Distribution Of Relaxation Times Research Articles

Humidity impact on polarization dynamics in polymer electrolyte membrane fuel cells through distribution of relaxation times analysis

The interaction among relative humidity, current density, and internal polarization plays a crucial role in optimizing the performance of polymer electrolyte membrane fuel cells (PEMFCs). However, achieving swift analysis and feedback on the internal humidity status of PEMFCs through on-vehicle impedance spectroscopy measurements remains a significant challenge. Conducting a series of impedance spectra under operating conditions of 30 %, 50 %, and 80 % relative humidity sheds light on the impact of humidity on performance. Correlations between specific distribution of relaxation times (DRT) peaks and internal polarization are established. Through DRT analysis, four polarization dynamics related to proton transfer at the proton exchange membrane interface, proton transport in the cathode catalyst layer, charge transfer, and the oxygen diffusion process are effectively identified based on characteristic frequencies and peaks. The rate-determining step of the polarization varies under idling, rated, and overload conditions, providing valuable insights. This study contributes analytical models and strategic guidance for tailoring relative humidity conditions to mitigate polarization, thereby enabling real-time control and enhancement of PEMFC performance.

Mixed polyanionic NaFe1.6V0.4(PO4)(SO4)2@CNT cathode for sodium-ion batteries: Electrochemical diffusion kinetics and distribution of relaxation time analysis at different temperatures

We report the electrochemical sodium-ion kinetics and distribution of relaxation time (DRT) analysis of a newly designed mixed polyanionic NaFe1.6V0.4(PO4)(SO4)2@CNT composite as a cathode. The specific capacity of 104 mAhg−1 is observed at 0.1 C with the average working voltage of ∼3 V. Intriguingly, a remarkable rate capability and reversibility are demonstrated up to very high current rate of 25 C. The long cycling test up to 10 C shows high capacity retention even after 2000 cycles. The detailed analysis of galvanostatic intermittent titration technique (GITT) and cyclic voltammetry (CV) data reveal the diffusion coefficient of 10−8–10−11 cm2s−1. We find excellent stability in the thermal testing between 25–55 °C temperatures and 80% capacity retention up to 100 cycles at 5 C. Further, we analyze the individual electrochemical processes in the time domain using the novel DRT technique at different temperatures. The ex-situ investigation shows the stable and reversible structure, morphology and electronic states of the long cycled cathode material. More importantly, we demonstrate relatively high specific energy of ≈155 Wh kg−1 (considering the total active material loading of both the electrodes) at 0.2 C for full cell battery having excellent rate capability up to 10 C and long cyclic stability at 1 C.

Evaluation of Polymetallic Phosphide Cathodes for Sodium-Air Batteries by Distribution of Relaxation Time

Evaluation of Polymetallic Phosphide Cathodes for Sodium-Air Batteries by Distribution of Relaxation Time

High-precision identification of polarization processes of proton exchange membrane fuel cells through relaxation time analysis: Targeted experimental design and verification

Distribution of relaxation time (DRT) technology can achieve more precise decoupling of polarization process of proton exchange membrane fuel cell (PEMFC). However, except for the two peaks of DRT at low frequency, which are widely acknowledged to the cathode charge transfer impedance and the oxygen mass transfer impedance, there has been ongoing debate regarding the interpretation of other peaks observed at high frequency. In this work, the single-state variable control method is introduced by design of the membrane electrode assembly (MEA) and corresponding working operating conditions to simulate performance degradation factors of PEMFC, enabling accurate identification and verification of each peak in DRT. Based on the previous understanding that peaks P1 and P2 are oxygen mass transfer impedance and cathode charge transfer impedance, peaks P3-P5, ranging from high to low time scales, are determined to correspond to the other three polarization impedances. Specifically, peaks P3 and P4 are influenced by ionomer content in cathode and anode catalyst layers, respectively, and exhibit a decline with increasing humidity. They correspond to proton transfer processes within their respective catalyst layers. And the peak P5 is affected by anode catalyst loading and displays an increase with rising current density at low loading, signifying its involvement in the charge transfer process of anodic hydrogen oxidation reaction. A novel ECM was developed, consisting of five series-connected Randles circuits with polarization significance. The cathode and anode were separated in this design. The results demonstrate the enhanced sensitivity of DRT analysis to the performance degradation of PEMFC caused by oxygen transfer, charge transfer, and proton migration. This perspective provides a clear refinement for prior work of DRT polarization characteristic peaks.

