Bulk Diffusion Coefficient Research Articles

Bulk-to-surface segregation measurements of Cu and S in a Ni-Cu(S) ternary system with Auger electron spectroscopy

The bulk-to-surface segregation measurement of Cu and S in Ni0.813Cu0.187 alloy crystals was investigated by using Auger electron spectroscopy (AES) to monitor the surface concentration of Cu and S during the constant temperature segregation measurement. The constant temperatures were carried out in the temperature range 770 K to 860 K at a 30 K interval. The results show that the initially both Cu and S segregated to the surface and the first segregation rate of Cu is higher than that of S. Once the Cu reached the maximum surface coverage, it started to desegregate until Cu was replaced by S. The segregation measured profile data with a constant temperature heating method were fitted by the modified Fick’s model extracted the bulk diffusion coefficient as DCu in Ni = 5.8 × 10−14exp(−160.1 kJ/RT) m2/s, DS in Ni = 1.2 × 10−2exp(–222.1 kJ/RT) m2/s, The segregation parameters obtained in this work were compared well with experimental data values obtained from published elsewhere.

Current fluctuations in the symmetric zero-range process below and at critical density.

Characterizing current fluctuations in a steady state is of fundamental interest and has attracted considerable attention in the recent past. However, the bulk of the studies are limited to systems that either do not exhibit a phase transition or are far from criticality. Here we consider a symmetric zero-range process on a ring that is known to show a phase transition in the steady state. We analytically calculate two density-dependent transport coefficients, namely, the bulk-diffusion coefficient and the particle mobility, that characterize the first two cumulants of the time-integrated current. We show that on the hydrodynamic scale, away from the critical point, the variance of the time-integrated current in the steady state grows with time t as sqrt[t] and t at short and long times, respectively. Moreover, we find an expression of the full scaling function for the variance of the time-integrated current and thereby the amplitude of the temporal growth of the current fluctuations. At the critical point, using a scaling theory, we find that, while the above-mentioned long-time scaling of the variance of the cumulative current continues to hold, the short-time behavior is anomalous in that the growth exponent is larger than one-half and varies continuously with the model parameters.

Medium-entropy strategy to inhibit the surface Sr segregation and enhance the stability of Sr2Fe1.5Mo0.5O6-δ cathode for CO2 direct electrolysis

Solid oxide electrolysis cell (SOEC) is a promising solid-state electrochemical device that can convert CO2 into CO with high efficiency. However, the poor catalytic activity and Sr segregation of the cathode diminish the electrode reaction, hindering the large-scale application. Herein, a medium-entropy strategy is proposed to suppress the Sr enrichment while enhancing the catalytic activity for CO2. The surface Sr content on Sr2Fe1.2Ni0.1Cu0.1Co0.1Mo0.5O6-δ (SFNCCM) is significantly reduced after the Ni, Cu, and Co co-doping at Fe-site. Moreover, the oxygen surface exchange and bulk diffusion coefficient at 800 °C for SFNCCM oxide reach 2.42 × 10−4 cm2 s−1 and 2.28 × 10−5 cm2 s−1, which are 1.35 and 1.39 times higher than parent Sr2Fe1.5Mo0.5O6-δ(SFM) oxide. At 850 °C and 1.5 V, single with SFNCCM-Sm0.2Ce0.8O6-δ(SDC) composite exhibits a current density of 2.22 A cm−2 with good stability for up to 100 h. The results suggest that the medium-entropy strategy is a promising method to inhibit Sr segregation and enhance the performance of CO2 direct electrolysis.

Efficient and Stable In Situ Self‐Assembled Air Electrodes for Reversible Protonic Ceramic Electrochemical Cells

AbstractReversible protonic ceramic electrochemical cells (R‐PCECs) have garnered significant attention owing to their proficiency in efficiently converting and storing energy. The performance of R‐PCECs is largely limited by the activity and durability of oxygen reduction/evolution reactions in air electrodes. Herein, an Nb and Y doped cobalt‐based double perovskite of PrBaCo1.8Nb0.1Y0.1O5+δ (denoted as PBCNY) is reported. The perovskite is however in situ assembled into a deficient‐PrBa1−xCo1.8Nb0.1−xY0.1−xO5+δ parental phase and a Ba2YNbO6 secondary phase during operation, accordingly demonstrating a low area‐specific resistance of 0.24 Ω cm2 at 600 °C. The high activity is attributed to the enhancement in oxygen vacancy concentration, oxygen surface exchange, and bulk diffusion coefficient, confirmed by X‐ray photoelectron spectroscopy and electrical conductivity relaxation. At 700 °C, when the PBCNY cathode is applied as air electrodes for R‐PCECs, a peak power density of 1.99 W cm−2 and a current density of −5.20 A cm−2 (at 1.3 V) are achieved in fuel cell (FC) mode, and electrolysis (EL) mode with appropriate Faradaic efficiencies. Furthermore, R‐PCECs with PBCNY air electrodes display promising operational stability in FC mode (over 100 h), EL mode (over 200 h), and reversible cyclic testing (29 cycles for 120 h).

