EIS analysis of electrode kinetics for La2NiO4 + δ cathode in contact with Ce0.8Sm0.2O1.9 electrolyte: from DRT analysis to physical model of the electrochemical process

Antonova, E.P.; Khodimchuk, Anna V.; Usov, G. R.; Tropin, E. S.; Фарленков, А. С.; Khrustov, A. V.; Ananyev, M.V.

doi:10.1007/s10008-019-04224-6

Cited by 32 publications

(11 citation statements)

References 18 publications

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“…The Rhf resistance was subtracted from the data set. All the spectra have the shape of asymmetric deformed semicircles, similar to the Gerischer impedance, and are well described by the Gerischer element connected in series with the (RQ) element, i.e., a parallel combination of a resistance and a CPE (constant phase element or Q-element: ( ) = ( ( ) ) −1 ), which correlates well with [60,61]. When using this equivalent circuit, the calculation error did not exceed 3-5%.…”

Section: Oxygen Mobility and Surface Reactivitymentioning

confidence: 72%

Correlation between Structural and Transport Properties of Ca-Doped La Nickelates and Their Electrochemical Performance

et al. 2021

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This work presents the results from a study of the structure and transport properties of Ca-doped La2NiO4+δ. La2−xCaxNiO4+δ (x = 0–0.4) materials that were synthesized via combustion of organic-nitrate precursors and characterized by X-ray diffraction (XRD), in situ XRD using synchrotron radiation, thermogravimetric analysis (TGA) and isotope exchange of oxygen with C18O2. The structure was defined as orthorhombic (Fmmm) for x = 0 and tetragonal (I4/mmm) for x = 0.1–0.4. Changes that occurred in the unit cell parameters and volume as the temperature changed during heating were shown to be caused by the excess oxygen loss. Typical for Ruddlesden–Popper phases, oxygen mobility and surface reactivity decreased as the Ca content was increased due to a reduction in the over-stoichiometric oxygen content with the exception of x = 0.1. This composition demonstrated its superior oxygen transport properties compared to La2NiO4+δ due to the enhanced oxygen mobility caused by structural features. Electrochemical data obtained showed relatively low polarization resistance for the electrodes with a low Ca content, which correlates well with oxygen transport properties.

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Section: Oxygen Mobility and Surface Reactivitymentioning

confidence: 72%

Correlation between Structural and Transport Properties of Ca-Doped La Nickelates and Their Electrochemical Performance

et al. 2021

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“…Similar behavior for the DRT function has been observed previously in [45] for Ni-SDC anodes. Based on the results, obtained in [44] we can conclude that the rate of the hydrogen oxidation is limited by oxygen ionic diffusion in SDC, reactions between adsorbed forms of the potential determining particles on the anode surface as well as the gas diffusion. For fuel electrodes, two peaks at the frequencies of 0.3 and 5 Hz can be found at the DRT function at 600 • C. While the temperature increases the DRT function becomes more complicated.…”

Section: Electrochemical Cells and Performancementioning

confidence: 82%

“…It can be seen that, for oxygen electrodes, the functions consist of several processes. The low-frequency step can be assigned to the gas diffusion [25], while the three steps in the middle-frequency region have been recently identified in [44] as oxygen ion diffusion on the electrode/electrolyte interface, charge transfer in the adsorption layer, and oxygen surface exchange and diffusion in the electrode material. Impedance spectra for symmetrical electrochemical cells are depicted in Figure 8A,B.…”

Section: Electrochemical Cells and Performancementioning

confidence: 99%

Application of Promising Electrode Materials in Contact with a Thin-Layer ZrO2-Based Supporting Electrolyte for Solid Oxide Fuel Cells

et al. 2020

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The paper presents the results of an investigation into thin single- and triple-layer ZrO2-Sc2O3-based electrolytes prepared using the tape-casting technique in combination with promising electrodes based on La2NiO4+δ and Ni-Ce0.8Sm0.2O2-δ materials. It is shown that pressing and joint sintering of single electrolyte layers allows multilayer structures to be obtained that are free of defects at the layer interface. Electrical conductivity measurements of a triple-layer electrolyte carried out in longitudinal and transverse directions with both direct and alternating current showed resistance of the interface between the layers on the total resistance of the electrolyte to be minimal. Long-term tests have shown that the greatest degradation in resistance over time occurs in the case of an electrolyte with a tetragonal structure. Symmetrical electrochemical cells with electrodes fabricated using a screen-printing method were examined by means of electrochemical impedance spectroscopy. The polarization resistance of the electrodes was 0.45 and 0.16 Ohm∙cm2 at 800 °C for the fuel and oxygen electrodes, respectively. The distribution of relaxation times method was applied for impedance data analysis. During tests of a single solid oxide fuel cell comprising a supporting triple-layer electrolyte having a thickness of 300 microns, a power density of about 160 mW/cm2 at 850 °C was obtained using wet hydrogen as fuel and air as an oxidizing gas.

