Interfacial Stability between Air Electrode and Ceria‐Based Electrolyte under Cathodic Polarization in Solid Oxide Fuel Cells

Quantitative estimation of triple phase boundaries in solid oxide fuel cell electrodes via artificial neural network

The rational design of healthier foods to control fat uptake in the diet is an emerging area of research. In order to address these dietary issues effectively one requires an improved understanding of the influence of food structure on the digestion of lipids. Despite the crucial roles played by interfaces in determining the stability of emulsions and the breakdown of emulsion structure on digestion, there are few systematic basic studies dealing directly with the effects of digestion conditions on interfacial structures. A major concern in the attempted manipulation of protein-based interfacial structures is the potential enzymatic breakdown of these structures during digestion. This study has been designed to investigate the effects of the proteolytic enzyme pepsin on β-lactoglobulin surface layers under in vitro gastric digestion. Interfacial dilatational rheology has been used to measure the evolution of the viscoelastic properties of the pre-formed interfacial protein networks. Furthermore, Atomic Force Microscopy (AFM) has been used to visualise directly the effects of degradation on model interfacial protein layers (β-lactoglobulin). The results obtained show that pepsin partially hydrolyses the surface-adsorbed β-lactoglobulin molecules under gastric conditions, but does not break the interconnected surface network. In order to investigate the influence of the presence of surfactants on the enzymatic digestion of emulsions, the effect of addition of the model surfactant Tween 20 on the pepsin-induced changes in interfacial structure under simulated gastric conditions was studied. Modification of the surface conformation of the proteins by surfactant, during ‘orogenic’ displacement, revealed an unexpected synergism which leads to enhanced hydrolysis of the proteins; hence, weakening the network and allowing rupture to occur at lower surface pressures. Such observations are important new generic features of the digestion process which could be potentially manipulated to control the enzyme hydrolysis, allowing rational design of food structures and manipulation of properties such as fat digestion.

Introduction Reversible solid oxide cells (r-SOCs) are attractive electrochemical energy devices that can operate as both solid oxide fuel cells (SOFCs) for power generation, and solid oxide electrolysis cells (SOECs) for steam electrolysis (1). Renewable power generation, such as wind and solar, depends on daily weather conditions and so that it is desirable to adjust the supply of fluctuating electricity to match demand using reversible energy devices such as r-SOCs. The operational concept of r-SOCs is schematically described in Figure 1. The aim of this study is to examine the electrochemical properties and durability of r-SOCs using alternative fuel electrode materials. Experimental Various r-SOCs were prepared using conventional and alternative fuel electrode materials. As the conventional materials, Ni-cermet with Sc2O3-doped ZrO2 (ScSZ) was used for the fuel electrode; dense 200 mm thick ScSZ membrane for the electrolyte; and La0.6Sr0.4Co0.2Fe0.8O0.3 oxide (LSCF) air electrode with Gd-doped CeO2 (Gd0.1Ce0.9O2) acting as a buffer layer between the ScSZ electrolyte and the LSCF air electrode. As alternative fuel electrode materials, GDC and/or La0.1Sr0.9TiO3 (LST) were used as the fuel electrode backbone. By applying the co-impregnation procedure of Ni and GDC, fuel electrodes with highly dispersed nanoparticles of Ni catalysts and GDC, denoted as Ni-GDC/LST-GDC, were prepared (2,3). A Pt-based reference electrode was deposited beside the air electrode, such that the fuel electrode potential was measured as the voltage between the fuel and reference electrodes.Current-voltage characteristics were characterized, including voltage cycle tests performed by switching the direction of current simulating r-SOC operation. Long-term durability tests in SOEC and SOFC modes were conducted at 800°C. Air was supplied to the air electrode, while 50%-humidified hydrogen gas was supplied to the fuel electrode. The current density in the SOFC and SOEC modes is denoted as positive and negative values, respectively. Results and discussion Figure 2 shows fuel electrode potential as a function of current density in both SOFC and SOEC modes. The cells with the Ni-zirconia cermet, GDC, LST, LST-GDC, and Ni-GDC/LST-GDC could be operated in both modes. In the SOFC mode, the conventional Ni-zirconia cermet exhibited the highest fuel electrode voltage among these materials studied. In contrast, in the SOEC mode, the GDC-containing materials exhibited lower (i.e. better) fuel electrode voltage compared to Ni-zirconia cermet even without Ni catalysts, indicating enhanced electrocatalytic activity of mixed-conducting GDC for the electrode reactions with water vapor at the fuel electrodes. Voltage cycle durability up to 1,000 cycles and long-term durability up to 1,000 hours could be measured. Latest results on the durability with various electrode materials will be presented. Acknowledgements A part of this study was supported by “Research and Development Program for Promoting Innovative Clean Energy Technologies Through International Collaboration” of the New Energy and Industrial Technology Development Organization (NEDO) (Project No. JPNP20005). References Q. Minh and M. B. Mogensen, Electrochem. Soc. Interface, 22, 55 (2013).Futamura, Y. Tachikawa, J. Matsuda, S. M. Lyth, Y, Shiratori, S. Taniguchi, and K. Sasaki, J. Electrochem. Soc., 164 (10), F3055 (2017).Futamura, A. Muramoto, Y. Tachikawa, J. Matsuda, S. M. Lyth, Y, Shiratori, S. Taniguchi, and K. Sasaki, International J. Hydrogen Energy, 44 (16), 8502 (2019). Figure 1