Microstructures and complex impedance analysis of spray pyrolysis-synthesized Ni doped ZnO for optoelectronic applications

This study focuses on the physical exploration, particularly examining the structural and electrical attributes of ZnO thin films produced through spray deposition, with variations in the Ni/Zn ratio (0.25%, 0.5%, and 0.75%). X-ray diffraction (XRD) analysis reveals that both undoped and Ni-doped ZnO films exhibit a hexagonal crystalline structure, with a preferred orientation along the (002) direction perpendicular to the substrate. The semiconductor nature of all prepared compounds is confirmed by the grain boundary resistance. An escalation in Ni concentration corresponds to an increase in grain boundary resistance. The activation energy values, derived from both relaxation time and grain boundary resistances, closely align. Impedance studies indicate the presence of two relaxation processes within the compounds. The Nyquist diagram illustrates the emergence of semicircles, with decreasing radii at higher temperatures, indicating thermally activated semiconductor behavior in these samples, as evidenced by electrical conductance and distribution of relaxation times.

Enhancing LSCF-based air electrode durability: Insights into sulfur poisoning and air purification

The electrochemical performance of perovskite-type air electrodes in solid oxide cells is strongly affected by a trace amount of SO2 as the air impurity. The present work aims to study air purification efficiency in suppressing the degradation rate for the LSCF-GDC air electrode while operating under different SO2 concentrations. For this purpose, the electrochemical performance of symmetrical cells was evaluated using impedance spectra measured over 320 h and compared with intrinsic electrode degradation in synthetic air. Accordingly, the intrinsic degradation rate was measured at 0.05 mΩ cm2 h−1 while exposing the cell to synthetic air containing 10 and 100 ppb SO2, causing a severe increase to 0.17 and 0.30 mΩ cm2 h−1, respectively. Nevertheless, the calculated degradation rate under purified air containing 100 ppb SO2 was similar to the LSCF-GDC intrinsic degradation rate, representing the high practicality of filter material to adsorb SO2 species. Interpreting the impedance spectra using a distribution of relaxation times (DRT) and a complex nonlinear least squares fit (CNLS) revealed that the intrinsic degradation mechanisms were the limitation of dissociative surface adsorption of oxygen and charge transfer to the adsorbed oxygen. At the same time, inhibition of the O2 adsorption caused by the deposition of SrO, SO32−, and SrSO4 phases and increasing surface diffusion resistance for the adsorbed oxygen atoms were the rate-determining steps in SO2-containing synthetic air. Lastly, the effective suppression of degradation rate by gas purification indicates an extensive use of filter material to extend the lifespan of SOCs.

A genetic optimisation and iterative reconstruction framework for sparse multi-dimensional diffusion–relaxation correlation MRI

Multi-dimensional diffusion–relaxation correlation (DRC) magnetic resonance imaging (MRI) techniques have recently been developed to investigate tissue microstructures. Sub-voxel tissue heterogeneity is resolved from the local correlation distributions of relaxation time and molecular diffusivity. However, the implementation of these techniques considerably increases the total acquisition time, and simply reducing the scan time may be at the expense of detailed structural resolution. To overcome these limitations, an optimised framework was proposed for acquiring microstructural maps of the human brain on a clinically feasible timescale. First, the acquisition parameters of the multi-dimensional DRC MRI method were sparsely optimised using a genetic algorithm with a fitness function according to the spectral resolution of the correlation map, hardware requirements, and total scan time. Next, the acquired DRC MRI data were processed using a proposed numerical algorithm based on the dynamic inverse Laplace transform (ILT). Prior knowledge from one-dimensional data was then utilised in the iterative procedure to improve the spectral resolution. Finally, the proposed framework was validated using Monte Carlo simulations and experimental data acquired from healthy participants on an MRI scanner. The results demonstrated that the suggested approach is feasible for offering high-resolution DRC maps that correspond to distinct microstructures with a limited amount of optimised acquisition data from two-dimensional DRC sampling space. By significantly reducing scan time while retaining structural resolution, this approach may enable multi-dimensional DRC MRI to be more widely used for quantitative evaluation in biological and medical settings.

