Model-assisted identification of solid oxide cell elementary processes by electrochemical impedance spectroscopy measurements

Caliandro, Priscilla; Nakajo, Arata; Diethelm, Stefan; herle, Jan Van

doi:10.1016/j.jpowsour.2019.226838

Cited by 113 publications

(111 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3.2 and Ref. [18]). The analysis predicts a decrease in θ Ni by up to 4-6 deg in the electrolysis experiments, but variations after fuel cell operation should not be observed.…”

Section: Changes In Ni Dihedral Angle Predicted By Thementioning

confidence: 89%

“…The "P5" surface specific resistance and capacitance were calculated using the area under the DRT and corresponding peak position, respectively. Both were estimated by optimization-based fitting that minimizes the difference between the sum of the estimated areas under each detected peak in the DRT and that under the total DRT [32]. The consistency of the sum of the deconvoluted resistances with the polarization resistance obtained from the Nyquist plot (R p ) was successfully verified.…”

Section: Methodsmentioning

confidence: 96%

“…3, using the experimental data and the DRT method described in Ref. [18]. The EIS sensitivity analyses were performed at 785°C, with a current density range from −0.7 A cm −2 (SOE) to 0.7 A cm −2 (SOFC) and a feed of 50% H 2 and 50% H 2 O.…”

Section: Methodsmentioning

confidence: 99%

“…The distributed charge transfer process attributed to the Ni-YSZ electrode is that referred as "P5" in Refs. [18,32]. The "P5" surface specific resistance and capacitance were calculated using the area under the DRT and corresponding peak position, respectively.…”

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Nakajo

Rinaldi

Caliandro

et al. 2020

Journal of Electrochemical Energy Conversion and Storage

Self Cite

View full text Add to dashboard Cite

Microstructural changes in Ni–yttria stabilized zirconia (YSZ) near the YSZ electrolyte were examined by three-dimensional (3D) electron microscopy after electrolysis and fuel cell operation up to 10,700 h and 15,000 h, respectively. The depletion of Ni and three-phase boundaries (TPBs) close to the electrolyte was detected upon cathodic polarization. It corresponded to spatial variations of dihedral angles (θ) at TPBs and Ni surface curvature along the direction perpendicular to the electrolyte, which comport with electrowetting and Zener pinning theory on several aspects. θNi decreased by up to 6 deg next to the electrolyte after electrolysis but remained uniform after fuel cell operation. This is in line with predictions from electrowetting theory with capacitances measured by electrochemical impedance spectroscopy and distribution of relaxation times. The decrease in θNi was concurrent to transition toward concave Ni/pore interfacial shapes and lower genus of the Ni phase, which suggests the pinch-off of Ni ligaments following surface diffusion-controlled Rayleigh instability. The increase in absolute mean curvature near the electrolyte interface is a driving force for outward transport of Ni. The decrease in θYSZ further suggests that TPB lines relocate on YSZ surface features that provide higher Zener pinning force. In contrast, few localized contact losses between Ni and YSZ that can also occur under high cathodic polarization and trigger Ni depletion were detected. The results are expected to advance the understanding of the driving forces that cause Ni depletion near the electrolyte in electrolysis for the design of improved solid oxide cell electrode microstructures.

show abstract

“…3.2 and Ref. [18]). The analysis predicts a decrease in θ Ni by up to 4-6 deg in the electrolysis experiments, but variations after fuel cell operation should not be observed.…”

Section: Changes In Ni Dihedral Angle Predicted By Thementioning

confidence: 89%

Section: Methodsmentioning

confidence: 96%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Nakajo

Rinaldi

Caliandro

et al. 2020

Journal of Electrochemical Energy Conversion and Storage

Self Cite

View full text Add to dashboard Cite

show abstract

“…This process involves four elementary electrode processes: CO 2 adsorption on the cathode surface (P3), dissociation of the carbonate intermediate (P4), transfer of O 2through the LSGM electrolyte (P1), and evolution of O 2into O 2 in the anode (P2). [45] First, the effects of CO 2 /CO partial pressure on the corresponding DRT plots for the LSCM-CMF composite oxide electrode are shown in Figure 7a. Although P1 and P2 are slightly different under various CO 2 /CO pressure values, the two processes are independent of the partial pressures of CO 2 and CO, whereas P3 and P4 are strongly affected by them.…”

Section: Electrocatalytic Effects Of Cmf-added Lscm For Co 2 Electrolysismentioning

confidence: 99%

Enhancing Electrochemical CO₂ Reduction using Ce(Mn,Fe)O₂ with La(Sr)Cr(Mn)O₃ Cathode for High‐Temperature Solid Oxide Electrolysis Cells

