Distribution Of Relaxation Times Research Articles

Effect of Confinement on the Translational Diffusivity of Small Dye Molecules in Thin Polystyrene Films and Its Connection to Tg-Confinement and Fragility-Confinement Effects.

Using fluorescence, we study the impact of nanoscale confinement on the translational diffusivity (D) of trace levels of a small-molecule dye, 9,10-bis(phenylethynyl)anthracene (BPEA), in supported polystyrene (PS) films via Förster resonance energy transfer (FRET). Reductions in BPEA diffusivity are observed in films thinner than ∼200 nm, with D decreasing by 80-90% in 100 nm-thick films compared to bulk. The activation energy of BPEA diffusivity increases from ∼210 kJ/mol in bulk films to ∼370 kJ/mol in 130 nm-thick films. BPEA exhibits a greater diffusivity-confinement effect than a larger dye, decacyclene, in terms of the length scale at which the effects of confinement become evident and the percentage reduction in diffusivity. For both BPEA and decacyclene, the diffusivity-confinement effect in supported PS films occurs at a length scale much larger than that for the glass transition temperature (Tg)-confinement effect and somewhat larger than that for the fragility-confinement effect. This difference in confinement-effect length scales can be rationalized as follows: small-molecule dye diffusivity relates predominantly to short times in the α-relaxation distribution, whereas Tg relates to long times in the α-relaxation distribution, and fragility reflects the overall breadth of this relaxation time distribution. If confinement results in a narrower relaxation time distribution in PS films with the short-time relaxations being shifted to longer times and the longest-time relaxation regimes being shifted to shorter times, then Tg, diffusivity, and fragility all decrease at sufficient levels of confinement. If the narrowing with confinement begins with the shortest relaxation time regimes, then fragility and small-molecule dye diffusivity are influenced by confinement at larger length scales than Tg.

Evaluation of the electrical behavior of tungsten trioxide and cobalt oxide nanoparticles filled poly (ɛ-caprolactone) composite for optoelectronic devices

This study obtains the electrical characterization of nanocomposites comprising Poly(ɛ-caprolactone) (PCL), tungsten trioxide (WO3), and cobalt oxide (Co3O4) nanoparticles. The fabrication of these nanocomposites through a casting method aimed to enhance their electrical conductivity and dielectric properties. The AC conductivity (σac) was analyzed across varying frequencies, revealing a notable increase with the addition of Co3O4 nanoparticles, particularly up to the high content of Co3O4 nanoparticles. This enhancement is attributed to the formation of ion transport pathways and the increased amorphous regions within the PCL matrix. Dielectric properties were assessed through ε′ and ε'') measurements, which exhibited a decrease with increasing frequency, indicating the dielectric relaxation processes of the composite. The complex electric modulus analysis demonstrated a significant relationship between the real and imaginary components, suggesting potential ionic conductivity in the nanocomposites. Additionally, the Argand plot revealed a depressed semicircle, indicating a distribution of relaxation times, which further confirmed the enhancement of conductivity with raising laser ablation time. Overall, the results indicate that the addition of WO3 and Co3O4 nanoparticles significantly improves the electrical properties of PCL, making these nanocomposites suitable for various electrical applications.

Interface Degradation of LaCl3-Based Solid Electrolytes Coupled with Ultrahigh-Nickel Cathodes.

Despite competitive compatibility with high-nickel cathodes, chloride solid electrolytes (SEs) still experience inevitable side reactions at the cathode/SE interface, causing capacity decay in all-solid-state lithium batteries (ASSLBs) during cycling. Herein, a three-electrode ASSLB testing device is developed to comprehensively reveal the interface failure mechanisms of the ultrahigh-nickel LiNi0.92Co0.05Mn0.03O2 (NCM92) cathode paired with LaCl3-based chloride SE Li0.447La0.475Zr0.059Ta0.179Cl3 (LLZTC). Distribution of relaxation time (DRT) analysis clearly shows the ASSLB degradation accompanied by a significant NCM92/LLZTC interface impedance increase, which becomes more pronounced at the higher cutoff charging voltage of 4.8 V vs Li+/Li. Furthermore, time-of-flight secondary ion mass spectrometry (ToF-SIMS) and focused ion beam scanning electron microscopy (FIB-SEM) analysis also confirm the deterioration arising from active lattice oxygen and loss of physical contact at the NCM92/LLZTC interface. These findings reveal both electrochemical degradation and physical contact failure at the cathode/SE interface as key causes of the ASSLBs' capacity decay.

