Temperature Dependence Of Diffusivity Research Articles

Fabrication and characterization of LuAG: Er ceramics with high optical transmission

Highly transparent ceramics based on LuAG with erbium content ranging from 1 to 50 at% were synthesized from powders prepared via chemical precipitation in an aqueous solution. The impact of hot isostatic pressing on the optical properties of these ceramics was investigated. It was demonstrated that employing hot isostatic pressing enhances the optical transmittance of LuAG:Er ceramics. The influence of erbium concentration on the average grain size of the ceramics was also examined. Additionally, temperature-dependent thermal diffusivity profiles of LuAG:Er ceramics as a function of erbium content were analyzed. Erbium concentrations yielding the highest luminescence intensity in spectral ranges around ∼1.5–1.6 μm and ∼2.7 μm were determined.

Multiscale, mechanistic modeling of irradiation-enhanced silver diffusion in TRISO particles

Tristructural isotropic (TRISO) particles are under consideration for use in several proposed advanced nuclear reactor concepts. The silicon carbide (SiC) layer in TRISO acts as a barrier to prevent the release of the fission products. However, despite remarkable retention, silver (Ag) release has been observed from intact particles, which requires investigation since the Ag isotope (110m Ag) has a long half-life. Previous work focused on developing a multiscale, mechanistic model for Ag diffusion accounting for temperature and microstructure effect and has been successfully validated. In this work, we expand the previous model to account for irradiation-enhanced Ag diffusivity in SiC and improve its accuracy over a wider grain size and temperature ranges relevant for advanced reactor conditions. A temperature, grain size, and flux dependent diffusivity is therefore derived using the mesoscale code MARMOT and implemented in the fuel performance code BISON. The irradiation-enhanced Ag diffusivity in SiC is compared against experimental data and validated using BISON against Ag release measurements from the Advanced Gas Reactor Fuel Development and Qualification Program (AGR-1 and AGR-2). Herein, we quantify the impact of SiC grain size, irradiation, and temperature on Ag release. In agreement with previous studies, we find accounting for SiC grain size improves agreement between BISON predictions and experimental observations for most cases. We also find that accounting for irradiation improves agreement for cases where Ag release was underestimated, but the impact was less significant than accounting for microstructure.

Regression modeling of Bödewadt slip flow dynamics involving Reiner-Rivlin nanofluid based on a modified Buongiorno approach

Regression models are useful in analyzing rotational flows as they enable accurate predictions of wall shear and heat transfer coefficient. In addition, Bödewadt flow is of paramount importance in fluid dynamics of rotating systems such as turbomachinery and geophysical flows. Moreover, nanofluid’s enhanced heat transfer properties can improve cooling efficiency in applications involving turbines and electronic systems. This study delves into the Bödewadt boundary layer flow of a Reiner-Rivlin fluid containing nanoparticles over a stationary porous disk under slip conditions. The two-phase Buongiorno model is employed, incorporating temperature-dependent diffusion coefficients for enhanced accuracy. To facilitate numerical simulations, the transport equations are converted into an ordinary differential system comprising four unknowns. In the present work, a highly reliable Keller-Box methodology is adopted which agrees very well with the MATLAB built-in program ‘bvp4c’. The computed 2-D and 3-D streamlines vividly capture the Bödewadt flow scenario with Reiner-Rivlin nanofluid. The principle aim to investigate the impact of non-Newtonian behaviour and slip on the flow pattern, while also examining the behavior of temperature/concentration field for nanoparticle working fluids. As thermophoretic diffusion increases, the thermal boundary layer thickens considerably, leading to a notable decrease in the cooling rate of the disk. In contrast, Brownian diffusion has only a minimal impact on the heat transport. In addition, wall suction effect is observed to significantly boost the disk’s cooling rate, though at the expanse of increasing skin friction coefficients. This study introduces linear and quadratic regression models designed to precisely predict both the surface drag and disk cooling rate, which are crucial factors in engineering processes.

