Data-driven diagnosis of high temperature PEM fuel cells based on the electrochemical impedance spectroscopy: Robustness improvement and evaluation

Utilizing machine learning techniques for data-driven diagnosis of high temperature PEM fuel cells is beneficial and meaningful to the system durability. Nevertheless, ensuring the robustness of diagnosis remains a critical and challenging task in real application. To enhance the robustness of diagnosis and achieve a more thorough evaluation of diagnostic performance, a robust diagnostic procedure based on electrochemical impedance spectroscopy (EIS) and a new method for evaluation of the diagnosis robustness was proposed and investigated in this work. To improve the diagnosis robustness: (1) the degradation mechanism of different faults in the high temperature PEM fuel cell was first analyzed via the distribution of relaxation time of EIS to determine the equivalent circuit model (ECM) with better interpretability, simplicity and accuracy;(2) the feature extraction was implemented on the identified parameters of the ECM and extra attention was paid to distinguishing between the long-term normal degradation and other faults;(3) a Siamese Network was adopted to get features with higher robustness in a new embedding. The diagnosis was conducted using 6 classic classification algorithms—support vector machine (SVM), K-nearest neighbor (KNN), logistic regression (LR), decision tree (DT), random forest (RF), and Naive Bayes employing a dataset comprising a total of 1935 collected EIS. To evaluate the robustness of trained models: (1) different levels of errors were added to the features for performance evaluation;(2) a robustness coefficient (Roubust_C) was defined for a quantified and explicit evaluation of the diagnosis robustness. The diagnostic models employing the proposed feature extraction method can not only achieve the higher performance of around 100% but also higher robustness for diagnosis models. Despite the initial performance being similar, the KNN demonstrated a superior robustness after feature selection and re-embedding by triplet-loss method, which suggests the necessity of robustness evaluation for the machine learning models and the effectiveness of the defined robustness coefficient. This work hopes to give new insights to the robust diagnosis of high temperature PEM fuel cells and more comprehensive performance evaluation of the data-driven method for diagnostic application.

Analysis of electrochemical impedance and XRD spectroscopy for complex self-assembled film on silver

Self-assembled monolayers （SAMs） of （3-mercaptopropy） trimethoxysilane （3-MtrF） chemisorbed on silver surfaces were chemically ＂modified by 1-octadecanethiol to form self-assembled mixed-monolayers （SAMM） and the co-polymer of N-vinylcarbazole and methyl methacrylate ester （to form complex selfassembled film （CSAF））. The oxidation resistance of these barriers on silver surfaces and some influential factors concerned processes were analyzed by electrochemical impedance spectroscopy （EIS） in a 10% NaOH aqueous solution at oxidation potential. X-ray diffraction （XRD） spectroscopy shows that the oxidation occurring on the silver surface may be restrained effectively due to the coating barrier, and CSAF（Ⅱ） is the best one. Studies also reveal that oxide processes of bare silver and a series of modified silver electrodes in a 10% NaOH aqueous solution are of more than two relaxation time constants.

Constituent phases of the passive film formed on 2205 stainless steel by dynamic electrochemical impedance spectroscopy

The passive film formed on 2205 duplex stainless steel（DSS） in 0.5 M NaHCO3＋0.5 M NaCl aqueous solution was characterized by electrochemical measurements,including potentiodynamic anodic polarization and dynamic electrochemical impedance spectroscopy（DEIS）.The results demonstrate that there is a great difference between the passive film evolutions of ferrite and austenite.The impedance values of ferrite are higher than those of austenite.The impedance peaks of ferritic and austenitic phases correspond to the potential of 0.15 and 0.25 V in the low potential range and correspond to 0.8 and 0.75 V in the high potential range.The evolutions of the capacitance of both phases are reverse compared to the evolutions of impedance.The thickness variations obtained from capacitance agree well with those of impedance analysis.The results can be used to explain why pitting corrosion occurs more easily in austenite phase than in ferrite phase.