Molecular interaction between thiamine hydrochloride-DMSO binary mixture: a TDR spectroscopic approach

ABSTRACT The dielectric measurements of thiamine hydrochloride (vitamin B1 hydrochloride) and dimethyl sulphoxide (DMSO) binary mixtures have been carried out in the frequency range of 10 MHz to 50 GHz at 25°C, 20°C and 15°C using the TDR technique. The dielectric parameters such as complex dielectric permittivity ɛ*(ω), static dielectric permittivity (ɛs), relaxation time (τ), and asymmetric distribution parameter (β) are obtained by using Cole-Davidson model. These parameters are used to compute thermodynamic properties, Kirkwood correlation factor (geff), and excess molar volume (VE). The heteromolecular H-bonding existing in the binary mixture is explained.

Distribution of relaxation times used for analyzing the electrochemical impedance spectroscopy of polymer electrolyte membrane fuel cell

In this paper, a 25 cm2 polymer electrolyte membrane single cell is prepared by ultrasonic spraying coating method. The polarization curves and Electrochemical Impedance Spectroscopies (EIS) data of this cell are collected under different conditions, such as cell temperature, humidity, back pressure and pure O2. EIS data are analyzed by Distribution of Relaxation Time (DRT), and some results are concluded: (i) with the increase of current density, the Oxygen Reduction Reaction (ORR) time constant became lower, and the ORR reaction resistance and oxygen diffusion resistance both increases. (ii) With the increase of back pressure, the DRT peak assigned to oxygen diffusion process in cathode moves to low frequencies, the peak area decreases simultaneously. (iii) the proportion of the ORR polarization resistance gradually increases from 77 % to 84 % with the cell temperature increase from 65 °C to 80 °C. (iv) With the increase of humidity, the performance of the cell is decreased. (v) The oxygen diffusion resistance is negligible in pure oxygen working condition analyzed by DRT method.

Optical and dielectric properties of divalent copper based double perovskite compound, Gd2CuTiO6

In this work, we have investigated high temperature dielectric properties and room temperature optical properties on rare earth ion based orthorhombic Gd2CuTiO6 (GCTO). Optical properties like reflectance and band gap were determined from ultra-violet visible (UV–Vis) diffuse reflectance spectroscopy technique and photoluminescence (PL) spectrum. The compound exhibited substantial optical absorption and emission in the visible region. Our findings reveal the presence of an intermediate band, as evidenced by the difference between the band gap values obtained from the Tauc plot using the diffuse reflectance spectrum (3.07 eV) and the PL spectrum (2.4 eV). Furthermore, thermogravimetric analysis demonstrated high thermal stability with <0.4% change in mass over a wide temperature range of 30 °C–1200 °C in air environment. Moreover, lead-halide free compound, GCTO is highly thermally stable oxide double perovskite with wide band gap and absorption in the UV–Vis range are highly suitable for optical applications In addition, dielectric properties of the compound have been examined using impedance spectroscopy as a function of frequency ranging from 500 Hz to 1 MHz and temperature between 300 K and 550 K. Compounds with relaxor behaviour at high temperatures and high thermal stability are desired for several applications. Because of the cation disorders present in this compound, GCTO displays dielectric relaxor behaviour indicative of a distribution of relaxation times. Furthermore, the frequency-dependent modulus illustrated a thermally activated conduction mechanism. Cole–Cole plots of electrical modulus suggest prominent grain contribution above 350 K.