Lee

Kim

Lee

et al. 2021

Advanced Energy Materials

View full text Add to dashboard Cite

is mostly dominated by the cathode reaction related to the CO/CO 2 redox couple on the electrode surface. SOECs mostly utilize materials and techniques relevant to solid oxide fuel cells (SOFCs), as they operate in the reverse mode of SOFCs. However, some materials have not been specifically tailored for CO 2 electrolysis conditions. Thus, several research groups have extensively searched for durable fuel electrodes that are suitable for both SOFC and SOEC conditions and provide high catalytic reactivity compared to the Ni-based blending electrodes for SOFCs. [15][16][17][18][19][20][21] The Ni-based cathode (fuel electrode) is easily deactivated by re-oxidation or carbon formation when directly exposed to the CO/CO 2 redox reaction and hydrocarbon atmosphere. [22,23] Therefore, the alternative cathode should have catalytic activity and electrical conductivity, and durability in terms of CO/CO 2 redox reaction. Consequently, redox stability and carbon coking tolerance have been considered as main factors when developing robust ceramic cathode (fuel electrode) candidates for CO 2 electrolysis in SOECs. Several conductive perovskite oxides have been reported to display re-oxidation resistance and coke tolerance as perovskite-type fuel electrode materials for the anode in SOFCs as well as the cathode in SOECs. [13][14][15][16][17][18][19][20] Among them, La(Sr)Cr(Mn)O 3-δ (LSCM) is one of the promising cathode materials for hydrocarbon-typed SOFCs because of its high redox stability and acceptable conductivity under the reducing conditions. [24] Irvine and Yue reported (La 0.75 Sr 0.25 ) 0.97 Cr 0.5 Mn 0.5 O 3-δ /Gd 0.1 Ge 0.9 O 1.95 (LSCM/GDC) as a composite ceramic cathode for CO 2 electrolysis. However the

show abstract

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

et al. 2022

View full text Add to dashboard Cite

metal oxide-based gas sensors, for which device performance relies on rapid oxygen exchange reactions at the gas-solid interfaces. [1][2][3][4][5][6][7] In SOFCs, the oxygen reduction reaction (ORR) occurs at the cathode and the corresponding polarization resistance depends on the adsorption/dissociation of oxygen species on the surface, followed by charge transfer between the surface and the adsorbed species, and finally the incorporation of charged oxygen ionic species into the electrode lattice. Although many studies related to improving the initial performance of mixed conducting metal oxides have been pursued to date, particularly focused on tuning the oxygen exchange coefficient (k chem ), the performance of such devices often degrades rapidly due to the inevitable poisoning by extrinsic sources over time during device operation. [8][9][10][11] Sources of Si-impurities are not only widely present in material processing and testing (e.g., the use of quartz reactors, furnace refractories, glass or glass-ceramic sealants, and thermal insulation materials), but also during device operation (e.g., volatile organic silicon compounds (VOSCs) and gas impurities). [11][12][13][14][15][16][17][18][19][20][21][22] Si-contamination is known to cause significant performance degradation of many electrochemical devices. [8] For example, Perz et al. showed that silica reacts with the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) surface, a mixed ionic and electronic conducting (MIEC) cathode commonly applied in SOFCs, forming a continuous La-Sr-silicate layer. [22] This impurity layer limits adsorption/dissociation of oxygen molecules on the LSCF surface, increasing the area-specific resistance (ASR) by a factor 6 after long-term operation (1340 h) at 700 °C. Zhao et al. reported the formation of a blocking siliceous layer on dense thin films of Pr 0.1 Ce 0.9 O 2-δ (PCO), originating from quartz tubes or furnace insulation utilized during measurement, leading to the degradation of the oxygen surface exchange coefficient (k chem ) by a factor 40. [19] Hertz et al. demonstrated the ability to reduce the ASR associated with thin film interdigitated Pt electrodes on a yttria-stabilized zirconia (YSZ) electrolyte by 1000-fold following HF etching of surface silica species, thereby allowing oxygen gas to readily access the triple phase reaction sites. [15] To date, most previous studies point to silica forming a continuous glassy blocking layer as the source of the degradation.Metal oxides are an important class of functional materials, and for many applications, ranging from solid oxide fuel/electrolysis cells, oxygen permeation membranes, and oxygen storage materials to gas sensors (semiconducting and electrolytic) and catalysts, the interaction between the surface and oxygen in the gas phase is central. Ubiquitous Si-impurities are known to impede this interaction, commonly attributed to the formation of glassy blocking layers on the surface. Here, the surface oxygen exchange coefficient (k chem ) is examined for Pr 0.1 Ce 0.9 O 2...

show abstract

Model-assisted identification of solid oxide cell elementary processes by electrochemical impedance spectroscopy measurements

Cited by 113 publications

References 31 publications

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Enhancing Electrochemical CO₂ Reduction using Ce(Mn,Fe)O₂ with La(Sr)Cr(Mn)O₃ Cathode for High‐Temperature Solid Oxide Electrolysis Cells

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

Contact Info

Product

Resources

About

Model-assisted identification of solid oxide cell elementary processes by electrochemical impedance spectroscopy measurements

Cited by 113 publications

References 31 publications

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Evolution of the Morphology Near Triple-Phase Boundaries in Ni–Yttria Stabilized Zirconia Electrodes Upon Cathodic Polarization

Enhancing Electrochemical CO2 Reduction using Ce(Mn,Fe)O2 with La(Sr)Cr(Mn)O3 Cathode for High‐Temperature Solid Oxide Electrolysis Cells

Tuning Surface Acidity of Mixed Conducting Electrodes: Recovery of Si‐Induced Degradation of Oxygen Exchange Rate and Area Specific Resistance

Contact Info

Product

Resources

About

Enhancing Electrochemical CO₂ Reduction using Ce(Mn,Fe)O₂ with La(Sr)Cr(Mn)O₃ Cathode for High‐Temperature Solid Oxide Electrolysis Cells