Identifying electrochemical processes by distribution of relaxation times in proton exchange membrane electrolyzers

Distribution of relaxation time (DRT) is used to interpret electrochemical impedance spectroscopy (EIS) for proton exchange membrane (PEM) water electrolyzers, with an attempt to separate overlapped relaxation processes in Nyquist plots. By varying operating conditions and catalyst loadings, four main relaxation peaks arising from EIS can be identified and successfully separated from low to high frequencies as (P1) mass transport, (P2) oxygen evolution reaction kinetics, (P3) reaction kinetics (with faster time constant than P2), and (P4) ionic transport. The shape, height, and frequency of the DRT peaks change with different membrane electrode assembly (MEA) configurations. Electron microscopy reveals distinct features from the cross-sectioned MEAs which verify critical DRT results in that increasing the iridium (Ir)-anode loading from 0.2 mgIr/cm2 to 1.5 mgIr/cm2 reduces kinetic losses due to higher site-access; a thick and compacted anode, however, also triggers higher ohmic resistances from membrane/catalyst layer hydration and increases transport losses due to longer ionomer pathways. DRT provides higher resolution to EIS for deconvoluting processes with different relaxation times and the quantification of DRT peaks improves the accounting of total losses from each process.

Experimental Study on Fluid Dissipation Effects in Core Samples by NMR Measurement

Laboratory core nuclear magnetic resonance (NMR) relaxation measurements offer geological information, including rock porosity and oil saturation, relevant to logging. When core samples drilled from wells are exposed to air, the fluids within their pores inevitably dissipate. This phenomenon may lead to discrepancies between the results of nuclear magnetic resonance relaxation experiments and the actual situation underground. To deeply explore the impact of fluid dissipation on NMR core analysis experimental results, a series of simulated dissipation experiments were designed under constant temperature and humidity conditions. Variations in one-dimensional and two-dimensional NMR measurement results of oil-saturated samples were examined under varying crude oil viscosities and dissipation times. The experimental results indicate that as exposure time increases, the T2 distribution of oil-saturated cores decreases, and the amplitude of the T2 distribution peaks decreases. Both oil and water relaxation components show a decreasing trend; however, the dissipation rate of the bounding water component significantly exceeds that of the crude oil component. By employing two-dimensional NMR relaxation time distribution fluid quantitative analysis technology, the relationship between the dissipation rates of various phase fluids and exposure time during the stable dissipation stage was analyzed. This offers a reference for adjusting the oil saturation of exposed cores based on NMR measurements.

Ultra-high rate and long cycle life sodium-based dual-ion batteries enabled by Li2TiO3-modified cathode-electrolyte-interphase