H-bonding interaction study for binary mixtures of methyl cellosolve and ethanol: a dielectric, FTIR spectroscopic and volumetric approach

The dielectric measurement of neat ethylene glycol monomethyl ether (EGMME), neat ethanol and their binary mixtures have been carried out using time domain technique in frequency range of 10 MHz to 50 GHz at the temperature range from 10 °C to 25 °C with a difference of 5 °C. The frequency domain technique within the frequency range of 20 Hz to 2 MHz is used to obtain complex dielectric permittivity ε*(ω), electrical modulus M*(ω), complex electrical conductivity σ*(ω) and loss tangent (tan δ) at 25 °C. The dielectric spectra obtained using TDR technique are fitted in Cole-Davidson model to extract the dielectric parameters such as static dielectric permittivity (ε s), relaxation time (τ) and asymmetric distribution parameter (β). These relaxation parameter values are used to predict intermolecular hydrogen bonding between EGMME and ethanol molecules. Furthermore, the inter-molecular interactions through H-bonding between EGMME and ethanol molecules have been confirmed and discussed using Kirkwood correlation factor, excess permittivity, thermodynamic parameter, Bruggeman factor, excess molar volume, excess dielectric permittivity at high frequency and Fourier transform infrared (FTIR) spectra.

Fabrication and performance investigation of high entropy perovskite (Sr0.2Ba0.2Bi0.2La0.2Pr0.2)FeO3 IT-SOFC cathode material

The high-entropy oxide (HEO) concept expands the design space of solid oxide fuel cell (SOFC) cathode materials. There is great potential for the development of HEO cathode materials that has not been fully explored, and the relationship between their chemical composition, grain size, and electrochemical performance is not yet fully understood. This experimental design involved the preparation of single-phase perovskite (Sr0.2Ba0.2Bi0.2La0.2Pr0.2)FeO3 HEO SOFC cathode materials, and we systematically studied the effects of synthesis temperature and microstructure on their electrochemical performance. The results show that as the synthesis temperature increases, structural transformations from multiphase to single-phase perovskite HEO can be observed. It exhibits excellent conductivity and electrochemical performance (the minimum polarization resistance reaches 0.033 Ω∙cm2, and the maximum power density is 664 mW∙cm−2). The single-phase perovskite HEO sample exhibits higher electrochemical performances compared to those of multiphase perovskite. Furthermore, it exhibits outstanding ability to suppress Sr segregation, chemical compatibility with Ce0.8Sm0.2O1.9(SDC), and CO2 tolerance performance. The Distribution of relaxation time(DRT) analysis shows that as the synthesis temperature (1000–1150 ℃) increase, HEO single-phase formed and the oxygen atom reduction ability of the SBBLP samples was improved; and the adsorption of gas oxygen on the electrode surface is limited with porosity decreases. The work shows it is interesting and valuable to optimize the performance of SOFC cathode materials using a high entropy design.

Semiconductor ionic Cu doped CeO2 membrane fuel cells

Operation of low-temperature solid oxide fuel cells (LT-SOFCs) in the range of 300–500 °C has emerged as a promising technology and desired operational temperature for clean and efficient energy conversion. However, the lack of suitable electrolyte materials for these temperatures presents a significant challenge. In this article, a novel approach is proposed to address the hurdle of operational temperature by tailoring copper-doped cerium oxide, Cu0.1Ce0.9O2 as a semiconductor ionic membrane (SIM) to act as an electrolyte in a cell. The Cu0.1Ce0.9O2 formed a single-phase cubic fluorite structure. As a SIM, it shows enhanced ionic conductivity and reduced electrolyte/electrode polarizations, therefore achieved good fuel cell performance and electro-kinetics, reaching a power density of 515 mW/cm2 at 500 °C, with an ionic conductivity exceeding 0.1 S/cm. The detailed investigation shows dominant protonic conduction (H+) behavior in the Cu0.1Ce0.9O2 membrane. Interesting phenomenon of coupling effect elaborated through the distribution of relaxation time (DRT) analysis depicted to understand the romance of protons and electrons conduction mechanism. These advancements lead to Cu0.1Ce0.9O2 as a new type of SIM in LT-SOFCs, emphasizing the need for further research and development in this promising field to unlock the SIM and fuel cell potential.