In-situ measurement of hydrogen isotope behavior in high temperature LBE: Diffusivity, permeability, and solubility

The Lead-Bismuth Fast Reactor (LBR) emerges as a promising concept due to its superior neutron economy, chemical stability, and thermal properties. From the nuclear safety standpoint, the focus has predominantly been on the behavior of 210Po and other fission products, while the issue of tritium in LBRs has not been sufficiently addressed due to the inconvenience of tritium experiments. Formation of tritium/helium bubbles induces significant local stress and volume expansion, leading to hardening and embrittlement of structural materials, thus expediting their degradation through irradiation effects. Current understanding of tritium transport within liquid Lead-Bismuth Eutectic (LBE) remains incomplete. To bridge this gap, a novel device employing the "permeation pot" method has been developed for the first experimental quantification of diffusivity, permeability, and solubility of hydrogen isotopes in liquid LBE. Notably, hydrogen diffusivity in this medium is found to be three to four orders of magnitude greater than in conventional 316L stainless steel structural material. Furthermore, the temperature-dependence of diffusivity in liquid metals is minimal compared to solids, as indicated by the activation energy. Conversely, solubility in 316L significantly surpasses that in LBE by three to four orders of magnitude. This discrepancy accelerates the tritium release from LBE to structural material, leading to the failure of the structural material.

Optimizing Operando Electrochemical and X-Ray Diffraction Parameters for High-Resolution Measurements of Lithium-Based Battery Materials

Advances in lithium-based batteries depend on understanding the mechanisms behind electrode performance. Operando methods are very powerful and useful for decoupling thermodynamic and kinetic (e.g. diffusion) limitations, but impose challenges with data collection and analysis. Electrode composition changes as lithium is inserted or removed (according to the electrochemical conditions); composition resolution is defined by the current, (temperature-dependent) diffusion rate within the electrode, and the time to collect a diffraction pattern. Many material systems of interest require less than 1 atomic percent composition resolution to verify (or question) the expected crystalline phases, and separate composition gradients imposed by slow diffusion from the presence of solid solutions. Solid-solution ranges can be particularly challenging as the cell potential may change quickly over a very small composition range. Some advanced techniques use machine learning to optimize pattern collection time by comparing the measured diffraction pattern with references, and focusing on specific scattering angles to identify materials.1 Although powerful, this method is not well suited for materials with metastable or unidentified phases, e.g. metal alloys for advanced lithium-based batteries.Here we will describe a robust and low-cost platform for operando electrochemical and crystallographic measurements of lithium-based electrode materials. Electrode composition can be monitored at low to moderate rate electrochemical conditions using laboratory diffractometers and at high rates using some synchrotron-based diffractometers. Our test cell is based on Conflat-style vaccum flanges and a beryllium window;2 this design enables all standard two electrode electrochemical tests on e.g. lithium-based negative electrode materials with hermetic sealing and controlled pressure.Results from the electrochemical lithiation and delithiation of gold will be presented as a case study. Operando studies of lithium-gold reactivity are of interest since many lithium-gold phases have poorly defined unit cells and solid solution ranges,3 and gold electrodes are a common choice for in-situ / operando measurements in electron microscopes. A wide range of scattering angle is required to collect a sufficient number of peaks for unit cell indexing, which necessarily increases collection time and impacts composition resolution. We will discuss the influence of detector type and scan time (collection plus movement) on composition resolution as a function of electrochemical conditions (current, potential range, and temperature). Results from point, 1D, and 2D detectors on laboratory and synchrotron diffractometers will be provided, along with general strategies to optimize method resolution.

High-fidelity phase-field simulation of solid-state sintering enabled by Bayesian data assimilation using in situ electron tomography data