Sodium-based dual-ion batteries (SDIBs) have received widespread attention due to their high voltage, low cost, safety, and eco-friendliness. Nevertheless, the irregular spherical graphite cathodes are limited by the mass transfer non-uniformity and sluggish reaction kinetics due to uneven anion migration through the highly tortuous pathways and the inductive anisotropic electric fields. Herein, we report a facile dissolution-precipitation-carbonation optimized modification strategy to synthesize a series of nano-Li2TiO3/C-modified graphite flake (GF-LTx, x = 1, 2.5, and 5) as cathode for SDIBs. The Li2TiO3-C-Cathode Electrolyte Interphase (Li2TiO3-C-CEI) trinity layer by in situ reactions shows good cycling performance. The intrinsic mechanism of Li2TiO3-C-CEI was further explored by DFT molecular orbital theory and distribution relaxation time (DRT) analysis. Notably, the GF-LT2.5 achieves 10,000 stable cycles at 3–5.2 V (vs. Na/Na+) with a initial capacity of 91.1 mAh g−1 and a decay rate of only 0.00217 % per cycle. Furthermore, GF-LT2.5 demonstrates an ultra-high rate performance of 100C with only 30 s for a single charge and 86 % capacity for low current density. Infrared thermography confirms the good thermal stability and safety of the gel-based flexible pouch cells. This work provides new insights into the design of high-rate performance, long-cycle stability, and high-safety energy storage systems.

In-situ impedance diagnosis experiment and equivalent circuit modeling based on distribution of relaxation time method for unitized regenerative proton exchange membrane fuel cells

The Distribution of Relaxation Times (DRT) method provides a powerful approach for analyzing Electrochemical Impedance Spectroscopy (EIS) in electronic components, enabling clear separation of different impedance types and accurate equivalent circuit modeling. In this study, the DRT method was applied to unitized regenerative proton exchange membrane fuel cells (UR-PEMFCs) for the first time, establishing an impedance quantification model for in-situ diagnostics of multiple impedances. This foundational framework supports future durability testing efforts. In-situ impedance diagnostics were conducted in both Fuel Cell (FC) and Electrolytic Cell (EC) modes using a custom mode-switching platform. Results show that under constant electrode conditions, the bifunctional membrane electrode enhances round-trip efficiency by 15.75% compared to the constant gas mode. Through DRT imaging in FC and EC modes, impedance information corresponding to distinct relaxation peaks was extracted and assigned based on operational experiments. The three main peaks identified in both modes were attributed to proton transfer impedance, charge transfer impedance, and mass transfer impedance. Additionally, variations in operating conditions led to the appearance of new transport mechanisms within the charge transfer impedance. In FC mode, the DRT-based equivalent circuit model achieved precise fitting. Applying DRT to UR-PEMFCs improves water and bubble management, offering efficient optimization pathways and valuable guidance for cell design, operational parameter refinement, and durability monitoring.

Molecular Dynamics and Self-Assembly in Double Hydrophilic Block and Random Copolymers.

We investigate the self-assembly and dynamics of double hydrophilic block copolymers (DHBCs) composed of densely grafted poly[oligo(ethylene glycol) methacrylate] (POEGMA) and poly(vinyl benzyl trimethylammonium chloride) (PVBTMAC) parent blocks by means of calorimetry, small- and wide-angle X-ray scattering (SAXS/WAXS), and dielectric spectroscopy. A weak segregation strength is evident from X-ray measurements, implying a disordered state and reflecting the inherent miscibility between the host homopolymers. The presence of intermixed POEGMA/PVBTMAC nanodomains results in homogeneous molecular dynamics, as evidenced through isothermal dielectric and temperature-modulated DSC measurements. The intermixed process undergoes a glass transition at a temperature approximately 40 K higher than the vitrification of bulk POEGMA segments, and it shifts to an even higher temperature by increasing the content of the hard block. At temperatures below the intermixed glass transition temperature, the confined POEGMA segments between the glassy intermixed regions contribute to a segmental process featuring (i) reduced glass transition temperature (Tg), (ii) reduced dielectric strength, (iii) broader distribution of relaxation times, and (iv) reduced fragility compared to the POEGMA homopolymer. We also observe two glass transition temperatures of dry PVBTMAC, which we attribute to the backbone and side chain segmental relaxation. To the best of our knowledge, this is the first time in the literature that these glass transitions of dry PVBTMAC have been reported. Finally, this study shows that excellent mixing of the two homopolymers is obtained, and this implies that different properties of this copolymer system can be tailored by adjusting the concentration of each homopolymer.