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“…In order to analyze the chromium influence on these stages, the obtained impedance spectra were analyzed by means of the DRT method. Recent studies on the electrode kinetics for the La 2 NiO 4+δ cathode in contact with the Ce 0.8 Sm 0.2 O 1.9 electrolyte (but without a chromium source) using EIS and DRT analysis are described in Reference66. DRT functions were calculated only for MEIAs with Pt and Crofer 22 APU interconnects due to the fact that the impedance data of MEIAs with the 08X17T interconnect were of insufficient quality.…”

Section: Resultsmentioning

confidence: 99%

Revealing the degradation mechanism of the lanthanum nickelates based double‐layer electrodes during long‐term tests in contact with chromium‐containing steel interconnects

Solodyankin

Еремин

Ananyev

et al. 2022

Intl J of Energy Research

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Summary This paper focuses on the long‐term tests for 1000 hours of different Membrane‐Electrode‐Interconnect Assemblies (MEIAs), consisting of a steel interconnect and an asymmetrical solid electrochemical cell based on the Ce0.8Sm0.2O2−δ electrolyte, the double‐layer working electrode with the La2NiO4+δ – Ce0.8Sm0.2O2−δ composite functional layer and the LaNi0.6Fe0.4O3−δ current collector layer, and the platinum reference electrode (O2, LaNi0.6Fe0.4O3−δ|La2NiO4+δ – Ce0.8Sm0.2O2−δ|Ce0.8Sm0.2O2−δ|Pt, O2). These tests were carried out on MEIAs with two types of Cr‐based stainless steels, Crofer 22 APU and 08X17T, with and without protective coatings at 850°C in air. The electrochemical performance of MEIAs was studied without polarization as well as under cathodic and anodic polarization (current density was 0.5 A cm−2) by means of electrochemical impedance spectroscopy (EIS) and the distribution of relaxation times method (DRT). It was found that the proposed protective coatings for the stainless steels inhibit chromium poisoning without polarization and under anodic polarization: for Crofer 22 APU the degradation of the polarization resistance after ~1100 hours of exposure was 0.35 ± 0.05 Ω cm2, and for 08X17T it was from 0.40 ± 0.05 Ω cm2. In the case of cathodic polarization, the degradation of the polarization resistance remained at a very high level, comparable to uncoated samples: for Crofer 22 APU and 08X17T with coatings, it was about 0.6 to 0.8 Ω cm2 after ~1100 hours. Post‐test analysis of the microstructure and chemical composition of the interconnect ‐ double‐layer electrode interface was carried out using scanning electron microscopy (SEM), wavelength dispersive X‐ray spectrometry (WDS), and respective image analysis of the obtained data. The influence of chromium poisoning on the degradation was considered for different stages of the electrode performance. It was demonstrated that chromium predominantly accumulates in the current collector layer in the case of anodic polarization and in the functional layer in the cases of open circuit and cathodic polarization. For the first time, a combined electrochemical‐chemical degradation mechanism of the La2NiO4+δ – Ce0.8Sm0.2O2−δ functional layer was discussed. Highlights Long‐term tests of Membrane‐Electrode‐Inteconnect Assembles (MEIAs) were done. Chromium poisoning was detected on MEIAs with the interconnects without coating. Cathodic polarization terminates the protective properties of the coatings. Chromium poisoning decreases electrode activity to oxygen exchange and diffusivity. A combined electrochemical‐chemical degradation mechanism of the functional layer was revealed.

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EIS analysis of electrode kinetics for La2NiO4 + δ cathode in contact with Ce0.8Sm0.2O1.9 electrolyte: from DRT analysis to physical model of the electrochemical process

Cited by 32 publications

References 18 publications

Correlation between Structural and Transport Properties of Ca-Doped La Nickelates and Their Electrochemical Performance

Correlation between Structural and Transport Properties of Ca-Doped La Nickelates and Their Electrochemical Performance

Application of Promising Electrode Materials in Contact with a Thin-Layer ZrO2-Based Supporting Electrolyte for Solid Oxide Fuel Cells

Revealing the degradation mechanism of the lanthanum nickelates based double‐layer electrodes during long‐term tests in contact with chromium‐containing steel interconnects

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