. Homogenous distribution of the grains is observed from the scanning electron microscope (SEM) whereas energy dispersive X-ray analysis (EDX) supports compositional consistency. Ultraviolet–visible (UV–vis) data provides a direct energy bandgap of 2.75 eV, which may be suitable for photovoltaic applications. The analysis of Maxwell-Wagner type of dielectric dispersion, resistance, relaxation, and transport mechanism are carried out using dielectric, impedance, modulus, and conductivity data recorded within an available range of frequency (1 kHz – 1 MHz) and temperature (25 °C – 500 °C). Both the theoretical fit of the Nyquist data using ZSIMPWIN software as well as temperature-dependent conductivity support a negative temperature coefficient of resistance (NTCR) nature. The scaling nature of modulus data supports the non-Debye type of relaxation. The obtained temperature-dependent thermistor constant (β), sensitivity factor (α), and activation energy make the prepared material suitable for thermistor-related device application. The study of polarization–electric field (P-E) loop suggests the possibility of ferroelectric nature in the reported material.

Development of a new approach for the kinetic modeling of the lithium reactive hydride composite (Li-RHC) for hydrogen storage under desorption conditions

Among some promising candidates for high-capacity energy and hydrogen storage is the Lithium-Boron Reactive Hydride Composite System (Li-RHC: 2 LiH + MgB2/2 LiBH4 + MgH2). This system desorbs hydrogen only at relatively high temperatures and presents a two-step series of reactions occurring in different time scales: first, MgH2 desorbs, followed by LiBH4. Hitherto, the dehydrogenation kinetic behavior of such a system has been described for different temperatures at specific values of operative pressure. However, a comprehensive model representing its dehydrogenation kinetic behavior under different operative conditions has not yet been developed. Herein, the separable variable method is applied to develop a comprehensive kinetic model, including the two-step dehydrogenation series reaction. The MgH2 decomposition is described with the one-dimensional interface-controlled reaction rate Johnson-Mehl-Avrami-Erofeyev-Kholmogorov (JMAEK) with a (Pequilibrium/Poperative) pressure functionality and an Arrhenius temperature dependence activation energy of 63 ± 3 kJ/mol H2. The LiBH4 decomposition is modeled applying the autocatalytic Prout-Tompkins model. A novel approach to describe the Prout-Tompkins t0 parameter as a function of the operative temperature and pressure model is proposed. This second reaction step presented a (Pequilibrium – Poperative/Pequilibrium)2 pressure dependence and an Arrhenius temperature dependence with activation energy 94 ± 13 kJ/mol H2. The proposed approach is experimentally and computationally validated, successfully describing the decomposition kinetic behavior of MgH2 and LiBH4 under three-phase gas, liquid and solid environment and shows good agreement between experimental and modeled curves.

Kinetics of the reaction CH2CO + O (3P): Are the CH2 and CO2 the most favorable products?

Overall thermal rate coefficients for the CH2CO + O (3P) ⟶ CH2 + CO2 reaction were estimated by combining the canonical variational theory with multidimensional small-curvature tunneling corrections (CVT/SCT) and multifaceted variable-reaction-coordinate transition state theory (VRC-TST) results. The energies, equilibrium geometries, and harmonic vibrational frequencies were calculated at M06-2X/aug-cc-pVTZ level of theory. Our thermal rate constants show excellent agreement with experimental data confirming the CH2 + CO2 as the most favorable channel. Fitted total thermal rate coefficients into a modified Arrhenius equation shows a temperature-dependent activation energy.

Statistical Optimization of Pyrolysis Process for Thermal Destruction of Plastic Waste Based on Temperature-Dependent Activation Energies and Pre-Exponential Factors

The massive increase in disposable plastic globally can be addressed through effective recovery methods, and one of these methods is pyrolysis. R software may be used to statistically model the composition and yield of pyrolysis products, such as oil, gas, and waxes to deduce an effective pyrolysis mechanism. To date, no research reports have been documented employing the Arrhenius equation in R software to statistically forecast the kinetic rate constants for the pyrolysis of high-density plastics. We used the Arrhenius equation in R software to assume two series of activation energies (Ea) and pre-exponential factors (Ao) to statistically predict the rate constants at different temperatures to explore their impact on the final pyrolysis products. In line with this, MATLAB (R2020a) was used to predict the pyrolysis products of plastic in the temperature range of 370–410 °C. The value of the rate constant increased with the temperature by expediting the pyrolysis reaction due to the reduced frequency factor. In both assumed series of Ea and Ao, a significantly larger quantity of oil (99%) was predicted; however, the number of byproducts increased in the first series analysis compared to the second series analysis. It was revealed that an appropriate combination of Ea, Ao, and the predicted rate constants could significantly enhance the efficiency of the pyrolysis process. The major oil recovery in the first assumed series occurred at 390 °C to 400 °C, whereas the second assumed series of Ea and Ao occurred at 380 °C to 390 °C. In the second series at 390 °C to 400 °C, the predicted kinetic rate constants behaved aggressively after 120 min of the pyrolysis process. The second assumed series and anticipated rate constants at 380 °C to 390 °C can be applied commercially to improve oil production while saving energy and heat.