Interpretation of electrochemical impedance spectroscopy(EIS) circuit model for soils

Based on three different kinds of conductive paths in microstructure of soil and theory of electrochemical impedance spectroscopy(EIS), an integrated equivalent circuit model and impedance formula for soils were proposed, which contain 6 meaningful resistance and reactance parameters. Considering the conductive properties of soils and dispersion effects, mathematical equations for impedance under various circuit models were deduced and studied. The mathematical expression presents two semicircles for theoretical EIS Nyquist spectrum, in which the center of one semicircle is degraded to simply the equivalent model. Based on the measured parameters of EIS Nyquist spectrum, meaningful soil parameters can easily be determined. Additionally, EIS was used to investigate the soil properties with different water contents along with the mathematical relationships and mechanism between the physical parameters and water content. Magnitude of the impedance decreases with the increase of testing frequency and water content for Bode graphs. The proposed model would help us to better understand the soil microstructure and properties and offer more reasonable explanations for EIS spectra.

Study on pitting process of 316L stainless steel by means of staircase potential electrochemical impedance spectroscopy

Pitting corrosion of 316L stainless steel in NaCl solution was investigated by means of staircase potential electrochemical impedance spectroscopy（SPEIS）.The investigation focused on the transition of stainless steel from the passive state to pitting corrosion.Based on the evolution of electrical parameters of the equivalent electrical circuit,it is suggested that the most probable mechanism of pit creation is the film breaking model.The result demonstrates that staircase potential electrochemical impedance spectroscopy is an effective method for the investigation of pitting corrosion.

Electrochemical impedance spectroscopy study on the corrosion of the weld zone of 3Cr steel welded joints in CO_2 environments

The welded joints of 3Cr pipeline steel were fabricated with commercial welding wire using the gas tungsten arc welding （GTAW） technique. Potentiodynamic polarization curves, linear polarization resistance （LPR）, electrochemical impedance spectroscopy （EIS）, scan- ning electron microscopy （SEM）, and energy-dispersive spectrometry （EDS） were used to investigate the corrosion resistance and the growth of a corrosion film on the weld zone （WZ）. The changes in electrochemical characteristics of the film were obtained through fitting of the EIS data. The results showed that the average corrosion rate of the WZ in CO2 environments first increased, then fluctuated, and finally de- creased gradually. The formation of the film on the WZ was divided into three stages： dynamic adsorption, incomplete-coverage layer forma- tion, and integral layer formation.

ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY STUDY OF CORROSION INHIBITION OF MODIFIED LIGNOSULPHONATE FOR CARBON STEEL

The corrosion inhibition for carbon steel in circulating cooling water by modified lignosulphonate has been investigated using electrochemical impedance spectroscopy technique. Results show that the inhibition efficiency of modified lignosulphonate GCL2 is a great improvement on that of lignosulphonate. The maximum inhibition efficiency of GCL2 reaches 99.21% at the concentration of 400mg·L^-1 at 303K. The corrosion inhibition of GCL2 is attributed to forming adsorption film on the metal surface for the electrochemical impedance spectroscopy in GCL2 solution shows more than one time-constant.Moreover,results also indicate that it is more efficient in stirring solution than in still solution for GCL2 because the constant of adsorption in stirring solution is much larger than that in still solution. The adsorption of inhibitor GCL2 follows Langmuir＇s adsorption isotherm.

Research progress of the electrochemical impedance technique applied to the high-capacity lithium-ion battery

The world's energy system is changing dramatically.Li-ion battery,as a powerful and highly effective energy storage technique,is crucial to the new energy revolution for its continuously expanding application in electric vehicles and grids.Over the entire lifetime of these power batteries,it is essential to monitor their state of health not only for the predicted mileage and safety management of the running electric vehicles,but also for an"end-of-life"evaluation for their repurpose.Electrochemical impedance spectroscopy(EIS)has been widely used to diagnose the health state of batteries quickly and nondestructively.In this review,we have outlined the working principles of several electrochemical impedance techniques and further evaluated their application prospects to achieve the goal of nondestructive testing of battery health.EIS can scientifically and reasonably perform real-time monitoring and evaluation of electric vehicle power batteries in the future and play an important role in vehicle safety and battery gradient utilization.

