Chemical Diffusion Coefficient Research Articles

Ti3C2Tx Filled in EMIMBF4 Semi-Solid Polymer Electrolytes for the Zinc-Metal Battery.

Zinc-ion batteries (ZIBs) are promising candidates for safe energy storage applications. However, undesirable parasitic reactions such as dendrite growth, gas evaluation, anode corrosion, and structural damage to the cathode under an acidic microenvironment severely affected cell performance. To resolve these issues, an MXene entrapped in an ionic liquid semi-solid gel polymer electrolyte (GPE) composite was explored. The molecular-level mixing of poly(vinylidene fluoride-co-hexafluoropropylene) (PVHF), zinc trifluoromethanesulfonate (Zn(OTF)2), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) ionic liquid, and Ti3C2Tx MXene provided a controlled Zn2+ shuttle toward the anode/cathode. Ti3C2Tx/EMIBF4/Zn(OTF)2/PVHF exhibited a breaking strength of 0.36 MPa with an associated extension of 23%. The Zn//Ti3C2Tx/EMIBF4/Zn(OTF)2/PVHF//Zn symmetric cell with continuous zinc plating/stripping exhibited excellent Zn2+ ion mobility toward the anode and cathode without undesired reactions. This was confirmed by post-mortem analysis after a symmetric cell compatibility test. The as-prepared GPE with a Na3V2(PO4)3 (NVP) cathode exhibited a high chemical diffusion coefficient of 1.14 × 10-7. It also showed an outstanding reversible capacity of 89 mAh g-1 at C/10 with an average discharge plateau voltage of 1.45 V, cycle durability, and controlled self-discharge. These results suggested that the Zn2+ ions in the Ti3C2Tx/EMIBF4/Zn(OTF)2/PVHF composite are reversibly labile in the anode and cathode directions.

Analytical Form of the Fluorescence Correlation Spectroscopy Autocorrelation Function in Chemically Reactive Systems.

Fluorescence correlation spectroscopy (FCS) applied to chemically reactive systems provides information about chemical reaction equilibrium constants and diffusion coefficients of reactants. These physical quantities are determined from the FCS-measured autocorrelation function, G(t), as a function of time, t. In most of the studied cases, the analytical form of G(t) is well-known for reactions that are much faster than the diffusion time of reactants across the focal volume probed by FCS or when they are much slower than the diffusion time. Here, we develop an analytical form of G(t) for reactions occurring at an intermediate time scale comparable to the diffusion time. G(t) depends on the reaction rates in such reactions. We focus on reversibly binding a fluorescently labeled small molecule to a macromolecule in a diluted solution in thermodynamic equilibrium. Our approach allows the analysis of FCS data over a wide range of diffusion coefficients, reaction rate constants, and brightness levels of fluorescent labels. Our G(t) is valid even when the fluorescent label changes its brightness upon binding. The easy-to-implement analytical form of the autocorrelation function greatly helps experimentalists study chemical reactions, determining the equilibrium constants of reactions and the reaction rates.

Anodes for Li‐ion batteries based on titanium fluorides

AbstractThe work is devoted to a comparative study of the electrochemical behavior and molecular level transformations in TiF3 and TiOF2 electrodes of Li‐ion batteries at charge‐discharge processes. Based on analysis of the electrode voltage profiles, we propose possible redox reactions which occur with the change of Ti oxidizing state. According to these models, titanium trifluoride has a reversible capacity of 600 mAh/g, TiOF2 of 395 mAh/g. It has been shown that titanium oxyfluoride is characterized by a long cycle life while specific capacity of the titanium trifluoride rapidly degrades. The degradation of TiF3 is associated with a temporal molecular ordering and decrease in the chemical activity of titanium and lithium fluoride formed during the reversible introduction of lithium. The related effect lies under the superreversibility phenomenon in TiOF2 electrodes (Coulomb efficiency more than 100%). The dependences of the equilibrium voltage and chemical diffusion coefficient of Li on the concentration of Li were determined from GITT analysis.