Electrochemical Performances of a Solid Oxide Electrolysis Short Stack Under Multiple Steady-State and Cycling Operating Conditions

Solid oxide electrolysis cells (SOECs) are increasingly utilized in hydrogen production from renewable energy sources, yet high degradation rates and unclear degradation mechanisms remain significant barriers to their large-scale application. Consequently, endurance testing of stacks under various operating conditions and studying the degradation mechanisms associated with these conditions is imperative. However, due to the generally poor performance consistency among stacks, multi-condition data from numerous stacks lack reliability. In this experimental study, having established a specific SOEC stack’s performance and optimal conditions, durability tests under varied conditions, including various current densities, current operation modes (cyclic or constant current), fuel utilization rates, and temperature cycles were conducted. Electrochemical analysis tools like electrochemical impedance spectroscopy and distribution of relaxation time were employed to analyze the causes of voltage fluctuations under high current densities. The results confirmed that the SOEC stack could handle current cycling at low current densities and constant-current electrolysis at high current densities and withstand at least two temperature cycles.

Room-temperature ionic liquid electrolytes for carbon fiber anodes in structural batteries

Structural batteries require thermally stable electrolytes paired with carbon fibers (CFs), which offer advantages of lightweight, high mechanical strength, and good electrical conductivity. This work evaluated various room-temperature ionic-liquids (RTILs) as compatible electrolytes for CF anodes and LiFePO4 (LFP) cathodes on CFs. This LFP/CF full-cell design eliminates Cu and Al current-collectors, potentially enhancing gravimetric energy and reducing costs. Among various RTILs, LiTFSI in N-propyl-N-methylpyrrolidinium (PYR13) – bis(fluorosulfonyl)imide (FSI) offered promising LFP/CF full-cell performances, attributed to the formation of solid electrolyte interphase (SEI) layer on the CF anode with components such as Li2Sx, Li2S–SO3, LiF, LixFy and F–SO2, identified through X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analyses further confirmed the electrochemical stability of the SEI layer on CF anodes. The LFP/CF cell delivered an initial capacity of 119 mAh/g and relatively high Coulombic efficiency when using the 1 M LiTFSI in PYR13-FSI. CF cycled in different electrolytes exhibit varying mechanical properties with up to 10.08 % loss in tensile strength, which may be related to CF surface degradation during cycling. The 1 M LiTFSI in PYR13-FSI is non-flammable, offering a significant thermal safety. This work successfully demonstrated the significant potential of 1 M LiTFSI in PYR13-FSI RTILs, which enables the use of CF as both an anode active material and cathode current collector for structural battery applications.

Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024)

Characterization of Microscopic Structures in Living Tumor by In Vivo Measurement of Magnetic Relaxation Time Distribution of Intratumor Magnetic Nanoparticles (Adv. Mater. 46/2024)

Analysis of Battery-like and Pseudocapacitive Ion Intercalation Kinetics via Distribution of Relaxation Times

Abstract Improving the kinetics of electrochemical ion intercalation processes is of interest for realizing high-power electrochemical energy storage. This includes classical battery-like intercalation and pseudocapacitive intercalation processes with a capacitor-like electrochemical signature. Electrochemical methods are needed to probe the kinetics of such complex multistep processes in detail. Here, we present the use of the distribution of relaxation times (DRT) analysis of electrochemical impedance data to identify the kinetic limits of intercalation reactions. We study the lithium intercalation reaction in TiS2 from organic and aqueous electrolytes as a model system. The material can exhibit both battery-like and pseudocapacitive intercalation regimes depending on the potential range, variable diffusion lengths by adjusting its particle size, and a tunable degree of solvent cointercalation by choosing the electrolyte solvent. Using DRT, we can distinguish between the kinetic limitations imposed by solid-state ion diffusion, interfacial ion adsorption and transport, and ion desolvation processes. Thus, DRT analysis can complement existing methods, such as voltammetry or 3D-Bode analysis, to better understand the kinetics of intercalation reactions.