Solid oxide fuel cells (SOFCs) attract attentions as high-efficiency energy-conversion devices. In order to establish high-performance SOFCs, the slow electrode kinetics, which is often a main cause of the energy loss, should be improved. In present SOFCs, mixed ionic-electronic conducting (MIEC) oxides, such as (La,Sr)CoO3 -δ and (La,Sr)(Co,Fe)O3 -δ , are typically used as the cathode materials. In such an MIEC cathode, it is generally believed that electrochemical oxygen reduction reaction takes place mainly at the oxide surfaces (double phase boundary, DPB) and the contribution of the reaction at the electrode/electrolyte/gas interface (triple phase boundary, TPB) is insignificant. Therefore, researches on the kinetics of SOFC cathodic reaction have mostly concerned to investigate the surface reaction on the electrode oxides. In our previous works, the reaction distributions in MIEC SOFC electrodes were experimentally evaluated by using operando micro X-ray absorption spectroscopy (operando μ-XAS) [1, 2]. For more quantitative and precise investigation of the reaction distribution, we proposed a patterned thin film electrode, which is a kind of the columnar electrode simplifying the microstructures of a porous electrode [2]. However, the patterned thin film electrode in our previous work did not have triple phase boundaries, and it was thus impossible to discuss the contribution of TPB reaction to the total reaction. In this work, a patterned thin film electrode having triple phase boundaries was fabricated. (La,Sr)CoO3- d (LSC) was chosen as the model MIEC oxide for SOFC cathodes. The reaction distribution in this new type of the patterned thin film electrode was experimentally determined by using operando μ-XAS, and the results were compared with ones obtained with the old type of the patterned thin film electrode without TPB. It was found the effective reaction area tended to shrink by the introduction of TPB to the patterned thin film electrode. This fact might suggest that the reaction at TPBs in SOFC cathodes is not negligible even when MIEC oxides are used as electrode materials.

Triple-Phase Boundaries (TPBs) in Fuel Cells and Electrolyzers

The atmospheric pressure plasma spray processes for functional layers of the tubular solid oxide fuel cell are developed to build a fuel cell structure consisting of air electrode, ceramic electrolyte, and fuel electrode. Further more the characteristics of each film are also investigated. The layers of LSM (La0.65Sr0.35MnO3) air electrode and Ni/8YSZ fuel electrode have porosities of 23 ~32 % sufficient for supplying fuel and oxidant gases efficiently to electrochemical reaction interfaces. The measured electrical conductivities of the electrodes are higher than 90 S/cm at 1000 °C, which satisfy the requirement as the current collecting electrodes. The YSZ electrolyte film has a high ionic conductivity of 0.07 S/cm at 1000 °C, but shows a bit too porous to block the oxygen molecule penetration through it. A unit tubular SOFC is fabricated by the optimized plasma spray processes for depositing each functional film and forming a porous cylindrical supporting tube of the cell, and turns out to have a promising capability of electricity generation.