Dynamic fluctuations of current and mass in nonequilibrium mass transport processes

We study steady-state dynamic fluctuations of current and mass in several variants of random average processes on a ring of L sites. These processes violate detailed balance in the bulk and have nontrivial spatial structures: their steady states are not described by the Boltzmann–Gibbs distribution and can have nonzero spatial correlations. Using a microscopic approach, we exactly calculate the second cumulants, or the variance, ⟨Qi2(T)⟩c and ⟨Qsub2(l,T)⟩c , of cumulative (time-integrated) currents up to time T across the ith bond and across a subsystem of size l (summed over bonds in the subsystem), respectively. We also calculate the (two-point) dynamic correlation function of the subsystem mass. In particular, we show that, for large L≫1 , the second cumulant ⟨Qi2(T)⟩c of the cumulative current up to time T across the ith bond grows linearly as ⟨Qi2⟩c∼T for initial times T∼O(1) , subdiffusively as ⟨Qi2⟩c∼T1/2 for intermediate times 1≪T≪L2 , and then again linearly as ⟨Qi2⟩c∼T for long times T≫L2 . The scaled cumulant liml→∞,T→∞⟨Qsub2(l,T)⟩c/2lT of current across the subsystem of size l and up to time T converges to the density-dependent particle mobility χ(ρ) when the large subsystem-size limit is taken first, followed by the large-time limit; when the limits are reversed, it simply vanishes. Remarkably, regardless of the dynamical rules, the scaled current cumulant D⟨Qi2(T)⟩c/2χL≡W(y) as a function of scaled time y=DT/L2 can be expressed in terms of a universal scaling function W(y) , where D is the bulk-diffusion coefficient; interestingly, the intermediate-time subdiffusive and long-time diffusive growths can be connected through a single scaling function W(y) . The power spectra for current and mass are also exactly characterized by the respective scaling functions. Furthermore, we provide a microscopic derivation of equilibrium-like Green–Kubo and Einstein relations that connect the steady-state current fluctuations to an ‘operational’ mobility (i.e. the response to an external force field) and mass fluctuation, respectively.

Time-dependent gas dynamic diffusion process in shale matrix: model development and numerical analysis

Gas diffusion is a pivotal process during shale gas recovery, which is determined by diffusion coefficient to a large extent. In previous studies, the gas diffusion coefficient is generally assumed as a constant. However, increasing experiments prove that the diffusion coefficient of shale gas is strongly time-dependent. Therefore, to perfect the theory of shale gas diffusion, this paper proposes a time-dependent diffusion model for shale gas, which incorporates time-dependent gas diffusion coefficient, composing of the bulk diffusion coefficient for free gas in organic and inorganic pores, as well as the surface diffusion coefficient for adsorbed gas in organic pores. To validate the accuracy of the new theory, we calibrate the theoretical results against experimental data, and the results show that they have strong correlation, and the time-dependent diffusion model is superior to classical model. Finally, the numerical analysis of gas dynamic diffusion process in shale matrix is conducted. The results show that at the end of diffusion, a large amounts of shale gas remain trapped in the matrix core due to the attenuation of gas diffusion coefficient. In addition, neglecting the time-dependent nature of gas diffusion in shale matrix leads to a significant overestimation of gas production.

Non-Dispersive Extraction of Chromium(VI) by Cyphos IL102/Solvesso 100 Using the Pseudo-Emulsion-Based Strip Dispersion Membrane Operation.