Experimental observation methods for understanding industrially important solid-state sintering are essential for the development of new materials and devices. To experimentally characterize solid-state sintering, the limitations posed by the complexity of target materials, experimental equipment, and observation conditions must be overcome. Therefore, hybrid techniques for predicting sintering behavior based on experimental datasets and physics-based simulation models are highly sought after. Herein, we propose a new technique for combining a physics-based model and experimental observation results from solid-state sintering using a nonsequential Bayesian data assimilation (DA) method. The proposed technique assimilates experimental data—obtained using in situ electron tomography/scanning transmission electron microscopy—into the corresponding phase-field (PF) model to enable high-fidelity PF simulations by estimating multiple material parameters included in the PF model. This study demonstrates the inverse estimation of seven parameters, including temperature-dependent diffusion coefficients, from the time-series information on the morphology of sintered nanoparticles observed in situ. The estimated parameters provide the high-fidelity PF simulation to capture the observed solid-state sintering of copper nanoparticles. Thus, this study contributes to the construction of digital twins for solid-state sintering based on DA-integrated PF simulations and in situ observation datasets and deepens our understanding of the sintering process.

Examining basic theorems and plane waves in the context of thermoelastic diffusion using a multi-phase-lag model with temperature dependence

This study employs a novel mathematical formulation of temperature-dependent thermoelastic diffusion with multi-phase delays (TDMT). The TDMT model, which is assumed, is obtained by converting the fundamental rules of Fourier’s and Fick’s laws into higher order time derivatives of the heat flow vector, the temperature gradient, diffusing mass flux, and the chemical potential gradient. Fundamental theorems such as energy, uniqueness, reciprocity theorems, and variational criterion are established using the fundamental equations for the assumed model TDMT. The reciprocity theorem is applied to a particular scenario by using instantaneous concentrated body forces, heat sources, chemical potential sources, and moving heat sources as examples. It is noted that both the variational criterion and these theorems depend on the field variables’ susceptibility as well as the fluctuations in the higher order temporal derivatives’ parameters. Additionally, the assumed model’s two-dimensional (2D) plane wave propagation is described. Three longitudinal waves are identified: the longitudinal (P) wave, the thermal (T) wave, the chemical potential (CP) wave, and the linked transverse (SV) wave. Wave properties (phase velocity and attenuation coefficient) are calculated numerically and shown visually. A few special examples are also investigated and compared with the established findings. The framework for additional research into basic issues in thermoelastic continua under various physical field variables is provided by this work. Numerous applications in material science, geomechanics, soil dynamics, and the electronic sector can be made of the current findings.

Stability analysis of a multilayer diffusion-reaction heat transfer problem with a very large number of layers

The stability of thermal conduction problems is of much practical interest in the context of Li-ion batteries, power electronic devices, chemical reactors and other engineering systems. While past work in predicting the thermal stability of a multilayer diffusion-reaction problem has been carried out using pole analysis or by determining imaginary eigenvalues of the problem, such techniques are impractical when the number of layers in the problem is very large. This work presents an exact analysis of the stability of a multilayer diffusion-reaction problem, in which the number of layers may be very large. Using homogenization and Heaviside functions based representation of thermophysical properties and parameters, it is shown that the stability of such a system may be easily predicted by computing the determinant of a matrix containing contributions from each layer/interface. Results from the present work are shown to correctly reduce to results from past work for pure-diffusion and single-layer special cases, as well as agree well with numerical simulations. Threshold for thermal stability of a representative Li-ion battery pack containing 1000 Li-ion cells is determined. It is shown that stability of the system is governed by a balance between temperature-dependent heat generation, diffusion and heat removal from the boundary. A key result of practical interest is that even small improvement in thermal diffusivity of Li-ion cells may greatly help reduce the risk of thermal instability. Additionally, practical guidelines for the maximum permissible operating time of a battery pack to avoid thermal runaway are discussed. This work advances the theoretical understanding of multilayer diffusion-reaction problems, and helps understand the thermal stability of Li-ion battery packs containing a very large number of cells, which is very difficult to analyze using traditional techniques.