Temperature dependent activation energies of exciton states on a single GaAs laterally coupled-quantum-dot molecule and quantum dot

The objective of this study was to perform spectroscopy measurements of a single GaAs laterally coupled quantum dot molecule and quantum dot. Compared to photoluminescence spectra between a single GaAs laterally coupled quantum dot molecule and a single quantum dot, the presence of optical coupling was confirmed through dipole-dipole interactions in a single coupled quantum dot molecule. Based on temperature dependence measurements, weak exciton-phonon interactions (25 meV) were observed from the ground exciton state of a single GaAs laterally coupled quantum dot molecule in comparison with a strong exciton-phonon interaction (49 meV) from the ground exciton state of a single GaAs QD. Such weak interactions were due to reduced confinement at exciton states in a single laterally coupled quantum dot molecule. In addition, weaker activation energy (∼15 meV) was observed in terms of confined electrons in a single laterally coupled quantum dot molecule, where a confinement effect became reduced due to enlarged dimensional area in one direction along [1 1‾ 0].

Quantification of solid-phase chemical reactions using the temperature-dependent terahertz pulsed spectroscopy, sum rule, and Arrhenius theory: thermal decomposition of α-lactose monohydrate

Transformations of the low-energy vibrational spectra are associated with structural changes in an analyte and closely related to the instability of weak chemical bounds. Terahertz (THz)/far-infrared optical spectroscopy is commonly used to probe such transformation, aimed at characterization of the underlying solid-phase chemical reactions in organic compounds. However, such studies usually provide quite qualitative information about the temperature- and time-dependent parameters of absorption peaks in dielectric spectra of an analyte. In this paper, an approach for quantitative analyses of the solid-phased chemical reactions based on the THz pulsed spectroscopy was developed. It involves studying an evolution of the sample optical properties, as a function of the analyte temperature and reaction time, and relies on the classical oscillator model, the sum rule, and the Arrhenius theory. The method allows one to determine the temperature-dependent reaction rate V1(T) and activation energy Ea. To demonstrate the practical utility of this method, it was applied to study α-lactose monohydrate during its temperature-induced molecular decomposition. Analysis of the measured THz spectra revealed the increase of the reaction rate in the range of V1 ≃ ~9 × 10-4-10-2 min-1, when the analyte temperature rises from 313 to 393 K, while the Arrhenius activation energy is Ea ≃ ~45.4 kJ/mol. Thanks to a large number of obtained physical and chemical parameters, the developed approach expands capabilities of THz spectroscopy in chemical physics, analytical chemistry, and pharmaceutical industry.

Facile synthesis of Cu2O nanorods in the presence of NaCl by successive ionic layer adsorption and reaction method and its characterizations.

Cuprous oxide (Cu2O) nanorods have been deposited on soda-lime glass substrates by the modified successive ionic layer adsorption and reaction technique by varying the concentration of NaCl electrolyte into the precursor complex solution. The structural, electrical and optical properties of synthesized Cu2O nanorod films have been studied by a variety of characterization tools. Structural analyses by X-ray diffraction confirmed the polycrystalline Cu2O phase with (111) preferential growth. Raman scattering spectroscopic measurements conducted at room temperature also showed characteristic peaks of the pure Cu2O phase. The surface resistivity of the Cu2O nanorod films decreased from 15 142 to 685 Ω.cm with the addition of NaCl from 0 to 4 mmol and then exhibited an opposite trend with further addition of NaCl. The optical bandgap of the synthesized Cu2O nanorod films was observed as 1.88–2.36 eV, while the temperature-dependent activation energies of the Cu2O films were measured as about 0.14–0.21 eV. Scanning electron microscope morphologies demonstrated Cu2O nanorods as well as closely packed spherical grains with the alteration of NaCl concentration. The Cu2O phase of nanorods was found stable up to 230°C corroborating the optical bandgap results of the same. The film fabricated in presence of 4 mmol of NaCl showed the lowest resistivity and activation energy as well as comparatively uniform nanorod morphology. Our studies demonstrate that the nominal presence of NaCl electrolytes in the precursor solutions has a significant impact on the physical properties of Cu2O nanorod films which could be beneficial in optoelectronic research.