Enhancing Hydrogen Evolution Reaction through the Improved Mass Transfer and Charge Transfer by Bimetal Nodes.

The high cost of hydrogen production by water electrolysis severely challenges its commercial application. It is highly desirable to develop efficient electrocatalysts and innovative electrolytic cells. Introducing additional metal nodes to form bimetallic metal-organic framework (MOF) is a simple, feasible strategy to overcome the poor electrocatalytic performance of single-metal MOF. In this study, the hydrothermal method is used to synthesize bimetallic NixCoy-BTC. It is found that for hydrogen evolution reaction (HER), Ni0.8Co0.2-BTC merely requires a potential of -0.203 V (vs reverse hydrogen electrode, RHE) to achieve 10 mA cm-2, which is significantly lower than that of Ni-BTC (-0.341 V vs RHE). Notably, electrochemical impedance spectroscopy (EIS) and distribution of relaxation time (DRT) analysis indicate that NixCoy-BTC has improved charge transfer and mass transfer process, compared with Ni-BTC. Electron paramagnetic resonance (EPR) confirms that Ni0.8Co0.2-BTC has more unpaired electrons than Ni-BTC. Density functional theory (DFT) calculations show that compared with Ni-BTC, NixCoy-BTC is more thermodynamically favorable for the adsorption of H+, OH-, and H2O. It demonstrates that the change of mass transfer caused by bimetallic nodes and the delicate variation of MOF surface play an important role in the electrochemical process. Moreover, a novel electrolytic cell was developed using a methanol oxidation reaction (MOR) to replace oxygen evolution reaction (OER). In this MOR-based electrolytic cell, a current density of 50 mA cm-2 can be achieved at only a cell voltage of 1.85 V, which is lower than the 2.22 V of OER-based electrolytic cell, suggesting that 16.7% electric energy can be saved. At the same time, the Faraday efficiency (FE, 98.2%) of the MOR-based cell is higher than that (94.5%) of the OER-based cell. This research offers a promising strategy for low-cost hydrogen production.

Introducing strong metal–oxygen bonds to suppress the Jahn-Teller effect and enhance the structural stability of Ni/Co-free Mn-based layered oxide cathodes for potassium-ion batteries

Mn-based layered oxides (KMO) have emerged as one of the promising low-cost cathodes for potassium-ion batteries (PIBs). However, due to the multiple-phase transitions and the distortion in the MnO6 structure induced by the Jahn-Teller (JT) effect associated with Mn-ion, the cathode exhibits poor structural stability. Herein, we propose a strategy to enhance structural stability by introducing robust metal–oxygen (M–O) bonds, which can realize the pinning effect to constrain the distortion in the transition metal (TM) layer. Concurrently, all the elements employed have exceptionally high crustal abundance. As a proof of concept, the designed K0.5Mn0.9Mg0.025Ti0.025Al0.05O2 cathode exhibited a discharge capacity of approximately 100 mA h g−1 at 20 mA g−1 with 79% capacity retention over 50 cycles, and 73% capacity retention over 200 cycles at 200 mA g−1, showcased much better battery performance than the designed cathode with less robust M–O bonds. The properties of the formed M–O bonds were investigated using theoretical calculations. The enhanced dynamics, mitigated JT effect, and improved structural stability were elucidated through the in-situ X-ray diffractometer (XRD), in-situ electrochemical impedance spectroscopy (EIS) (and distribution of relaxation times (DRT) method), and ex-situ X-ray absorption fine structure (XAFS) tests. This study holds substantial reference value for the future design of cost-effective Mn-based layered cathodes for PIBs.