Using Brownian model to study the effect of temperature on diffusion coefficient

This study employs molecular simulation techniques, particularly the Brownian motion model, to investigate the influence of temperature on diffusion coefficients. Leveraging Einsteins relationship for calculating diffusion coefficients and a one-dimensional random walk model, we systematically explore the impact of simulation direction, particle quantity, and simulation duration on diffusion behavior. The research extends its scope to three-dimensional Brownian motion simulations, offering insights into the stochastic motion of particles in a fluid. The primary objective is to analyze the relationship between temperature and diffusion coefficients. Through rigorous linear regression analysis, a significant and strong linear association is identified, demonstrating that an increase in temperature correlates with an increase in the diffusion coefficient. The research not only contributes to the fundamental understanding of molecular motion but also provides practical recommendations for simulation parameters, especially in resource-constrained computational environments. The study acknowledges certain limitations in the current Brownian motion algorithm and proposes avenues for future research to enhance computational efficiency and precision. This abstract encapsulates the key methodologies, findings, and implications of the research, laying the foundation for a comprehensive exploration of temperature-dependent diffusion coefficients in molecular systems.

Universal thermal profiles with polynomial thermal diffusivity in a channel flow

Fluids used in heat transfer applications range in a wide spectrum of Prandtl numbers. An aspect that is commonly neglected is the influence of variable thermal diffusivity in turbulent heat transfer. A mathematical model was developed in the past few years [1, 2] to address the influence of the variable thermal diffusivity on the turbulent heat transfer. In this work we explore the influence of the friction Reynolds number Reτ, the molecular Prandtl number Pr and the coefficients λi+ of the temperature dependent thermal diffusivity, up to the fourth-order, to the Universal Profiles in a channel flow. This choice minimizes the influence of the boundary and initial conditions. The numerical simulations in the limit of constant thermal diffusivity are validated against literature DNS data. The results show that the influence of the friction Reynolds number is limited, while high molecular Prandtl numbers increase the fluctuating thermal diffusivity heat flux. The factor that influences the solution the most is the thermal diffusivity coefficients, showing that, in certain conditions, the fluctuating thermal diffusivity heat flux is non-negligible even for low Prandtl numbers. The results show that the terms introduced by the model proposed in [1, 2] are non-negligible when the thermal diffusivity in the boundary layer doubles compared to its bulk value. It is suggested that the model presented in [1, 2] could be particularly suitable in cryogenic applications.

A reactive molecular dynamics model for uranium/hydrogen containing systems.

Uranium-based materials are valuable assets in the energy, medical, and military industries. However, understanding their sensitivity to hydrogen embrittlement is particularly challenging due to the toxicity of uranium and the computationally expensive nature of quantum-based methods generally required to study such processes. In this regard, we have developed a Chebyshev Interaction Model for Efficient Simulation (ChIMES) that can be employed to compute energies and forces of U and UH3 bulk structures with vacancies and hydrogen interstitials with accuracy similar to that of Density Functional Theory (DFT) while yielding linear scaling and orders of magnitude improvement in computational efficiency. We show that the bulk structural parameters, uranium and hydrogen vacancy formation energies, and diffusion barriers predicted by the ChIMES potential are in strong agreement with the reference DFT data. We then use ChIMES to conduct molecular dynamics simulations of the temperature-dependent diffusion of a hydrogen interstitial and determine the corresponding diffusion activation energy. Our model has particular significance in studies of actinides and other high-Z materials, where there is a strong need for computationally efficient methods to bridge length and time scales between experiments and quantum theory.

Carbon solute drag effect on the growth of carbon supersaturated bainitic ferrite: Modeling and experimental validations

The carbon partitioning and lengthening rate of bainitic ferrite (αb) are excellent experimental parameters to estimate our level of understanding of the mechanism of bainitic transformation from a continuum perspective and our ability to capture it in analytical expressions. For Fe-C alloys and relatively simple steels the classical Zener-Hillert theory captures the bainitic transformation rather well but mispredicts the level of carbon in solution in the bainite and overestimates the lengthening rates for transformations at lower temperatures. To address this issue, this paper presents a new thermo-kinetic model based on the Zener-Hillert theory and the Gibbs energy balance concept to simulate the lengthening behavior of αb in the Fe-C and low alloyed steels. The model incorporates the effect of the temperature dependent carbon diffusion within the migrating interface via a temperature dependent ferrite/austenite interfacial energy and a temperature dependent diffusion coefficient but does not impose local equilibrium across the interface. The good agreement between the model predictions and nine sets of published experiments indicates that both the carbon supersaturation in αb and the slower lengthening rate are caused by carbon diffusion within the migrating interface. It is found that the degree of carbon supersaturation in αb increases significantly with decreasing temperature. Consequently, the enhanced carbon solute drag effect, resulting from carbon diffusion within the interface, strongly retards the lengthening rates of αb at lower temperatures. Transformation strain is shown to have a modest effect on the lengthening rates but to lower the degree of carbon supersaturation.