The removal of chromium(VI) from an acidic (HCl) medium through non-dispersive extraction with strip dispersion (NDXSD) was investigated using a microporous PVDF membrane support in a permeation cell. The ionic liquid Cyphos IL102 (phosphonium salt) in Solvesso 100 was used as an organic phase. In NDXSD, the stripping phase (NaOH) is dispersed in the organic phase on the cell side with an impeller stirrer adequate to form a strip dispersion. This pseudo-emulsion phase (organic + strip solutions) provides a constant supply of the Cyphos IL102/Solvesso 100 to the membrane phase. Various hydrodynamic and chemical parameters, such as variation in the feed and pseudo-emulsion stirring speeds, HCl and Cr(VI) concentrations in the feed phase, and carrier concentration, were investigated. Results indicated that the best chromium(VI) transport was obtained under the following conditions: feed and pseudo-emulsion stirring speeds of 1000 min-1 and 600 min-1, respectively; an HCl concentration in the feed phase of 0.1 M; a chromium concentration of 0.01 g/L in the same phase; and carrier concentration in the organic phase in the 2-5-10% v/v range. From the experimental data, several mass transfer coefficients were estimated: a bulk diffusion coefficient of 3.1·10-7 cm2/s and a diffusion coefficient of 6.1·10-8 cm2/s in the membrane phase and mass transfer coefficients in the feed (5.7·10-3 cm/s) and membrane phases (2.9·10-6 cm/s). The performance of the present system against other ionic liquids and the presence of base metals in the feed phase were investigated.

Accelerating bulk proton transfer in Sr2Fe1.5Mo0.5O6-δ perovskite oxide for efficient oxygen electrode in protonic ceramic electrolysis cells

Protonic ceramic electrolysis cells (PCECs) have attracted significant attention as a promising technology for green hydrogen production and conversion. However, traditional PCECs oxygen electrodes exhibit poor electrochemical performance because of their limited hydration ability and lack of intrinsic protonic conductivity. In this study, a W-doped perovskite oxide, Sr2Fe1.5Mo0.4W0.1O6-δ (SFMW), with a strong hydration capacity and an accelerated proton mobility, was designed to serve as the oxygen electrode in PCECs. The results indicate that W doping enhances the concentration of oxygen vacancies in Sr2Fe1.5Mo0.5O6-δ (SFM) and facilitates the adsorption of H2O onto the oxygen electrode, thereby significantly accelerating proton mobility. The bulk diffusion coefficient of protons (DH) in SFMW, estimated through electrical conductivity relaxation measurement, can reach up to 2.86 × 10−5 cm∙s−1 at 750 °C, which is significantly higher than that of SFM (7.96 × 10−6 cm∙s−1). Consequently, SFMW exhibited impressive electrochemical performance, as evidenced by its lower polarization resistance (0.072 Ω⋅cm2, 700 °C in air) and higher current density (945 mA/cm2 with a voltage of 1.3 V at 650 °C) in PCECs. These results suggest that accelerating bulk proton transfer by W doping is highly feasible and holds great potential for the development of oxygen electrodes for high-activity PCECs.

Time-dependent properties of run-and-tumble particles. II. Current fluctuations.

We investigate steady-state current fluctuations in two models of hardcore run-and-tumble particles (RTPs) on a periodic one-dimensional lattice of L sites, for arbitrary tumbling rate γ=τ_{p}^{-1} and density ρ; model I consists of standard hardcore RTPs, while model II is an analytically tractable variant of model I, called a long-ranged lattice gas (LLG). We show that, in the limit of L large, the fluctuation of cumulative current Q_{i}(T,L) across the ith bond in a time interval T≫1/D grows first subdiffusively and then diffusively (linearly) with T: 〈Q_{i}^{2}〉∼T^{α} with α=1/2 for 1/D≪T≪L^{2}/D and α=1 for T≫L^{2}/D, where D(ρ,γ) is the collective- or bulk-diffusion coefficient; at small times T≪1/D, exponent α depends on the details. Remarkably, regardless of the model details, the scaled bond-current fluctuations D〈Q_{i}^{2}(T,L)〉/2χL≡W(y) as a function of scaled variable y=DT/L^{2} collapse onto a universal scaling curve W(y), where χ(ρ,γ) is the collective particle mobility. In the limit of small density and tumbling rate, ρ,γ→0, with ψ=ρ/γ fixed, there exists a scaling law: The scaled mobility γ^{a}χ(ρ,γ)/χ^{(0)}≡H(ψ) as a function of ψ collapses onto a scaling curve H(ψ), where a=1 and 2 in models I and II, respectively, and χ^{(0)} is the mobility in the limiting case of a symmetric simple exclusion process; notably, the scaling function H(ψ) is model dependent. For model II (LLG), we calculate exactly, within a truncation scheme, both the scaling functions, W(y) and H(ψ). We also calculate spatial correlation functions for the current and compare our theory with simulation results of model I; for both models, the correlation functions decay exponentially, with correlation length ξ∼τ_{p}^{1/2} diverging with persistence time τ_{p}≫1. Overall, our theory is in excellent agreement with simulations and complements the prior findings [T. Chakraborty and P. Pradhan, Phys. Rev. E 109, 024124 (2024)1539-375510.1103/PhysRevE.109.024124].