Angular momentum and chemical transport by azimuthal magnetorotational instability in radiative stellar interiors

Context. The transport of angular momentum and chemical elements within evolving stars remains poorly understood. Asteroseismic and spectroscopic observations of low-mass main sequence stars and red giants reveal that their radiative cores rotate orders of magnitude slower than classical predictions from stellar evolution models and that the abundances of their surface light elements are too small. Magnetohydrodynamic (MHD) turbulence is considered a primary mechanism to enhance the transport in radiative stellar interiors but its efficiency is still largely uncertain. Aims. We explore the transport of angular momentum and chemical elements due to azimuthal magnetorotational instability, one of the dominant instabilities expected in differentially rotating radiative stellar interiors. Methods. We employed 3D MHD direct numerical simulations in a spherical shell of unstratified and stably stratified flows under the Boussinesq approximation. The background differential rotation was maintained by a volumetric body force. We examined the transport of chemical elements using a passive scalar. Results. We provide evidence of magnetorotational instability for purely azimuthal magnetic fields in the parameter regime expected from local and global linear stability analyses. Without stratification and when the Reynolds number Re and the background azimuthal field strength are large enough, we observed dynamo action driven by the instability at values of the magnetic Prandtl number Pm in the range 0.6 − 1, which is the smallest ever reported in a global setup. When considering stable stratification at Pm = 1, the turbulence is transitional and becomes less homogeneous and isotropic upon increasing buoyancy effects. The transport of angular momentum occurs radially outward and is dominated by the Maxwell stresses when stratification is large enough. We find that the turbulent viscosity decreases when buoyancy effects strengthen and scales with the square root of the ratio of the reference rotation rate Ωa to the Brunt–Väisälä frequency N. The chemical turbulent diffusion coefficient scales with stratification similarly to the turbulent viscosity, but is lower in amplitude so that the transport of chemicals is slower than the one of angular momentum, in agreement with recent stellar evolution models of low-mass stars. Conclusions. We show that the transport induced by azimuthal magnetorotational instability scales somewhat slowly with stratification and may enforce rigid rotations of red giant cores on a timescale of a few thousand years. In agreement with recent stellar evolution models of low-mass stars, the instability transports chemical elements less efficiently than angular momentum.

Intercalation in Li-ion batteries: thermodynamics and its relation to non-ideal solid-state diffusion

Intercalation is the key phenomenon taking place in lithium-ion batteries: while its thermodynamics sets the equilibrium voltage of active materials, solid-state diffusion of intercalated lithium determines the rate at which the battery can operate. This study revisits the thermodynamics of intercalation by treating the active material as a binary mixture of filled and empty sites, thus relating the equilibrium potential to the chemical potential difference of intercalated lithium. By setting a reference to unitary activity at half state-of-lithiation, the non-ideal behaviour of the active material is quantified via a revisited form of the thermodynamic enhancement factor, revealing that common solid-solution cathode materials as LiNi x Mn y Co1-x-y O2, LiNi0.8Co0.15Al0.05O2, and LiCoO2 show strong super-ideal behaviour. The latter is related to the thermodynamic enhancement of the diffusion coefficient of intercalated lithium. A comprehensive overview of the functional forms of Li diffusion flux according to linear irreversible thermodynamics is provided and related to the chemical diffusion coefficient obtained by conventional characterisation techniques. A literature analysis made on solid-solution cathode active materials reveals that while the chemical diffusion coefficient varies significantly with state-of-lithiation, there exists a convenient functional form of diffusion flux according to linear irreversible thermodynamics that enables a fairly stable diffusion coefficient with state-of-lithiation. This has clear benefits from both modelling and experimental viewpoints and potentially sheds light on the mechanistic fundamentals of solid-state diffusion.

Accurate Calculation of Solid-State Li+ Diffusion Coefficient and Kinetic Activation Energies for an Artificial Graphite Anode

The slow electrochemical reaction kinetics of artificial graphite is one of the limiting factors for safety of lithium-ion batteries, especially the lack of systematic research on activation energies of various kinetic processes. In this work, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic intermittent titration technique (GITT) were used to investigate key kinetic parameters of artificial graphite such as solid-state Li+ diffusion coefficient (D Li+) and activation energy. The results reveal the evaluation of the chemical diffusion coefficient of same material is independent of the technique and shows a similar value, with D Li+ ranging from 10−11 to 10−13 cm2·s−1. The activation energies measured by EIS and GITT for solid-state Li+ diffusion in graphite at 50% depth of discharge are 74.5 kJ·mol−1 and 66.8 kJ·mol−1, which are in the same order of magnitude as the activation energies of charge transfer resistance (59.5 kJ·mol−1), electrode/electrolyte interface membrane impedance (56.1 kJ·mol−1), and ohmic impedance (6.6 kJ·mol−1). It demonstrates that the solid-state Li+ diffusion, interface charge transfer process, and Li+ transmission through SEI membrane are significantly affected by temperature. This work provides a reliable parameter basis for establishing more accurate thermal-electrochemical coupling models and designing safer battery thermal management systems for lithium-ion batteries.