Diffusion and magnetization of metal adatoms on single-layer molybdenum disulfide at elevated temperatures

The present work models temperature-dependent (500−1300K) diffusion dynamics of Ag, Au, and Cu adatoms on MoS2 as well as electronic and magnetic properties of adatom (Ag, Au, and Cu)/MoS2 systems. Modeling is done by means of ab initio molecular dynamics (AIMD) simulations that account for van der Waals corrections and electronic spin degrees of freedom in the framework of density functional theory. It is found that Ag and Au adatoms exhibit super-diffusive motion on MoS2 at all temperatures, while Cu adatoms follow a random walk pattern of uncorrelated surface jumps. The observed behavior is consistent with AIMD-calculated effective migration barriers Ea (EaAg=190±50meV, EaAu=67±7meV, and EaCu=300±100meV) and can be understood on the basis of the considerably flatter potential energy landscapes encountered by Ag and Au adatoms on the MoS2 surface (corrugation of the order of tens of meV), as compared to Cu adatoms (corrugation >100meV). Moreover, evaluation of the electronic and magnetic properties of AIMD configurations suggest that Ag, Au, and Cu monomer adsorption induces semimetallic features in at least one spin channel of the adatom/MoS2 electronic structure at elevated temperatures. The overall results presented herein may provide insights into fabricating 2D-material-based heterostructure devices beyond graphene.

Comparison of Two Methods for Measuring the Temperature Dependence of H2 Permeation Parameters in Nitrile Butadiene Rubber Polymer Composites Blended with Fillers: The Volumetric Analysis Method and the Differential Pressure Method.

Hydrogen uptake/diffusivity in nitrile butadiene rubber (NBR) blended with carbon black (CB) and silica fillers was measured with a volumetric analysis method in the 258-323 K temperature range. The temperature-dependent H2 diffusivity was obtained by assuming constant solubility with temperature variations. The logarithmic diffusivity decreased linearly with increasing reciprocal temperature. The diffusion activation energies were calculated with the Arrhenius equation. The activation energies for NBR blended with high-abrasion furnace CB and silica fillers increased linearly with increasing filler content. For NBR blended with medium thermal CB filler, the activation energy decreased with increasing filler content. The activation energy filler dependency is similar to the glass transition temperature filler dependency, as determined with dynamic mechanical analysis. Additionally, the activation energy was compared with that obtained by the differential pressure method through permeability temperature dependence. The same activation energy between diffusion and permeation in the range of 33-39 kJ/mol was obtained, supporting the temperature-independent H2 solubility and H2 physisorption in polymer composites.

Triply periodic minimal surfaces based topology optimization for the hydrodynamic and convective heat transfer

Triply periodic minimal surfaces (TPMS), possessing diverse and crucial properties for thermal convection analysis, hold significant promise for topology optimization in convective and hydrodynamic systems. This study aims to develop an innovative topology optimization method based on TPMS for channel shape design. We focus on maximizing heat dissipation and mass flux while maintaining a constant mean curvature. The channel structures undergo free evolution during the optimization process, resulting in efficient and intricate geometries based on the TPMS assumption. To incorporate TPMS properties, we modify the original energy formulation, which comprises kinetic energy, thermal energy, and Ginzburg–Landau energy. The governing system encompasses the phase field model, the Darcy–Stokes model, and the reaction–diffusion heat transfer model. The hydrodynamic response within the phase change structure is computed by solving the transient Darcy–Stokes equation augmented with a temperature-dependent diffusion term. To achieve second-order temporal and spatial accuracy, we employ the Crank–Nicolson method for the time scale and the central difference method for the spatial scale. Through the utilization of the Lagrange multiplier method, we establish the unconditional decrease of the discretized original energy. This implies that the proposed scheme can utilize a large time step. To verify the robustness of our proposed method, we conduct several numerical tests from both qualitative and quantitative perspectives. The results demonstrate the effectiveness of our method in enhancing heat and mass transfer capabilities.