Construction of high performance fuel electrode in solid oxide electrolysis cells by tuning the surface oxygen defect to promote electrochemical reduction of CO2

B-site Co–Fe-based perovskite materials have shown potential as ceramic cathodes in solid oxide electrolysis cells (SOECs) for direct CO2 electrolysis. Nevertheless, their operational utilization is constrained by insufficient catalytic activity and durability in pure CO2. In this work, F− doping and A-site deficiency strategies are proposed and La0.6Sr0.4Co0.2Fe0.8O3 (LSCF), F-doped La0.6Sr0.4Co0.2Fe0.8F0.1O2.9 (LSCFF) and A-site deficiency combined with F-doped (La0.6Sr0.4)0.95Co0.2Fe0.8F0.1O2.9 (LSCFF95) are prepared as cathode materials for CO2 electrolysis. After doping with F−, the valence states of both Co and Fe elements decrease, while generating more oxygen vacancies. With the further introduction of A-site deficiency, the valence states further decrease, resulting in more oxygen vacancies. The enhancement of oxygen vacancies leads to an improvement in the oxygen surface exchange coefficient (kchem) and the bulk diffusion coefficient (Dchem) of LSCFF and LSCFF95 materials. At 800 °C, kchem of LSCFF and LSCFF95 reach 24.21 × 10−4 and 33.54 × 10−4 cm s−1, respectively, which are 51% and 110% higher than the value of 16.03 × 10−4 cm s−1 for LSCF. Meanwhile, the Dchem values of LSCFF and LSCFF95 are measured to be 37.52 × 10−5 and 47.81 × 10−5 cm2 s−1, respectively. These values are 49% and 90% higher than the value of 25.22 × 10−5 cm2 s−1 for LSCF. Consequently, F− doping and A-site deficiency significantly increase the electrochemical performance. For example, F− doping decreases the polarization resistance (Rp) value of the SOEC with LSCF cathode from 0.19 Ω cm2 to 0.13 Ω cm2 at 800 °C. Furthermore, when the A-site deficiency is introduced, the Rp value is further reduced to 0.11 Ω cm2. Therefore, the SOEC with the LSCFF95 cathode exhibits excellent performance. Specifically, it has demonstrated an impressively high current density of 2.85 A cm−2 at 800 °C and 1.5 V, and has exhibited exceptional durability over prolonged operation.

Time-dependent properties of run-and-tumble particles: Density relaxation.

We characterize collective diffusion of hardcore run-and-tumble particles (RTPs) by explicitly calculating the bulk-diffusion coefficient D(ρ,γ) for arbitrary density ρ and tumbling rate γ, in systems on a d-dimensional periodic lattice. We study two minimal models of RTPs: Model I is the standard version of hardcore RTPs introduced in [Phys. Rev. E 89, 012706 (2014)10.1103/PhysRevE.89.012706], whereas model II is a long-ranged lattice gas (LLG) with hardcore exclusion, an analytically tractable variant of model I. We calculate the bulk-diffusion coefficient analytically for model II and numerically for model I through an efficient Monte Carlo algorithm; notably, both models have qualitatively similar features. In the strong-persistence limit γ→0 (i.e., dimensionless ratio r_{0}γ/v→0), with v and r_{0} being the self-propulsion speed and particle diameter, respectively, the fascinating interplay between persistence and interaction is quantified in terms of two length scales: (i) persistence length l_{p}=v/γ and (ii) a "mean free path," being a measure of the average empty stretch or gap size in the hopping direction. We find that the bulk-diffusion coefficient varies as a power law in a wide range of density: D∝ρ^{-α}, with exponent α gradually crossing over from α=2 at high densities to α=0 at low densities. As a result, the density relaxation is governed by a nonlinear diffusion equationwith anomalous spatiotemporal scaling. In the thermodynamic limit, we show that the bulk-diffusion coefficient-for ρ,γ→0 with ρ/γ fixed-has a scaling form D(ρ,γ)=D^{(0)}F(ρav/γ), where a∼r_{0}^{d-1} is particle cross sectionand D^{(0)} is proportional to the diffusion coefficient of noninteracting particles; the scaling function F(ψ) is calculated analytically for model II (LLG) and numerically for model I. Our arguments are independent of dimensions and microscopic details.