Localized Electrochemical Impedance Spectroscopy Study on the Corrosion Behavior of Fe-Cr Alloy in the Solution with Cl^- and SO_4^(2-)

The corrosion behaviors of Fe-Cr alloy under three different pH values solutions with C1- and SO42- were investigated by localized electrochemical impedance spectroscopy （LEIS） measurements and the corrosion products were analyzed by laser Raman spectrometry. The results show that the high corrosion resistance of Fe-Cr Alloy is attributed to a passive film which is formed more easily when the alloy contains a large quantity of Cr element. However, its corrosion resistance varies in the solutions with different pH values, especially in the initial corrosion. The average impedance values in neutral and alkaline solution are much higher than that in acidic solution because the passive film is more likely to dissolve in the acidic condition. Moreover, the destructive effect of C1- and SO42 ions on the passive film is also demonstrated in corrosion process through the change of the impedance value with the steeping time.

Fast Evaluation of Degradation Degree of Organic Coatings by Analyzing Electrochemical Impedance Spectroscopy Data

The degradation coefficient is proposed to evaluate the degradation degree of organic coatings by directly anaIyzing the Bode plots of the electrochemical impedance spectroscopy （EIS） data. This paper investigated the degradation of phenolic epoxy coating/tinplate system by EIS and the degradation coefficient value, which correlates well with the results of breakpoint frequency and variation of phase angle at 10 Hz. Furthermore, the degradation process was confirmed by scanning electron microscope （SEM） and scanning probe microscopy （SPM）. It is concluded that degradation coefficient can be used for the fast evaluation of degradation degree of organic coatings in practical appli- cations.

Semi-supervised estimation of capacity degradation for lithium ion batteries with electrochemical impedance spectroscopy

Machine learning-based methods have emerged as a promising solution to accurate battery capacity estimation for battery management systems.However,they are generally developed in a supervised manner which requires a considerable number of input features and corresponding capacities,leading to prohibitive costs and efforts for data collection.In response to this issue,this study proposes a convolutional neural network(CNN)based method to perform end-to-end capacity estimation by taking only raw impedance spectra as input.More importantly,an input reconstruction module is devised to effectively exploit impedance spectra without corresponding capacities in the training process,thereby significantly alleviating the cost of collecting training data.Two large battery degradation datasets encompassing over 4700 impedance spectra are developed to validate the proposed method.The results show that accurate capacity estimation can be achieved when substantial training samples with measured capacities are given.However,the estimation performance of supervised machine learning algorithms sharply deteriorates when fewer samples with measured capacities are available.In this case,the proposed method outperforms supervised benchmarks and can reduce the root mean square error by up to 50.66%.A further validation under different current rates and states of charge confirms the effectiveness of the proposed method.Our method provides a flexible approach to take advantage of unlabelled samples for developing data-driven models and is promising to be generalised to other battery management tasks.

Electrochemical impedance characteristics of LC4 aluminum alloy treated with ZH1 technique

Zhl technique was used to form a corrosion resistant layer on LC4alloy. the composition of the layer was studied by X-rayphotoelectron spectroscopy (XPS). It is found that the layer iscomposed of oxides of metals on the sub- strate, such as Al_2O_3,ZnO, MgO_, CuO, and MnO_2. The elecrochemical impedance spectrums(EIS) of LC4 aluminum alloy specimen were measured in NaCl solutionsto study the mechanism of the corrosion resistance of the alloytreated with Zh1 technique.