Sintering Mechanism and Enhanced Piezoelectric and Crystal Structural Properties of (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 Lead Free Ceramics

A lead-free piezoelectric ceramic, (1-x)Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 (hereafter (1-x)BZT-xBCT), was investigated for functional device applications. Lead-free piezoelectric materials with high piezoelectric charge coefficients and voltage coefficients are indispensable for functional industrial applications. Piezoelectric ceramic specimens tend to shrink in size during the sintering process without melting. This study focused on this phenomenon as a unique characteristic of piezoelectric ceramic materials, and derived the materials’ activation energies from this phenomenon, employing the Arrhenius relationship. Then the estimated activation energy was employed to determine the relationship between the piezoelectric properties and crystalline properties, while varying sintering temperature and chemical stoichiometric composition. Piezoelectric properties can change depending on the sintering temperature and process conditions. Crystalline properties and piezoelectric properties can be influenced by the sintering temperature and holding times. In this research, sintering temperature dependent structural and dielectric properties were investigated. (1-x)BZT-xBCT ceramics showed the highest piezoelectric coefficient of 470 pC/N. Sintering temperature dependent shrinkage rate and activation energy were estimated and calculated for the various sintering processes. In this research, two different activation energies for the shrinkage process were estimated.

Bioconvection Cross Diffusion Effects on MHD Flow of Nanofluids over Three Different Geometries with Melting

Currently, nanofluid is a hot area of interest for researchers. The nanofluid with bioconvection phenomenon attracted the researchers owing to its numerous applications in the field of nanotechnology, microbiology, nuclear science, heat storage devices, biosensors, biotechnology, hydrogen bomb, engine of motors, cancer treatment, the atomic reactor, cooling of devices, and in many more. This article presents the bioconvection cross-diffusion effects on the magnetohydrodynamic flow of nanofluids on three different geometries (cone, wedge, and plate) with mixed convection. The temperature-dependent thermal conductivity, thermal diffusivity, and Arrhenius activation energy applications are considered on the fluid flow with melting phenomenon. The flow is analyzed under thermal and solutal Robin’s conditions. The problem is formulated in the mathematical formulation of partial differential equations (PDEs). The similarity transformations are applied to diminish the governing nonlinear coupled boundary value problems into higher-order non-linear ordinary differential equations (ODEs). The resulting expressions/equation numerically tackled utilizing the famous bvp4c package by MATLAB for various interesting parameters. The results were physically and numerically calculated through graphics and tables for the velocity field, energy distribution, nanoparticles concentration, and microorganisms profile for numerous parameters. From the obtained results, we discern that the transfer of heat and mass coefficient is high over a plate and cone in the flow, respectively. The velocity profile is reduced via a larger magnetic parameter. Temperaturedependent thermal conductivity enhances the thermal field. Larger thermophoresis enhanced the concentration of nanoparticles. The microorganisms’ Biot number boosts the microorganism’s profile.

Model Catalysis with HOPG-Supported Pd Nanoparticles and Pd Foil: XPS, STM and C2H4 Hydrogenation

A surface science based approach was applied to model carbon supported Pd nanoparticle catalysts. Employing physical vapour deposition of Pd on sputtered surfaces of highly oriented pyrolytic graphite (HOPG), model catalysts were prepared that are well-suited for characterization by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Analysis of the HOPG substrate before and after ion-bombardment, and of Pd/HOPG before and after annealing, revealed the number of “nominal” HOPG defects (~ 1014 cm−2) as well as the nucleation density (~ 1012 cm−2) and structural characteristics of the Pd nanoparticles (mean size/height/distribution). Two model systems were stabilized by UHV annealing to 300 °C, with mean Pd particles sizes of 4.3 and 6.8 nm and size/height aspect ratio up to ~ 10. A UHV-compatible flow microreactor and gas chromatography were used to determine the catalytic performance of Pd/HOPG in ethylene (C2H4) hydrogenation up to 150 °C under atmospheric pressure, yielding temperature-dependent conversion values, turnover frequencies (TOFs) and activation energies. The performance of Pd nanocatalysts is compared to that of polycrystalline Pd foil and contrasted to Pt/HOPG and Pt foil, pointing to a beneficial effect of the metal/carbon phase boundary, reflected by up to 10 kJ mol−1 lower activation energies for supported nanoparticles.Graphical