Oxygen exchange kinetics on La0.6Sr0.4FeO3−δ

Equilibrium properties and kinetic properties of strontium-doped lanthanum ferrite La0.6Sr0.4FeO3−δ were studied by an original approach involving two methods: oxygen partial pressure relaxation (with determination of equilibrium exchange rate R0 and a chemical diffusion coefficient in oxide: Dchem) and a quasi-equilibrium oxygen release [with construction of equilibrium isothermal diagram “lg pO2 vs. (3 − δ) vs. T”]. Activation energies determined for R0 and Dchem were 120 ± 20 and 30 ± 2 kJ/mol, respectively. It was shown that the linear free-energy relationship—between activation energy of the reaction rate constant and standard Gibbs energy of the reaction—is of the Brønsted–Evans–Polanyi type.

Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.References Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta 354, 136771 (2020).Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage 56, 105955 (2022).Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films 519, 3373–3377 (2011).

The Effects of Small Amounts of Cobalt in LiNi1-XCoxO2 on Lithium Diffusion

Lithium-ion batteries with Co-free Ni-rich cathodes have attracted interest due to lower cost and supply chain issues compared to cobalt-containing cathodes1. However, cobalt is thought to provide some benefits in cycling stability and rate performance. In this work, cobalt substitution for nickel in the positive electrode material LiNi1-xCoxO2 at 0 ≤ x ≤ 0.10 is systematically investigated to determine the impact of Co and material synthesis conditions on Li diffusivity, measured using the Atlung Method for Intercalant Diffusion (AMID)2,3 in coin cells vs Li metal negative electrodes. Cobalt was found to have no impact on Li diffusivity in the intermediate voltage range (4.2 V to 3.7 V), while cation mixing (%Ni in Li layer) was found to have a strong correlation to slow Li diffusivity. At high voltage (4.3 V to 4.2 V), 0 to 10% cobalt incrementally suppresses the H2-H3 phase transition4,5 enabling significantly faster lithium diffusion. Cation mixing can be minimized through synthesis conditions, improving Li diffusivity for the low and intermediate voltage regions, without using Co. In summary, with optimal positive electrode material synthesis conditions and limiting cell upper cutoff voltage to 4.2 V, Co-free Ni-rich materials can be made with similar rate performance as 10% Cobalt-containing materials. Additionally, cobalt was found to have minimal impact on the following material properties: crystallinity of LiNi1-xCoxO2, surface impurities, particle size, and electronic conductivity. Cobalt substituted for nickel from 0% to 10% was found to decrease first cycle discharge capacity in the voltage range between 3.0 V and 4.3 V and improve capacity retention in coin cell cycling vs Li metal negative electrodes. The capacity retention improvement is most likely due to the suppression of the H2-H3 phase transition as Co is added5. Figure 1. (a), (b) shows %Ni in Li layer vs Cobalt content, obtained from powder XRD Rietveld refinement from a series of LiNi1-xCoxO2 materials. (a), (b) were synthesized under two different O2 flow velocities, both at 700oC for 20 hours, with a Li:TM ratio of 1.02:1. (c), (d) Show the lithium chemical diffusion coefficient vs cell voltage for the materials from (a), (b), respectively, measured using the Atlung Method for Intercalant Diffusion (AMID), in coin cells at 30oC. The protocol consists of 2C to C/160-rate discharge steps per voltage interval (0.1V), with OCV relaxation in between discharge steps. Figure 1

Research on mathematical algorithm to determine the chemical diffusion coefficient of hydrogen in CaZrO3 based proton conductor at high temperature

To study hydrogen diffusion properties is of importance in design of new proton conductors. In the past, the chemical diffusion coefficient of hydrogen in proton conductor was usually obtained by the manual calculation method that largely depends on judgment ability of researchers, so calculation accuracy is difficult to control. To solve this problem, a mathematical algorithm and C language computer program were designed to calculate the chemical diffusion coefficient based on Fick's second law and Romberg numerical integral, in which the chemical diffusion coefficient is obtained by fitting measured electrical resistance relaxation curve based on. In addition, the algorithm can be extended to calculate the chemical diffusion coefficient in some special cases with incomplete measured electrical resistance relaxation curve or inaccurate measured values of R0 and R∞ based on modified algorithm of R0 and R∞, what cannot be handled by the manual calculation method. The chemical diffusion coefficient of self-synthesized Yb doped CaZrO3 proton conductor were calculated by using the algorithm and compared with the manual calculation method. The results show that the algorithm has the advantages of high precision and powerful computing function. The new algorithm is potential to be widely applied to the calculation of the chemical diffusion coefficient for hydrogen in proton conductors to replace the manual calculation method.