On the role of defects in modelling approaches for thin film gas barrier coatings on polymer substrates: I. Model development

We present a method to model the gas permeation through silicon-oxide thin film coatings that are afflicted with nanoscale defects. With it, we are able to give an estimation of the diffusion coefficient in bulk by subtracting the influence of the defects. The model is based on data obtained from positron annihilation spectroscopy, which is processed to yield possible defect allocation patterns of the coatings. For a systematic evaluation of these patterns, a path through the coating is calculated and then subjected to in-depth analysis to evaluate the used approach as well as to interpret the results for insights on the permeation mechanisms. The model appears to function as intended and no unexpected behaviour is observed. The defect volume share is overestimated, which can be retraced to the underlying algorithm, and a correction method is applied to the resulting bulk diffusion coefficient. The model gives reasonable results both for oxygen and water vapor permeation. These results can be used in following works that build on the presented model.

Tailoring Ba0.5Sr0.5FeO3-δ cobalt-free perovskites with zinc as triple-conducting cathodes for protonic ceramic fuel cells

Developing triple-conducting cathode is an available way to enhancing the electrochemical performance of protonic ceramic fuel cells (PCFCs). Here we report a systematical investigation on the performance of cobalt-free perovskites Ba0.5Sr0.5Fe1-xZnxO3-δ (x = 0, 0.1, and 0.2; BSF, BSFZ0.1, and BSFZ0.2) as triple-conducting cathodes for PCFCs. Zn doping improves the hydration capacity, oxygen vacancy concentration, surface exchange coefficient, and bulk diffusion coefficient of BSFZx (x = 0.1 and 0.2) as compared to the bare BSF. Theory calculations show that Zn doping benefits the oxygen vacancy formation, which is conducive to the promotion of cathodic oxygen reduction reaction (ORR). Among materials investigated, the BSFZ0.2 perovskite possesses an abundance of oxygen vacancies, strong hydration capacity and exceptional triple conductivity (H+/O2−/e−), and thus showing the lowest polarization resistance (Rp) of 0.328 Ω cm2 at 700 °C under wet air. At 700 °C, the cell reaches a maximum power density of 497 mW cm−2 in H2 using BSFZ0.2-30 wt% BaZr0.4Ce0.4Y0.15Zn0.05O3-δ (BZCYZ) composite cathode based on 25-μm-thick BZCYZ electrolyte, and there is no obvious deterioration in performance after operation for 100 h. The rate-limiting steps of ORR on BSFZ0.2-BZCYZ composite cathode are determined to be the surface oxygen incorporated into lattice reaction processes. These findings demonstrate that the proposed BSFZ0.2 holds great potential as a cobalt-free triple-conducting cathode for PCFCs.

Tuning the ORR catalytic activity of LaFeO3-δ-based perovskite cathode for solid oxide fuel cells by doping with alkaline-earth metal elements

Co-based perovskite cathodes have demonstrated impressive catalytic activity for oxygen reduction reaction (ORR) at intermediate temperatures. However, these cathodes face the challenges such as high cost and thermal expansion coefficient (TEC) mismatch. On the other hand, Fe-based perovskite oxides like LaFeO3 exhibit more stable properties and lower TEC, but their ORR activity is not as remarkable as that of Co-based cathodes. In this study, La3+ at the A-site of LaFeO3 was substituted by aliovalent alkaline-earth metal cations. The research findings reveal that the doping of alkaline-earth metal ions induces the formation of structural defects and alters the valence state of Fe. This leads to an increase in the conductivity and oxygen vacancy concentration, which are critical for ORR kinetics in both H–SOFC and O–SOFC. Among the various dopants, Sr doped LaFeO3 (LSrF) exhibits the most outstanding ORR catalytic activity. This can be attributed to its highest total conductivity, O2− conductivity, oxygen surface exchange coefficient, and oxygen bulk diffusion coefficient. At 700 °C, single cell with LSrF cathode achieves peak power densities of 0.781 and 0.894 W cm−2, for O2--conducting solid oxide fuel cell (SOFC) and H+-conducting SOFC, respectively. These performances are essentially twice that of single cell with LaFeO3 cathode. The findings of this study provide valuable insights into doping strategies for Fe-based perovskite cathodes and contribute to the advancement of IT-SOFC cathode research.