YSZ ( yttria-stabilized zirconia)-modified LSM composite cathodes were fabricated by formation of YSZ film on triple phase boundary (TPB) of LSM/YSZ/gas. The YSZ coating film greatly enlarged electrochemical reaction sites from the increase of additional TPB. The composite cathode was formed on thin YSZ electrolyte (about 30 Um thickness) supported on an anode and then I-V characterization and AC impedance analyses were performed at temperature between . As results of the impedance analysis on the cell at with humidified hydrogen as the fuel and air as the oxidant, R1 around the frequency of 1000 Hz represents the anode Polarization. R2 around the frequency of 100Hz indicates the cathode polarization, and R3 below the frequency of 10 Hz is the resistance of gas phase diffusion through the anode. The cell with the composite cathode produced power density of at air and oxygen atmosphere, respectively. The I-V curve could be divided into two parts showing distinctive behavior. At low current density region (part I) the performance decreased steeply and at high current density region (part II) the performance decreased gradually. At the part I the performance decrease was especially resulted from the large cathode polarization, while at the part H the performance decrease related to the electrolyte polarization.

The mechanical properties and formation mechanism of Al/Mg composite interface prepared by spark plasma sintering under different sintering pressures

Due to its chemical stability in acidic environments and high ionic conductivity, Nafion has proven to be an essential material in proton exchange membrane fuel cell (PEMFC) designs. Nafion functions as both a membrane – separating the two electrodes – and as a conductive binder in each catalyst layer (CL). Nano-thin films of Nafion ionomer allow protons to reach carbon-supported Pt catalysts. In addition to protons, oxygen and water also move through the nano-thin Nafion ionomer to and from reactive Pt sites. These physical transport processes directly impact PEMFC performance. Therefore, measuring and determining ways to improve upon each of these processes is critical in the development of high performance PEMFCs.In regards to thick Nafion membranes, conductivity and diffusion measurements can be readily performed in most laboratories. Nano-thin Nafion films on the other hand prove more challenging to study due to experimental limitations. Nevertheless, neutron reflectometry (NR) has been reported in literature as a capable technique to provide simultaneous quantitative structural and composition profiles for thin-film Nafion [1-5]. Results for Nafion at native silicon oxide interfaces show complex multi-layered structures forming distinct water-rich and water-poor regions [1-3]. Despite these advancements in our understanding of thin-film Nafion, it is still unclear how these observed structures may impact PEMFC performance. This is because silicon does not interface with Nafion in PEMFC CLs. Instead, carbon and Pt are the primary and secondary materials that interface with the thin-film ionomer. In the latter case, thin-film Nafion at Pt interfaces has been briefly studied in literature and shows significantly less structure than Nafion at silicon oxide interfaces [4,5]. Beyond the limited number of studies for Pt-Nafion interfaces, carbon-Nafion interface studies are even more scarce in literature [5]. This is likely because carbon black (i.e. the electron conductor in PEMFC CLs) is too rough to be used with NR. Therefore, to confidently assume the structure of Nafion at carbon black interfaces, trends from NR work on other carbon-based samples need to be compiled and compared, while considering their bonding structures and surface chemistries.In this work, we extend the understanding of thin-film Nafion at carbon interfaces by testing four different carbon-based substrates. Using thin-film Nafion (< 100 nm) deposited on each carbon sample, NR was performed in both dry and humidified environments. Fitting the data to these experiments, results suggest a variety of polymer structures at the carbon-Nafion interface. These include complex multi-layered structures, similar to those at silicon oxide interfaces, as well as simple homogenous films with little-to-no interfacial structure. During this presentation, the implications of these results on species transport in PEMFC CLs will be discussed. Additionally, PEMFC performance predictions that incorporate learnings from this study will be made using an extended model from our earlier work [6].[1] S.C. DeCaluwe, A.M. Baker, P. Bhargava, J.E. Fischer, and J.A. Dura, “Structure-property Relationships at Nafion Thin-film Interfaces: Thickness Effects on Hydration and Anisotropic Ion Transport,” Nano Energy, vol. 46, pp. 91–100, 2018.[2] J.A. Dura, V.S. Murthi, M. Hartman, S.K. Satija, and C.F. Majkrzak, “Multilamellar Interface Structures in Nafion,” Macromolecules, vol. 42, no. 13, pp. 4769–4774, 2009.[3] U.N. Shrivastava, H. Fritzsche, and K. Karan, “Interfacial and Bulk Water in Ultrathin Films of Nafion, 3M PFSA, and 3M PFIA Ionomers on a Polycrystalline Platinum Surface,” Macromolecules, vol. 51, no. 23, pp. 9839–9849, 2018.[4] V.S. Murthi, J. Dura, S. Satija, and C. Majkrzak, “Water Uptake and Interfacial Structural Changes of Thin Film Nafion Membranes Measured by Neutron Reflectometry for PEM Fuel Cells,” ECS Transactions, vol. 16, no. 2, 2019.[5] D.L. Wood, J. Chlistunoff, J. Majewski, and R.L. Borup, “Nafion Structural Phenomena at Platinum and Carbon Interfaces,” Journal of the American Chemical Society, vol. 131, no. 50, pp. 18096–18104, 2009.[6] C.R. Randall and S.C. DeCaluwe, “Physically Based Modeling of PEMFC Cathode Catalyst Layers: Effective Microstructure and Ionomer Structure–Property Relationship Impacts,” Journal of Electrochemical Energy Conversion and Storage, vol. 17, no. 4, Jan. 2020.