Electrochemical Characteristics of Li‐Ion Battery Anodes Based on Titanium Oxyfluoride

The properties of titanium oxyfluoride‐based anodes are studied by galvanostatic cycling and galvanostatic intermittent titration technique in a TiOF2—Li half‐cells. This anode material is shown to have a high degradation resistance and a specific gravimetric capacity comparable to that of carbon and Li4Ti5O12. The chemical diffusion coefficient of Li+ in TiOF2 varies by two orders of magnitude in the range from 2.3 × 10−13 to 2.5 × 10−15 cm2 s−1 depending on the degree of lithiation and the direction of charge or discharge process. The electrode electrical resistance changes with cycling and its value is always lower in the lithiated state than in the delithiated state. The phenomenon of superreversibility inherent in this material has been studied. This phenomenon consists in the excess of the discharge capacity (Li extraction) over the charge capacity (Li insertion), that is, the Coulomb efficiency (CE) exceeds 100%. In the first few tens of cycles, the phenomenon is due to the extraction of excess lithium, which was previously stored in the electrode during the first cycle. On subsequent cycles, the CE stabilizes at a level above or below 100%, depending on the ratio between the charge and discharge currents, and is not related to the accumulation or spending of Li.

Enhancing oxygen exchange kinetics of solid oxide fuel cell cathode: Unleashing the potential of higher order Ruddlesden-Popper phase surface modification

Tailoring the electrode surface represents a promising strategy to enhance electrochemical performance while preserving base material integrity. Achieving appropriate surface coverage with catalytic active oxide material is critical for efficient oxygen transport at the triple phase boundary (TPB). To further explore this approach, the perovskite structure La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) is decorated with a higher order Ruddlesden-Popper phase Pr4Ni3O10+δ (PNO). This combination is being investigated using electrical conductivity relaxation (ECR) technique to study the oxygen exchange kinetics. Samples with varying surface coverage of PNO are examined in a temperature range of 650 °C–850 °C, with a step change in pO2 between 0.1 atm and 0.21 atm. The chemical diffusion coefficient, Dchem, remains invariant across all the samples, however, the surface exchange coefficient, kchem, varies with the surface coverage of PNO. Notably, the coated sample with a PNO loading content of 0.28 mg cm−2, referred to as PNO5, demonstrates a significant enhancement of nearly two orders of magnitude in kchem compared to bare LSCF at 650 °C. This substantial improvement is ascribed to the increased active sites of ORR within the TPB region and the facilitated electron access through tunneling from LSCF to the coated phase. Pulse isotopic exchange (PIE) measurements on the fractionated powders confirm the fast surface exchange kinetics of PNO. Such remarkable oxygen exchange characteristics encourage the use of PNO, along with LSCF, as potential candidates for SOFC cathodes.

Pr‐ and Co‐substitution in rare earth nickelates: Application as SOEC air electrodes

AbstractIn this work, fundamental material properties of compounds in the system (La,Pr)2(Ni,Co)O4+δ as well as their performance as air electrodes in solid oxide electrolysis cells were investigated. Nickelates co‐doped with Pr and Co were characterized on a material basis by means of X‐ray diffraction and thermogravimetry. Conductivity and conductivity relaxation measurements were performed in order to obtain the electronic conductivity as well as the chemical surface exchange coefficient and the chemical diffusion coefficient of oxygen as a function of temperature and oxygen partial pressure. These parameters can be regarded as the most essential properties at the material level required to assess the suitability of mixed ionic‐electronic conducting ceramics for application as air electrode in solid oxide cells. The electrode performance of the materials was then tested on fuel electrode‐supported button cells at 800°C. The electrodes were applied by screen‐printing and the effect of varying the Pr‐content and Co‐content of the electrode powder was investigated. Cell tests were performed by means of current‐voltage measurements in electrolysis mode. While no significant impact of Pr‐doping on the investigated material properties was observed, the electrode performance of Pr‐containing materials was significantly better than for the Pr‐free compound, which has been discussed in detail.