Effect of sulphate-reducing bacteria on the electrochemical impedance spectroscopy characteristics of 1Cr18Ni9Ti

The electrochemical characteristics of 1Cr18Ni9Ti in sulphate-reducing bacteria （SRB） solutions and the biofilm of SRB on the surface of the 1Cr18Ni9Ti electrode were studied by electrochemical, microbiological, and surface analysis methods. Electrochemical impedance spectroscopy （EIS） of 1Cr18Ni9Ti was measured in the solutions with and without SRB at the culture time of 2, 4, 8 d, respectively. The measurement used two test methods, the nonimmersion electrode method and the immersion electrode method. It was found that the polarization resistance （Rp） of 1Cr18Ni9Ti in the solutions without SRB is the greatest for each test method. When using the nonimmersion electrode method, Rp shifts negatively at first and then positively, and the time constant is only one. Although using the immersion electrode method, the Rp shifts positively at first and then negatively, and the time constant also changes when the biofilm forms. The biofilm observed through SEM is with pores. It was demonstrated that SRB has accelerated corrosion action on 1Cr18Ni9Ti. The protection effect of the biofilm on the electrode depends on the compact degree of the film.

Evaluation of electrochemical impedance and biocorrosion characteristics of as-cast and T4 heat treated AZ91 Mg-alloys in Ringer’s solution

The present study aims at understanding the electrochemical impedance and biocorrosion characteristics of AZ91 Mg-alloy in Ringer’s solution.As-cast AZ91 Mg-alloy was subjected to T4 heat treatment in a way to homogenize its microstructure by dissolving most of theβ-Mg 17 Al 12 phase at the vicinity of grain boundaries.The electrochemical impedance and biocorrosion performances of these two different microstructures(as-cast and T4 heat treated AZ91 Mg-alloys)in Ringer solution were evaluated by electrochemical impendence spectroscopy,potentiodynamic polarization and weight loss method.EIS spectra showed that both microstructures exhibit similar dynamic response as a function of the immersion time;however,the value of impedance and maximum phase angle are about 50%higher in as-cast AZ91 Mg-alloy as compared to that of homogenized AZ91 Mg-alloy.Weight loss measurement indicated that corrosion resistance of as-cast AZ91 was significantly better than that of homogenized AZ91.Microstructural and XRD analysis revealed that as-cast AZ91 contains a passive film of MgCO_(3)and CaCO_(3)precipitates with near spherical morphologies,whereas homogenized AZ91 comprised mainly unstable Mg(OH)_(2)film featured by irregular plate-like morphologies.

Comparative investigation on copper atmospheric corrosion by electrochemical impedance and electrical resistance sensors

Electrochemical impedance(EIS)and thin electrical resistance(ER)sensors were invented for atmospheric corrosion measurement of copper(Cu)during cyclic wetting−drying/high−low temperature tests and field exposure tests.Three-month field exposure results showed that average corrosion rate of Cu measured by ER sensor was well in accordance with that by weight loss method.During cyclic wetting−drying test,EIS was proven to reflect sensitively time of wetting and drying on the surface of sensor.Although corrosion rate obtained from EIS had a similar tendency to that obtained from ER sensors,the former was more dependent on environmental humidity than the latter.When relative humidity was low than 60%,corrosion rate of Cu measured by EIS was much lower than that by weight loss method,mainly attributing to the fact that impedance sensor failed to detect corrosion current of interlaced Cu electrodes due to the breakdown of conductive passage composed of absorbed thin liquid film under low humidity condition.Promisingly,ER sensor was proven to be more suitable for atmospheric corrosion monitoring than electrochemical techniques because it could sensitively monitor thickness loss of Cu foil according to the Ohmic law,no matter how dry or wet the sensor surface is.

Electrochemical impedance analysis of nanoporous TiO_2 electrode at low bias potential

TiO2 colloid was prepared by the sol-gel method and was bladed on transparent conduction glass to made nanoporous electrode. The impedance performance of TiO2 electrode was studied at various bias potential.A simplified equivalent circuit was proposed to investigate the charge transport impedance of TiO2 film and good fitting results were obtained.

ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY DURING CORROSION PROCESS OF 8090 Al-Li ALLOY IN EXCO SOLUTION

The corrosion behavior and electrochemical impedance spectroscopy (EIS) features of 8090 Al-Li alloys in EXCO solution were investigated, and the EIS was simulated using an equivalent circuit. At the beginning of immersion in EXCO solution, the EIS is comprised by a depressed capacitive arc at high-mediate frequency and an inductive arc at low frequency, and the inductive component decreases and disappears with im- mersion time. Once exfoliation or severe pitting corrosion is produced, two capacitive arcs appear in the EIS. These two capacitive arcs are originated from the two parts of the corroded alloy surface, the original flat alloy surface and the new inter-face exposed to the aggressive EXCO solution due to the exfoliation or pitting corrosion. Some corrosion development features of 8090 Al-Li alloys in EXCO solution can be obtained through simulated EIS information.