Thermokinetic behavior of the Al2O3-PbO-B2O3 glasses

Thermokinetic behavior of the Al2O3-PbO-B2O3 glassy system was investigated by means of differential scanning calorimetry, X-ray diffraction analysis and Raman spectroscopy. The glass transition kinetics was described in terms of the Tool–Narayanaswamy–Moynihan model. The compositional evolution of the relaxation parameters was explained in terms of the structural changes and movements of the characteristic structural units detected by Raman spectroscopy. Crystal formation in the studied glassy matrices was investigated in dependence on composition and particle size. The crystal growth was suppressed by increasing particle size as well as by increasing Al2O3 content; formation of crystalline boron oxides was replaced by formation of mixed Al2O3/PbO oxides and Pb4B2O7 phase. The nucleation-growth Johnson-Mehl-Avrami model and the empirical autocatalytic model of Šesták and Berggren were used to describe the complex crystallization kinetics. The Avramov-Šesták concept of temperature dependent activation energy was successfully applied and tested on the real-life experimental data. The corresponding methodology was critically reviewed.

A probabilistic model for assessing uncertainty and sensitivity in the prediction of monochloramine loss in French river waters

Monochloramine (NH2Cl) is increasingly used as alternative disinfectant to free chlorine in industrial plants. After use in cooling systems, the waters are released to the environment and residual NH2Cl may be discharged into the receiving waters. As NH2Cl is suspected to exhibit toxicity towards aquatic organisms, a proper risk assessment of its occurrence in environmental waters is needed to prevent adverse effects on wildlife.For this purpose, a comprehensive model simulating monochloramine loss in natural riverine waters was developed. This model incorporates the following processes: (i) autodecomposition; (ii) reaction with nitrite and bromide; (iii) oxidation with Dissolved Organic Carbon (DOC); (iv) oxidation with organic fraction of Suspended Particulate Matter (SPM); (v) reactions in bottom sediments and (vi) volatilization. The model was also designed to conduct uncertainty and sensitivity analysis. It was tested on several French rivers submitted to discharges of monochloraminated effluents and on several seasonal conditions.Uncertainty analysis allowed evaluation of confidence intervals related to NH2Cl half-lives in natural waters. It was shown that simulation intervals are in good agreement with experimental data obtained on the same rivers. Sensitivity analysis using an EFAST variance decomposition approach allowed identification of the most influential parameters on half-life determination. It was shown that the kinetic rate describing rapid reaction of NH2Cl with DOC is by far the most sensitive parameter, demonstrating the predominance of such reactions in the loss process. Variables or parameters involved in temperature dependence (temperature and activation energy) can also significantly influence model results. To a lesser extent, wind velocity is the most sensitive parameter explaining uncertainty in the prediction of volatilization, with a high level of interactions with other parameters, showing that loss through volatilization can be essential in some specific conditions only. This study then identified the most important research priorities for improving the prediction of NH2Cl half-lives in natural rivers.

The Temperature Dependence of the Electrical Conductivity Activation Energy of the of Aqueous Electrolyte Solutions

The procedure for determining the activation energy of conductivity Еκ is analyzed depending on the temperature step ΔT. It is shown that with increasing ΔT, the error in the calculation of Eκ decreases, but the calculated value of Eκ decreases. In order not to lose the temperature dependence of the activation energy, it is necessary to choose the optimal value of Δt. In our opinion, this value should not exceed 5 – 10 °C. Taking into account the decrease in concentration with increasing temperature due to a decrease in density has virtually no effect on the accuracy of determining Eκ, provided that ΔT is 5 – 10 °C. It has been shown that in the temperature range 20 – 80 °C, the activation energy of conductivity decreases with increasing temperature. This decrease is due to the rupture of intermolecular hydrogen bonds of the solvent with increasing temperature. It was suggested that the movement of ions in an aqueous solution may be accompanied by the breaking of hydrogen bond of the solvent.

Magnetic, dielectric and structural properties of spinel ferrites synthesized by sol-gel method

Sol-gel procedure was taken into consideration to produce ferrite series with chemical formula MnYbyFe2-yO4 with y = 0.00 to 0.10 (step = 0.025). Structural, electrical and magnetic aspects of ytterbium (Yb) switched Mn-ferrites were the main focus. Every sample exhibited cubic phase spinel assembly. Exchange of ytterbium with iron in the system produced enlargement in coercivity while abridgment in remanence and saturation magnetization. Involvement of Yb ion in the ferrite assembly led to reduction of both real and imaginary constituents of permittivity. The ytterbium introduction in the lattice enhanced the value of impedance. The examination of hysteresis loop was done under the range of -2K to +2KOe. Temperature dependent resistivity, activation energy and drift mobility were carried out by two probe method. The characterization outcomes recommended that the compounds are appropriate for microwave absorption usages.