Dynamics and diffusion limit of traveling waves in a two-species chemotactic model with logarithmic sensitivity

This paper discusses the traveling wave analysis of the two-species chemotaxis model with logarithmic sensitivity, which describes diverse biological phenomena such as the initiation of angiogenesis using reinforced random walks theory and the chemotactic response of two interacting species to a chemical stimulus. The objectives are to quantitatively establish the existence of traveling wave solutions only for the parameters in certain parameter regimes. Moreover, we incorporate recent results and discuss many other aspects of traveling wave solutions such as asymptotic decay rates and convergence as the chemical diffusion coefficient goes to zero. The main techniques are analyzed and the analytical results are reviewed graphically.

Synergistic effects of A-site deficiency and anion doping on Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 cathode for H2O electrolysis and CO2 electrolysis

In this work, a strategy of A-site deficiency and F-doping was proposed to prepare Pr0.4Sr0.55Ni0.2Fe0.7Mo0.1F0.1O2.9 (PSNFMF) cathode. Compared with the reduced Pr0.4Sr0.6Ni0.2Fe0.7Mo0.1O3 (R-PSNFM), the reduced PSNFMF facilitate the exsolution reaction and generate more oxygen vacancies. Moreover, at 800 °C, the chemical oxygen surface exchange coefficient (kchem) of R-PSNFMF is 4.31 × 10−4 cm s−1, 21.8% higher than the value of 3.54 × 10−4 cm s−1 for R-PSNFM, and the oxygen chemical bulk diffusion coefficient (Dchem) of R-PSNFMF is 34.21 × 10−5 cm2 s−1, 24.3% higher than the value of 27.53 × 10−5 cm2 s−1 for R-PSNFM, suggesting faster oxygen transport kinetics are obtained for R-PSNFMF. Meanwhile, the synergistic effect of A-site deficiency and anion doping can also promote the electrolysis of H2O and CO2. For H2O electrolysis, the current density of R-PSNFMF based cell at 0.4 V (vs. OCV) is −0.75 A cm−2, 31.6% higher than the value of −0.56 A cm−2 for R-PSNFM based cell. And for CO2 electrolysis in harsh condition at 800 °C, the current density of R-PSNFMF based cell at 0.4 V (vs. OCV) is −0.43 A cm−2, 38.7% higher than the value of −0.31 A cm−2 for R-PSNFM based cell.

Layered Titanium Sulfide Cathode for All‐Solid‐State Magnesium Batteries

AbstractMagnesium solid‐state batteries attract significant attention as a future mean of energy storage. Here we present the first cathode study of an inorganic all‐solid‐state magnesium battery using a magnesium metal anode, a nanocomposite electrolyte Mg(BH4)2 ⋅ 1.6NH3‐MgO (75 wt %), and a layered titanium disulfide (TiS2) as cathode active material. The structural transformations of TiS2 particles with different sizes are investigated at different stages of battery life. Reversible Mg2+ intercalation occurs via three structurally distinct phases of MgxTiS2, identified by powder X‐ray diffraction. Magnesium intercalates initially on octahedral sites and at higher depth of discharge on tetrahedral sites in the interlayers of TiS2, which leads to an expansion initially mainly along the c‐axis and later along both the a‐ and c‐axes. A maximum discharge capacity of 172 mAh g−1 (Δx=0.36 in MgxTiS2) is observed for smaller TiS2 particles. Parasitic reactions could be reduced by decreasing the cut‐off voltage by a constant current constant voltage cycling procedure. The chemical diffusion coefficient of the entire cell is found from galvanostatic intermittent titration technique experiments to be in the order of 10−15 to 10−19 cm2 s−1.

Doping effects of alkaline earth element on oxygen reduction property of high-entropy perovskite cathode for solid oxide fuel cells