Enhancement of Performance and Sulfur Tolerance of Ceria-Based Fuel Electrodes in Low Temperature SOFC

The trend of operating the solid oxide fuel cell at significantly lower operation temperatures enables the application of electrodes with finer microstructure or even nanostructured electrodes with increased active surface and enhanced performance. To maintain the high performance in hydrocarbon fuels commonly impurified with sulfur compounds, a required sulfur tolerance has to be maintained. In this study we compare performance and H2S-poisoning of four ceria-based electrodes: conventional Ni/Ce0.9Gd0.1O2−δ cermets and sub-μm scaled Ce0.8Gd0.2O2−δ -electrodes with and without infiltrated nickel. Symmetrical cells were operated in a hydrogen/steam/nitrogen gas mixture with and without minor amounts of H2S at 600 °C. The performance is analyzed by electrochemical impedance spectroscopy. The distribution of relaxation times is applied to deconvolute the electrochemical processes followed by a complex nonlinear least square fit to quantify the loss processes and the impact of sulfur. Whereas two different Ni/Ce0.9Gd0.1O2−δ cermet electrodes exhibit polarization resistances at 600 °C without/with 0.1 ppm H2S of 2.89/5.56 Ωcm2 and 2.15/2.75 Ωcm2, the single phase Ce0.8Gd0.2O2−δ electrode reaches 0.98/2.37 Ωcm2. With an infiltration of Ni-nitrate forming nickel nanoparticles on the gadolinia-doped ceria-surfaces, the ASR could be drastically reduced to 0.32/0.37 Ωcm2.

Short Term Silver Electrode Microstructure Changes Under Epoxidation Conditions for Solid Oxide Electrolysis Cells

Ethylene epoxidation is an important reaction forming ethylene oxide (EO), which is a precursor to many other critical chemicals. This study links short-term EO production to the effects on the microstructure of Ag/yttria-stabilized zirconia cells with and without electrochemical promotion of catalysis (EPOC). Nano-scale features, called striations, were observed on the silver under all epoxidation reaction conditions tested, using a scanning electron microscope. While appearing in both cases, the striations for the EPOC case are finer in size (∼150 to 250 nm) compared to the no current case (∼400 to 500 nm). These features did not appear when epoxidation conditions were not present. Striation formation was further linked to the epoxidation reaction through electrochemical impedance spectroscopy and gas chromatography. Ethylene conversion to EO declines over the course of hours as striations form, indicating that striations have a negative influence on the reaction. Distribution of relaxation times was performed to determine the effect striation formation has on the electrochemical performance of the cells. It was observed that the low-frequency peaks in the DRT analysis significantly decrease as striations formed over the course of 10 h.

On the futility of the Fuoss-Kirkwood relation

The Fuoss-Kirkwood (FK) relation is used to derive analytical expressions for the distribution of uncorrelated relaxation times (DRT), particularly of probed biochemical and electrochemical systems, often without scrutiny. Its futility is proven simply by using the parity of impedance with complex frequencies. However, given the futile nature of the FK relation, these expressions are not suitable for validation of computed DRT spectra. Despite this, the need for such expressions persists. Addressing this need and the oversight of the dependency of the DRT value on the underlying data, the DRT is extended into the complex plane using the Hilbert transform (HT). It makes the DRT universal for any complex-valued quantity to not only quantify the extent of relaxations but also to assess their nature. keyword: distribution ; integral transforms ; relaxation time ; superposition

State of health (SOH) assessment for LIBs based on characteristic electrochemical impedance

With the continuous development of high energy density cell technology, the electric transport industry proposed higher requirements for the accuracy and real-time performance of automotive lithium batteries (LIBs) health status assessment. A state of health (SOH) assessment is suggested based on electrochemical impedance at characteristic frequency in the study. The distribution of relaxation time is used to deconstruct the internal electrochemical reaction of the battery and the impedance value of electrochemical process is quantified as a feature to avoid the effect of state of charge (SOC) in the evaluation. The imaginary part of impedance feature is applied to characterize the internal temperature of the lithium battery based on the analysis of impedance differences. Thus, the correlation between the state of health and impedance characteristics is examined to obtain the SOH assessment model of lithium battery in the full SOC and wide temperature spectrum. In conclusion, the assessment demonstrates an exceptional goodness-of-fit, with an accuracy of 0.99 in evaluating the SOH of LIBs and internal temperature, thereby indicating the robustness and reliability of the approach.