Comparative investigation of composition, microstructure and property influences on electrocatalysis of two representative cathodes: BaCo0.4Fe0.4Zr0.1Y0.1O3-δ versus Ba0.5Sr0.5Co0.8Fe0.2O3-δ

BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) and Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) perovskites are two representative high-performance cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Here, symmetric cell tests demonstrate that polarization resistance values of BCFZY cathode are only 0.21–0.29 times those of BSCF cathode at 740–660 °C, and 0.21–0.26 times those of BSCF cathode at the oxygen partial pressures of 1.00–0.10 atm. Distribution of relaxation times (DRT) is applied to detect individual electrode processes overlapped in impedance spectra, which finds that the dominant processes of oxygen dissociation, subsequent species transfer and reduction on BCFZY cathode are superior to those of BSCF cathode. By temperature-programmed desorption of oxygen (O2-TPD), thermal expansion coefficient (TEC) measurements, scanning electron micrograph (SEM) and energy dispersive spectra measurements, the strong oxygen combination ability with higher activation energy of oxygen desorption (Ed = 84 kJ mol-1), peculiar surface state with evident nano-particle structure, more matchable TEC (19.0 × 10-6 K−1) and excellent interfacial connection with the electrolyte are observed on BCFZY cathode to account for its distinctive catalysis, as compared to BSCF cathode (Ed = 68 kJ mol-1, TEC = 24.2 × 10-6 K−1).

Fast acquisition method of battery electrochemical impedance spectra based on impedance fragments

Electrochemical impedance spectroscopy (EIS) is often used for battery characterization and monitoring. However, there are still difficulties in acquiring battery impedance spectra in large quantities and wide frequency bands in practical applications. The lower the frequency range of acquisition, the longer the measurement time spent, and the higher the frequency range of measurement, the more expensive the measurement equipment, and these problems seriously limit the wide application of impedance information. To address this problem, this study proposes a method for fast acquisition of electrochemical impedance spectra of lithium-ion batteries based on impedance fragments. Firstly, impedance segments at specific frequencies in the EIS are selected as features based on the distribution of relaxation times (DRT). Then, a Long Short-Term Memory (LSTM) neural network model is used to reconstruct the complete impedance spectrum, and a population optimization algorithm is used to optimize the hyperparameters in the model. The validation results indicate that the reconstructed RMSE error is only 14.26 mΩ, corresponding to a MAPE of 1.65 %, while the measurement time is reduced to 27.01 % of the original measurement time. Finally, the performance of this method in identifying fractional-order model parameters is further discussed.

Rapidly Screening the Correlation between the Rotational Mobility and the Hydrogen Bonding Strength of Confined Water.

Automated Deuterium Relaxation-Ordered SpectroscopY in solution (ADROSYS), an automated two-dimensional deuterium NMR methodology, discriminates between D2O populations (as well as deuterium-labeled alcohol groups) whose properties differ as a result of being confined inside nanoscale volumes. In this contribution, a proof-of-principle demonstration on reverse micelles (RMs) yields the insight that as the length scale of the confinement decreases from several nanometers down to less than a nanometer, the position of the signal peak migrates through the two-dimensional (2D) spectrum, tracing out a distinctive path in the 2D space (of relaxation time vs chemical shift). The signals typically follow a relatively gentle linear path for water confined on the scale of several nanometers, before curving once the surfactants confine the water molecules to length scales smaller than 1-2 nm. The qualitative shape of this path, especially in the regime of strong confinement, can change with different choices of surfactants, i.e., a different choice of chemistry at the edges of the confining environment. An important facet of this research was to demonstrate the relatively wide applicability of these techniques by showing that both: (1) Standard modern NMR instrumentation is capable of deploying an automated measurement, even though the choice of a deuterium nucleus is nonstandard and frequently requires companion proton spectra in order to reference the chemical shifts; and (2) well-established (though underutilized) modern techniques can process the resulting signal even though it involves the somewhat unusual combination of chemical shifts along one dimension and a distribution of relaxation times along another dimension. In addition to demonstrating that this technique can be deployed across many samples of interest, detailed facts pertaining to the broadening or shifting of resulting signals upon inclusion of various guest molecules are also discussed.