Empirical and Numerical Modelling of Gas–Gas Diffusion for Binary Hydrogen–Methane Systems at Underground Gas Storage Conditions

The physical process in which a substance moves from a location with a higher concentration to a location with a lower concentration is known as molecular diffusion. It plays a crucial role during the mixing process between different gases in porous media. Due to the petrophysical properties of the porous medium, the diffusion process occurs slower than in bulk, and the overall process is also affected by thermodynamic conditions. The complexity of measuring gas–gas diffusion in porous media at increased pressure and temperature resulted in significant gaps in data availability for modelling this process. Therefore, correlations for ambient conditions and simplified diffusivity models have been used for modelling purposes. In this study, correlations in dependency of petrophysical and thermodynamic properties were developed based on more than 30 measurements of the molecular diffusion of the binary system hydrogen–methane in gas storage rock samples at typical subsurface conditions. It allows reproducing the laboratory observations by evaluating the bulk diffusion coefficient and the tortuosity factor with relative errors of less than 50 % with minor exceptions, leading to a strong improvement compared to existing correlations. The developed correlation was implemented in the open-source simulator DuMux and the implementation was validated by reproducing the measurement results. The validated implementation in DuMux allows to model scenarios such as Underground Hydrogen Storage (UHS) on a field-scale and, as a result, can be used to estimate the temporary loss of hydrogen into the cushion gas and the purity of withdrawn gas due to the gas–gas mixing process.

Perovskite/Pyrochlore Composite Mineral-like Ceramic Fabrication for 90Sr/90Y Immobilization Using SPS-RS Technique

A novel solid-phase synthetic approach was developed to produce a mineral-like composite ceramic based on strontium titanate (SrTiO3) and yttrium titanate (Y2Ti2O7) matrices for immobilizing radionuclides such as 90Sr and its daughter product 90Y, as well as lanthanides and actinides, via reactive spark plasma sintering technology (SPS-RS). Using XRD, SEM, and EDS analyses, the sintering kinetics of the initial mixed oxide reactants of composition YxSr1–1.5xTiO3 (x = 0.2, 0.4, 0.6 and 1) and structure-phase changes in the ceramics under SPS-RS conditions were investigated as a function of Y3+ content. In addition, a detailed study of phase transformation kinetics over time as a function of the heating temperature of the initial components (SrCO3, TiO2, and Y2O3) was conducted via in situ synchrotron XRD heating experiments. The composite ceramic achieved relatively high physicomechanical properties, including relative density between 4.92–4.64 g/cm3, Vickers microhardness of 500–800 HV, and compressive strength ranging from 95.5–272.4 MPa. An evaluation of hydrolytic stability and leaching rates of Sr2+ and Y3+ from the matrices was performed, demonstrating rates did not exceed 10−5–10−6 g·cm−2·day−1 in compliance with GOST R 50926-96 and ANSI/ANS 16.1 standards. The leaching mechanism of these components was studied, including the calculation of solution penetration depth in the ceramic bulk and ion diffusion coefficients in the solution. These findings show great promise for radioactive waste conditioning technologies and the manufacturing of radioisotope products.

Effectively boosting hydration capacity and oxygen reduction activity of cobalt-free perovskite cathode by K+ doping strategy for protonic ceramic fuel cells

Development of triple-conducting cathode can extend the electrochemically active region to the entire cathode to more effectively promoting oxygen reduction reaction (ORR). Herein, a cobalt-free perovskite Sr1.75K0.25Fe1.5Mo0.5O6−δ (SKFM) was developed as a single-phase triple-conducting cathode material for protonic ceramic fuel cells (PCFCs). Introduction of K into Sr-site leads to a 21.54 % increase in the hydration capacity compared to the undoped Sr2Fe1.5Mo0.5O6−δ (SFM). The bulk diffusion coefficient and surface exchange coefficient of SKFM are 3.8 and 5.2 times higher than those of SFM at 550 °C, respectively. XAS and EPR results demonstrate that the average valence state of Fe and the concentration of surface oxygen vacancies in SKFM are higher than those in SFM. The polarization resistances (Rp) value of SKFM cathode in wet air is 0.06 Ω cm2 at 700 °C, while it is 0.11 Ω cm2 for SFM cathode, which is reduced by 45.5 %, indicating significantly improved ORR activity. The Rp is dominated by the adsorption and diffusion process of oxygen associated with low-frequency part in wet air. The single cell with a configuration of Ni-BZCY4/21-μm-thick BZCY4/SKFM delivers a power output of 1000.8 mW cm−2 in wet H2 at 700 °C and steady operation at 600 °C for a total of 100 h.