MLi2Ti6O14 (M = 2Na, Sr, Ba, Pb) Titanate Anodes for Lithium-Ion Capacitors (LICs)

Presence of shared edge, particularly of shared face, decreases the stability of ionic structures, for e.g., the least number of [TiO₆] shared edges (two) makes rutile (hcp) the most stable TiO₂ polymorph (Pauling’s IIIrd rule) [1]. Further, on insertion of (one or three) Li into spinel LiTi₂O₄ (ccp) or Li-substituted defect-spinel Li₄Ti₅O₁₂ (LTO), Li in 8a [LiO₄] sites migrate along with incoming Li to vacant 16c [LiO₆] sites, effectively avoiding face sharing of [TiO₆]-[TiO₆], [LiO₆]-[TiO₆] or [LiO₄]-[TiO₆] polyhedra in the intermediate states. This is unlike the face shared polyhedra that form mid-way during lithium insertion in case of rutile (hcp), brookite (hcp/ccp) or anatase (ccp) [2]. A unique zero-strain two-phase separation occurs favourably at a 1.5 V flat Ti(IV)/Ti(III) redox voltage vs Li, which is far above the deposition potential of lithium. This makes LTO a safe, dendrite-free, high-power, and long-life anode that is widely used commercially (Altair Nano, Toshiba SCiB, Yinlong) as an alternative to graphite. LTO is also reported (Hydro Quebec) to cycle over 30000 times vs LiFePO₄ while retaining 90% capacity.Along these lines, orthorhombic Cmca MLi₂Ti₆O₁₄ (MLTO) (M = 2Na, Sr, Ba, Pb) [3-5] prepared by rapid combustion-synthesis exhibit similar voltage (1.3-1.45 V) and capacity (100-160 mAh/g, upto 4 Li uptake). The first reported compound in this family, BaLi₂Ti₆O₁₄, had a high ionic conductivity (10-3 S/cm, 300ᵒC) and was found by serendipity during attempts to stabilize - a high-temperature type-III superionic Ramsdellite phase (MnO₂) of Li₂Ti₃O₇ - by addition of Ba [6]. Ramsdellite crystallizes in a rutile-type arrangement of 2X1 [TiO₆] polyhedras and reversibly inserts 2.24 Li [7]. Lithium diffusivity - migration pathways, their temperature dependent activation energies and diffusion coefficient - in MLTO was probed using a combination of methods involving bond valence site energy (BVSE) analysis, AC bulk-conductivity analysis, and electrochemistry versus Li was demonstrated. Further, motivated by Amatucci’s pioneering work on high power LTO/Activated Carbon (AC) asymmetric lithium-ion capacitors (LIC) showing electrochemical performance between high-energy battery and high-power capacitors, we employed MLTO electrodes in LICs for the first time. MLTOs were first loaded with lithium (pre-discharged) before assembling them in MLTOs/AC LIC hybrids. AC cathode adsorbs PF6 - ions rapidly in a capacitor-like sloped profile (40 mAh/g) at a higher voltage, while MLTOs (de)intercalate Li (100 mAh/g, 1-2 V) at Ti-redox potential.

Sub-Arrhenius diffusion in a classical system: Binary colloidal mixture in an external potential

In the transport processes in many physical systems, the temperature dependence of diffusivity is assumed to be exhibit Arrhenius behavior, i.e., a linear relationship log(D)∝1∕T . When extended to lower temperatures, deviations are observed in many physical systems. The phenomenological description of these deviations identifies them as sub-Arrhenius and super-Arrhenius regimes based on the concave or convex nature of log(D)∝1∕T curve and the activation energy becomes temperature dependent. In general, super-Arrhenius behavior is observed in classical systems such as supercooled liquids where correlated motions play an important role in the dynamical behavior of the system, whereas sub-Arrhenius behavior is proposed to be intimately related to quantum tunneling effect of penetration of an energy barrier along the reaction path as in the case of chemical reactions. In this article, we show that a purely classical system, such as binary colloidal mixture under an external repulsive potential, can undergo sub-Arrhenius diffusion. The depletion interactions between the repulsive potential barrier and larger particles in the presence of the smaller particles contribute to the temperature dependence of activation energy which in turn lead to the sub-Arrhenius diffusion of larger particles in the mixture.