Insights into kinetic and transfer mechanisms for alkaline decoupled water electrolysis based on distribution of relaxation times

Electrochemical water splitting is crucial for the decarbonization of industrial processes and the coupling of renewable energy sources. Evaluation of individual HER and OER contributions to the transfer process is essential for optimizing electrolysis system performance. This study uses nickel-cobalt layered double hydroxide (NiCo-LDH) as a solid-state redox mediator (SRM), achieving efficient H2 and O2 separation. This study provides an in-depth analysis of kinetic and ion/charge/mass transfer mechanisms linked to various characteristic impedances in alkaline decoupled water electrolysis (DWE) system by integrating Electrochemical Impedance Spectroscopy (EIS) and Distribution of Relaxation Times (DRT) methods. The characteristic frequency evolution is consistent with the charge-discharge state of SRM and mass transfer frequency is related to the bubble size and gas diffusion rate of electrocatalysts at different current densities. The charge transfer Rct dominates the total polarization impedance in decoupled HER, and mass transfer Rm decreases remarkably in decoupled OER. OER shows lower Rct with Fe species existence and lower total polarization impedance than HER. Rm in decoupled HER increases by 38.24% and OER by 29.82% during prolonged decoupled test. This study provides valuable insights into the impedance contributions and kinetic mechanisms through novel electrolysis approaches, guiding further optimization of decoupled electrolyzer and electrode.

Detection of Impedance Inhomogeneity in Lithium-Ion Battery Packs Based on Local Outlier Factor

The inhomogeneity between cells is the main cause of failure and thermal runaway in Lithium-ion battery packs. Electrochemical Impedance Spectroscopy (EIS) is a non-destructive testing technique that can map the complex reaction processes inside the battery. It can detect and characterise battery anomalies and inconsistencies. This study proposes a method for detecting impedance inconsistencies in Lithium-ion batteries. The method involves conducting a battery EIS test and Distribution of Relaxation Times (DRT) analysis to extract characteristic frequency points in the full frequency band. These points are less affected by the State of Charge (SOC) and have a strong correlation with temperature, charge/discharge rate, and cycles. An anomaly detection characteristic impedance frequency of 136.2644 Hz was determined for a cell in a Lithium-ion battery pack. Single-frequency point impedance acquisition solves the problem of lengthy measurements and identification of anomalies throughout the frequency band. The experiment demonstrates a significant reduction in impedance measurement time, from 1.05 h to just 54 s. The LOF was used to identify anomalies in the EIS data at this characteristic frequency. The detection results were consistent with the actual conditions of the battery pack in the laboratory, which verifies the feasibility of this detection method. The LOF algorithm was chosen due to its superior performance in terms of FAR (False Alarm Rate), MAR (Missing Alarm Rate), and its fast anomaly identification time of only 0.1518 ms. The method does not involve complex mathematical models or parameter identification. This helps to achieve efficient anomaly identification and timely warning of single cells in the battery pack.

Enhanced temporal prediction of electrochemical impedance spectroscopy using long short-term memory neural networks

Large-scale applications of many electrochemical energy devices, such as batteries, fuel cells, and electrolyzers, are hindered by insufficient lifetime and durability. Traditional methods for assessing device reliability are time-consuming and resource-intensive, necessitating alternative approaches. This study presents a novel prediction framework that integrates electrochemical impedance spectroscopy (EIS) with advanced long short-term memory (LSTM) neural networks, leveraging a distribution of relaxation time (DRT)-assisted approach. Compared to the previously proposed direct EIS prediction framework, the DRT-assisted prediction framework significantly enhances the accuracy of DRT predictions and ensures the physical validity of EIS forecasts. Despite the improved prediction accuracy, forecasts extending to more distant future dates increase uncertainty, highlighting a trade-off between prediction duration and reliability. Overall, this framework provides valuable insights for optimizing the performance and lifetime predictions of electrochemical devices, offering a more robust tool for future research and application.