Electrochemical Impedance Analysis of Biofunctionalized Conducting Polymer-Modified Graphene-CNTs Nanocomposite for Protein Detection

We report an electrodeposited poly(pyrrole-co-pyrrolepropylic acid) copolymer modified electroactive graphene-carbon nanotubes composite deposited on a glassy carbon electrode to detect the protein antigen(cTnI). The copolymer provides pendant carboxyl groups for the site-specific covalent immobilization of protein antibody, antitroponin I. The hybrid nanocomposite was used as a transducer for biointerfacial impedance sensing for cTnI detection.The results show that the hybrid exhibits a pseudo capacitive behaviour with a maximum phase angle of 49° near 1 Hz,which is due to the inhomogeneous and porous structure of the hybrid composition. The constant phase element of copolymer is 0.61(n = 0.61), whereas, it is 0.88(n = 0.88) for the hybrid composites, indicating a comparatively homogeneous microstructure after biomolecular functionalization. The transducer shows a linear change in charge transfer characteristic(R_(et)) on cTnI immunoreaction for spiked human serum in the concentration range of 1.0 pg mL^(-1)–10.0 ng mL^(-1). The sensitivity of the transducer is 167.8 ± 14.2 Ω cm^2 per decade, and it also exhibits high specificity and good reproducibility.

Electrochemical impedance spectra of V_2O_5 xerogel films with intercalation of lithium ion

Vanadium pentoxide xerogel films used for lithium rechargeable batteries were prepared from crystalline c-V2O5 by melt quenching method,then the electrochemical process of lithium intercalation into vanadium pentoxide xerogel films was simulated with an equivalent circuit model, which was derived from the mechanism of electrode reactions. Measured electrochemical impedance spectra at various electrode potentials were analyzed by using the complex non-linear least-squares fitting method. The results show that impedance spectra consist of 2 high-to- medium frequency depressed arcs and a low frequency straight line. The high frequency arc is attributed to the absorption reaction of lithium ions into the oxide film, the medium frequency arc is attributed to the charge transfer reaction at the vanadium oxide/electrolyte interface and the low frequency is characterized by a straight line with a phase angle of 45° corresponding to the diffusion of lithium ion through vanadium oxide phase. The experimental and calculated results are compared and discussed focusing on the electrochemical performance and the state of charge of the electrode. Moreover, the high consistence of the fitted values of the model to the experimental data indicates that this mathematical model does give a satisfying description of the intercalation process of vanadium pentoxide xerogel films.

Exfoliation corrosion susceptibility of 8090 Al-Li alloy examined by electrochemical impedance spectroscopy

The exfoliation corrosion susceptibility and electrochemical impedance spectrosc opy(EIS) of rolled and peak-aged 8090 Al-Li alloys in EXCO solution were studi ed,and the EIS after exfoliation was simulated. Once exfoliation occurs,two ca pacitive arcs appear in the EIS at high-mediate frequency and mediate-low freq uency respectively. The exfoliation-attacked alloy surface consists of two part s,an original flat alloy surface and a new inter-face exposed to EXCO solution due to the exfoliation. The capacitance corresponding to the new exfoliation in ter-face increases approximately linearly with time at early exfoliation stage,due to the enlargement of the new inter-face. Then it maintains stable,due to the corrosion product covering on the new inter-face. The exfoliation suscepti bility can be judged through the average slope of the capacitance vs time curve of the early exfoliation stage. This average slope of the rolled 8090 alloy is m uch higher than that of the peak-aged 8090 alloy,accordingly the rolled 8090 a lloy is more susceptible to exfoliation than the peak-aged 8090 alloy.