An Overview of the mechanism-based thermomechanical fatigue method (DTMF) in the design of automotive components

The DTMF damage Parameter described in the paper is the generalization of the creep fatigue parameter (DCF) proposed by Riedel, which quantifies the amount of damage produced by a non-isothermal loading cycle. The entire design methodology is outlined in the text, starting with the calibration of Chaboche's viscoplastic model and then the determination of the thermomechanical fatigue (TMF) parameters. Chaboche is generally a good choice for its ability to describe well both kinematic and isotropic hardening behaviors, also enabling stress relaxation and strain rate dependency to be considered. The DTMF method is based on the fracture mechanics concept of cyclic crack tip opening displacement (ΔCTOD) where the effective stress range takes the crack closure effect into account. This method is typically used to describe the thermomechanical low cycle fatigue behavior of cast irons, cast steels, stainless steels, Inconel, HiSiMo and nickel-based alloys. These materials are used in components that need to withstand high temperatures (higher than half of the melting point) in service as exhaust manifolds, cylinder heads, valves, turbochargers and disk brakes. Three failure mechanisms are detailed here: oxidation, creep and fatigue. Oxidation is a complex phenomenon that may occur when the material is hot under tensile in-phase loading or hot under compressive out-of-phase loading. Creep is a time and temperature dependent diffusion process which is incorporated into the DTMF parameter as a multiplicative factor. In this context fatigue life is defined as the number of cycles to propagate an existent microcrack up to an arbitrary size that is defined on a case-by-case basis.

Temperature dependence of hydrogen diffusion in reservoir rocks: implications for hydrogen geologic storage

This study presents a comprehensive experimental dataset on the temperature-dependent diffusion of hydrogen (H2) in reservoir rocks. The results demonstrate that H2 diffuses through reservoir rocks up to 100 times faster than methane (CH4).

Interfacial Degradation Processes in Solid-State Batteries during High Temperature Processing and the Mitigation Strategies

Garnet-type solid electrolytes have been extensively investigated in recent times as potential candidates for solid-state batteries. Among them, garnets with nominal composition Li7La3Zr2O12(LLZO) have received particular attention due to their high Li-ion conductivity (10-3 Scm-1) at room temperature and chemical stability against metallic lithium besides possessing a large electrochemical window >5V.[1] Despite of striking properties, LLZO suffers from several challenges such as interfacial instability with cathodes, e.g., LCO, during high temperature processing, resulting in a huge interface resistance, which is one of the fundamental reasons for the failure of solid-state batteries based on LLZO.[2-4] So far, the high interfacial impedance has been related to LLZO|LCO interface decomposition occurring due to diffusion of Co across the cathode-electrolyte interface. Herein, we investigated the hypothesis that interfacial degradation originate from the incorporation of Co into the LLZO lattice. The solubility limit of Co is determined to be 0.16 per formula unit, whilst the concentrations beyond promote phase transition (cubic LLZO-to-tetragonal LLZO). We investigated in detail the temperature-dependent Co diffusion into LLZO and concluded that detrimental cross diffusion could take place at any relevant process condition. Besides, the optimal protective Al2O3 coating thickness for relevant temperatures was studied, which allowed to create a process diagram to provide mitigation strategies towards enabling stable LCO|LLZO interface in all-solid-state batteries. Keywords: Solid-state batteries, Interfaces, cross diffusion, interfacial degradation AcknowledgementsD.R. acknowledges financial support by the Austrian Federal Ministry for Digital and Economic Affairs, the National Foundation for Research, Technology and Development and the Christian Doppler Research Association (Christian Doppler Laboratory for Solid-State Batteries). D.R. and J. F. acknowledges financial support by the Austrian Science Fund (FWF) in the frame of the project InterBatt (P 31437). D.K. acknowledges funding by the European Union’s Horizon 2020 Research and Innovation Programme (Grant No. 823717, project “ESTEEM3”) and by the Zukunftsfond Steiermark.Reference[1] Murugan, R., Thangadurai, V. and Weppner, W., 2007. Fast Lithium Ion Conduction in Garnet‐type Li7La3Zr2O12. Angew. Chemie. Int. Edt., 46(41), 7778-7781.[2] Chen, X., Xie, J., Zhao, X., & Zhu, T., 2021. Electrochemical Compatibility of Solid‐State Electrolytes with Cathodes and Anodes for All‐Solid‐State Lithium Batteries: A Review. Adv. Energy Sustain. Res., 2(5), 2000101.[3] Sakuda, A., Hayashi, A., Tatsumisago, M., 2010. Interfacial Observation Between LiCoO2 Electrode and Li2S-P2S5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy. Chem. Mater., 22(3), 949–956.[4] Ihrig, M., Kuo, L.Y., Lobe, S., Laptev, A.M., Lin, C.A., Tu, C.H., Ye, R., Kaghazchi, P., Cressa, L., Eswara, S. and Lin, S.K., 2023. Thermal Recovery of the Electrochemically Degraded LiCoO2/Li7La3Zr2O12: Al, Ta Interface in an All-Solid-State Lithium Battery. ACS Appl. Mater. Interfaces.