Effective Promotion of the Activity and Stability of Cathodes for Protonic Ceramic Fuel Cells

AbstractProtonic ceramic fuel cells (PCFCs) are emerging as effective devices for their excellent capability of converting energy. However, the sluggish oxygen reduction reaction (ORR) and poor durability of cathodes greatly limit their widespread commercialization. Herein, a multi‐cationic oxide nano‐catalyst with a nominal composition of Pr0.2Ce0.2Ni0.2Co0.2Fe0.2Ox (denoted as PCNCFO) is designed and reported, which significantly enhanced the ORR activity and durability of a typical PrBaCo2O5+δ (PBC) cathode. The PCNCFO‐coated PBC cathode delivered impressive cell performance with a small polarization resistance of only 0.18 Ω cm2 at 600 °C on symmetrical cells and a high peak power density (PPD) of 1.31 W cm−2 at 650 °C on single cells. Meanwhile, the PCNCFO‐coated PBC cathode exhibits excellent operational stability both on symmetrical and single cells. It is indicated that the Ce oxide in the nano‐catalyst coating can react with the segregated Ba to form active species, while others can activate the surface of the cathode, as indicated by the transmission electron microscope (TEM) and distribution of relaxation time (DRT) analyses.

Research on online passive electrochemical impedance spectroscopy and its outlook in battery management

Current lithium-ion battery (LIB) management technique relying solely on the limited time-domain measurements appears to reach its limit, and incorporating new sensing information, particularly the impedance of LIB, offers a promising path for improvement. Using the non-stationary random driving profile of electric vehicle (EV), a method to extract online passive electrochemical impedance spectroscopy (OPEIS) is proposed and validated, with relevant factors influencing its efficacy also investigated. The particularity of actual driving profile is revealed both theoretically and experimentally, and beyond expectation, the highly differentiated driving profiles yield a similar spectral pattern, which facilitates the acquisition of OPEIS. Continuous OPEIS characterized by the distribution of relaxation time (DRT) ranging from 0.2 Hz to 3 kHz are analyzed in detail under different battery conditions. Compared with offline reference EIS, most of the measurement errors are <3%. Based on the acquired spectral information and OPEIS, a safety-relevant detector and an internal temperature estimator for LIB are presented, and they can both realize a near instant electrochemical sensing up to 1 Hz. As the underlying opportunities of OPEIS are outlined, challenges in its reliable acquisition and engineering implementation are evaluated as well. By comprehensively discussing the realization of OPEIS, research in this paper is expected to provide valuable references for a more effective battery management.

An innovative perovskite oxide enabling improved efficiency for low-temperature ceramic electrochemical cells

In recent years, energy carriers for renewable sources and devices that convert chemical energy into electrical energy, such as solid oxide fuel cells (SOFCs) and solid oxide electrolysis cells (SOECs), have made hydrogen production economically viable and have numerous industrial uses. We have designed SrFe0.3TiO3 (SFT) materials to function as SOFC and H-SOEC electrolytes at low operational temperatures of 520–420 °C. The SFT (600 °C) shows a higher fuel cell power density of 650 mW/cm2 and a reasonable current density of 1.14 A/cm2 in fuel cell and electrolysis cell mode at 520 °C. The formation of the surface layer enables high ionic and Proton conduction due to a high number of oxygen vacancies, and the core–shell type interface enables easy and quick proton transportation restricted to the surface. Energy band alignment and distribution relaxation time (DRT) were also evaluated to study ion transport in SFT materials. These results open up advanced avenues for the design of high-performance, sophisticated proton-conducting electrolytes for ceramic electrochemical cells.