The nearly infinite arrangement and combination of multiple components in high entropy materials provide a huge platform for the modification and performance regulation of new materials. It is an attractive idea to introduce the concept of high entropy into material design and improve its electrochemical performance through component regulation. In this paper, cobalt-based high-entropy perovskite oxides with different alkaline earth metal contents were successfully synthesized. The phase structure, direct current conductivity, oxygen mobility characters and electrochemical properties of these materials are studied. It is found that with the continuous substitution of rare earth elements by alkaline earth elements in high-entropy materials, the content of oxygen vacancies increases and the electrochemical performance is enhanced. The chemical oxygen diffusion coefficient (Dchem) and surface exchange coefficient (Kchem) of the high-entropy oxide La0.2Pr0.2Ba0.2Sr0.2Ca0.2CoO3 are 2.8 × 10−6 cm2 s−1 and 9.1 × 10−3 cm s−1 at 700 °C, respectively. The electrochemical impedance spectroscopy measurement results show that La0.2Pr0.2Ba0.2Sr0.2Ca0.2CoO3 has the minimum polarization resistance, which is 0.03 Ω cm2 at 700 °C in air. The anode-supported fuel cell with the high entropy oxide reaches a peak power density of 792 mW cm−2 at 700 °C and exhibits attractive long-term stability and excellent CO2 resistant properties.

Oxygen exchange and transport properties of the first-order Ruddlesden-Popper phase La2Ni0.9Co0.1O4+δ

The rare earth nickelate La2Ni0.9Co0.1O4+δ (LNCO) was synthesized via the citrate/EDTA method. X-ray powder diffraction confirmed that the material is single-phase and crystallizes in the orthorhombic K2NiF4-type structure. In-situ dc-conductivity and conductivity relaxation measurements on a bar-shaped sample were applied to determine the electronic conductivity as well as the chemical surface exchange coefficient and chemical diffusion coefficient of oxygen from 600 °C to 850 °C and 0.01 ≤ pO2 / bar ≤ 0.1. The results indicate that substitution of nickel with cobalt in La2Ni0.9Co0.1O4+δ leads to significantly higher values of the surface exchange coefficient compared to La2NiO4+δ, while the electronic conductivity is somewhat reduced. The oxygen non-stoichiometry of LNCO was studied by thermogravimetry in the same temperature and oxygen partial pressure range. The measured thermal expansion coefficients of LNCO fit well with those of common solid electrolytes such as GDC and YSZ. Self-diffusion coefficients of oxygen and ionic conductivities were calculated from the experimentally determined diffusivities and the thermodynamic factor of oxygen by using the Nernst-Einstein relation. The results indicate that LNCO offers an attractive option for application as air electrode in solid oxide cells.

The inhibiting effect of Re-rich layer on the interdiffusion between NiAl and Ni3Al-based superalloy and its degradation

A NiAl alloy/ Ni3Al-based superalloy diffusion couple with an electroplated NiRe layer was prepared. High-temperature interdiffusion performance of the diffusion couple was analyzed at 1100 ℃ under argon atmosphere and compared with that of the blank group without NiRe layer. A Re-based diffusion barrier formed during the diffusion. The microstructural instability of the superalloy was found to be alleviated by the Re-based diffusion barrier, and the detailed microstructure of the diffusion barrier was identified to be Re-rich σ phases and Mo-rich α phase detected by TEM. The chemical diffusion coefficient of Al was reduced by about two orders of magnitude with the modification of the Re-based diffusion barrier. A microstructural degradation of the Re-based barrier layer was observed after high-temperature diffusion of 300 h, which can be attributed to the internal diffusion of Mo.

Comparison of Lithium Diffusion Coefficient Measurements in Tellurium Electrodes via Different Electrochemical Techniques

Both thin (55 μm) composite and thick (350 μm) all active material battery porous electrodes were prepared for estimating the diffusion coefficient of Li+ ( in tellurium (Te) during electrochemical lithiation. Galvanostatic intermittent titration technique (GITT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) were applied to quantify the chemical lithium solid-state diffusion coefficient within the Te active material in the electrodes. Multiple methods of GITT and EIS were assessed. For the composite Te electrodes, the was on the order of 10−11 cm2 s−1 from both CV and GITT methods, but 10−9 cm2 s−1 from EIS. For the thick tellurium electrodes, both GITT and EIS resulted in lithium diffusion coefficient estimates in the range of 10−11–10−12 cm2 s−1. The general trend across all methods that quantified the diffusion coefficient as a function of lithiation of tellurium was that the decreased rapidly when the Te material was initially lithiated. The at the phase transition voltage plateau (∼1.7 V, vs Li/Li+, where both Te and Li2Te were expected) had the lowest while the both before and after the plateau was generally higher. Among all the electrochemical measurements of the modified GITT method with modelling the relaxation region resulted in relatively low scatter in the data, provided values as a function of lithiation, and was well suited to thick electrodes with a flat discharge plateau as was the case herein.