Unveiling the transport properties of protic ionic liquids: Lithium ion dynamics modulated by the anion fluorine reservoir

Protic ionic liquids (PILs) show great potential as electrolyte components for energy storage devices. A comprehensive understanding of their transport properties must be achieved to optimize the design of safer and efficient electrolytes. This study focuses on a series of PILs based on the DBUH+ cation (protonated 1,8-diazabicyclo[5,4,0]‑undec-7-ene superbase) and three anions derived from strong acids: TFO− (triflate), IM14− (perfluorobutyl-trifluoromethylsulfonylimide) and TFSI− (bis(trifluoromethylsulfonyl)imide). Neat PILs and PILs doped with LiTFO, LiIM14, and LiTFSI were studied using temperature-dependent NMR diffusion and relaxation techniques. The ionicity of these systems was also evaluated. Results revealed that the dynamic behaviour of lithium ions, as well as ionicity, strongly depend on the structural features of the anions, particularly in the case of IM14−, whose main feature is the uneven distribution of the fluorinated sidegroups. The 19F relaxation rates in IM14− provide insights into the rotational reorientation of that anion. DBUH-IM14 exhibited diffusion coefficients lower than the expected ones on the basis of its viscosity, likely due to fluorophilic intermolecular interactions involving the fluorinated terminal groups. The presence of Li+ in the DBUH-IM14 electrolyte led to unexpected and relatively faster translational mobility of Li+ ions, resulting in a higher lithium apparent transference number. However, the trends observed in ionicity indicate a more complex interplay between intermolecular interactions and ion correlations. While DBUH-TFSI showed minimal effect of Li+ addition, DBUH-TFO and DBUH-IM14 exhibited a significant decrease in ionicity, possibly attributed to strong interactions between ions.

Modeling of CO Oxidation by Diffusion of Oxygen Atoms in Ceria-Zirconia Particulates in a Three-Way Catalyst Particle Membrane Filter

In order to design a microporous membrane filter comprising Three-way Catalyst (TWC) particles with a size distribution of 1 to 2 microns, isothermal CO oxidation experiments and numerical simulations were conducted to investigate the transport of oxygen atoms within primary Ceria-Zirconia (CZ) particulates. These spherical TWC particles were fabricated through the agglomeration of primary CZ and alumina particulates, incorporating Pd and Rh catalysts. By comparing experimental CO2 emissions with simulation results over time, a temperature-dependent diffusion coefficient was determined. The simulation results reveal that the effective distance of oxygen atom transport within CZ particulates, heterogeneously distributed in the spherical TWC particle, is limited to approximately 100 nm from the surface of agglomerated spherical TWC particles within a temperature range of 175 to 225°C.