Estimating Degradations of La0.57Sr0.38Co0.2Fe0.8O3-δ Oxygen Diffusion and Surface Exchange Coefficients by Effective Reaction Thickness

The degradation of La0.57Sr0.38Co0.2Fe0.8O3-δ (LSCF) cathode is investigated by focusing on the change in effective reaction thickness. The durability tests showed severe degradation for the thinner electrodes, which suggests that the degradation in surface exchange coefficient (k) is the dominant degradation factor rather than the bulk diffusion coefficient (D). For the quantitative evaluation of k and D, the electrochemical impedance spectroscopy analyses demonstrated that the degradation rate of k was larger than that of D, and both degraded larger for thinner electrodes. The changes in effective reaction thickness are estimated by numerical simulation with the obtained degradation rates of D and k. The effective reaction thickness elongated in thinner electrodes due to the excessive decrease in k. This implies that the degradation is accelerated in thinner electrodes where effective reaction thickness exceeds physical electrode thickness and larger local overpotential is imposed.

Nd-doping-induced perovskite/Ruddlesden-Popper heterointerfaces boost the ORR activity and CO2 tolerance for SrFeO3-δ-based cathode

The development of cathode materials with high oxygen reduction reaction (ORR) activity is crucial to realize the wide application of solid oxide fuel cells. Nd-doped SrFeO3-δ (SNF) two-phase nanocomposite was fabricated by a dopant-induced in situ self-assembly process. The SNF nanocomposite comprises 63.4 wt% perovskite main phase (P–SNF) and 36.6 wt% Ruddlesden-Popper second phase (RP-SNF). The average thermal expansion coefficient (TEC) of SrFeO3-δ is reduced by 36.5 % and down to 13.9 × 10−6 K−1. At 750 °C, SNF demonstrates an impressive output power of 779 mW cm−2, which is twice that of the single-phase SrFeO3-δ. The superior performance stems from the heterointerface effect of the in situ self-assembled two phases. This effect increases the content of oxygen vacancies, thereby enhancing both chemical oxygen surface exchange coefficient and bulk diffusion coefficient. Moreover, the SNF composite exhibits excellent CO2 tolerance than the single-phase SrFeO3-δ. This work presents a promising avenue for exploring multifunctional materials through interface engineering, offering new possibilities for future energy conversion devices.

Understanding Characteristic Electrochemical Impedance Spectra of Redox Flow Batteries with Multiphysics Modelling

Electrochemical impedance spectroscopy (EIS) is a non-destructive technique for analyzing electrochemical systems (such as redox flow batteries – RFBs). Battery researchers widely adopt equivalent circuit models (ECMs) to analyze EIS spectra of RFBs and attempt to use the circuit to deduce prevalent transport and kinetic properties [1]. Straightforward adoption of these ECMs suffers from some setbacks which need rectifying. There is a major issue of poor or inconsistent physical interpretation of the different circuit elements. ECMs of batteries are commonly used in real-time applications due to their simplicity and importance for determining properties like state-of-charge. However, prediction performance in low state-of-charge areas has to be improved [2], which reinforces the need to relate recorded spectra to the physical properties of cell components.Using an experimentally validated full Multiphysics model of single-cell vanadium RFB analyzed in the frequency domain, we approach understanding the EIS spectra characteristics based on the influence of cell features and operating parameters. To achieve our analyses, we investigate the effects of different cell properties and operating parameters on the Multiphysics model produced EIS spectra and the resulting ECM circuit element parameters that fit the spectra. Five different values for each cell property or operating parameter are considered for the following components: Electrode: Electrical conductivity, porosity vis a vie specific surface area and hydraulic permeability, reaction rate constants for the positive and negative sides.Membrane: Ionic conductivity, fixed charge concentration, porosity, and hydraulic permeability.Electrolyte: State-of-charge, Composition vis a vie bulk diffusion coefficients of species, density, and viscosity.