Plasma spraying is employed to prepare porous La0.8Sr0.2MnO3 (LSM) cathode for solid oxide fuel cells (SOFCs) using both liquid suspension and solid feedstocks. The surface morphology and microstructure of the LSM deposits are characterized by SEM. The electrochemical behavior is investigated through the impedance spectroscopy. The specific surface resistance of 0.36 Ω•cm2 and 0.74 was obtained at 1000oC for SPS and APS LSM cathodes, respectively. The polarization of SPS LSM cathode is lower than APS LSM cathode by a factor of 2 to 2.4 in the temperature range from 850 to 1000 oC.

Dissimilar materials brazing of Ti2AlNb alloy to GH99 superalloy is of great pragmatic importance in the aerospace field, especially the lightweight space aircraft components manufacturing. In this work, TiZrCuNi amorphous filler alloy was used as brazing filler, and experiments were carried out at different brazing temperatures and times to investigate the changes in interfacial structures and properties of the joints. The typical interfacial microstructure was Ti2AlNb alloy/B2/β/Ti2Ni (Al, Nb) + B2/β + (Ti, Zr)2(Ni, Cu) + (Ti, Zr)(Ni, Cu)/(Cr, Ni, Ti) solid solution + (Ni, Cr) solid solution/GH99 superalloy when being brazed at 1000 °C for 8 min. The interfacial microstructure of the joints was influenced by diffusion and reaction between the filler alloy and the parent metal. The prolongation of brazing process parameters accelerated the diffusion and reaction of the liquid brazing alloy into both parent metals, which eventually led to the aggregation of (Ti, Zr)2(Ni, Cu) brittle phase and increased thickness of Ti2Ni (Al, Nb) layer. According to fracture analyses, cracks began in the Ti2Ni (Al, Nb) phase and spread with it as well as the (Ti, Zr)2(Ni, Cu) phase. The joints that were brazed at 1000 °C for 8 min had a maximum shear strength of ~216.2 MPa. Furthermore, increasing the brazing temperature or extending the holding time decreased the shear strength due to the coarse Ti2Ni (Al, Nb) phase and the continuous (Ti, Zr)2(Ni, Cu) phase.

Ferromagnetic resonance and X-ray specular reflectivity measurements were performed on Ni 81 Fe 19 /Ir 20 Mn 80 / Co 90 Fe 10 exchange bias trilayers, which were grown using the pulsed-DC magnetron sputtering technique on Si(100)/SiO 2 (1000 nm) substrates, to investigate the evolution of the interface roughness and exchange bias and their dependence on the NiFe layer thickness. The interface roughness values of the samples decrease with increasing NiFe thickness. The in-plane ferromagnetic resonance measurements indicate that the exchange bias field and the peak-to-peak line widths of the resonance curves are inversely proportional to the NiFe thickness. Furthermore, both the exchange bias field and the interface roughness show almost the same dependence on the NiFe layer thickness. The out-of plane angular dependent measurements indicate that the exchange bias arises predominantly from a variation of exchange anisotropy due to changes in interfacial structure. The correlation between the exchange bias and the interface roughness is discussed.

Metastable carbonates play important roles in geochemistry, biomineralization and serve as model systems for nonclassical theories of nucleation and growth. Balcite (Ca0.5Ba0.5CO3) is a remarkable carbonate phase that is isostructural with a high-temperature modification of calcite (CaCO3), yet can be synthesized at ambient conditions. Here, we investigate crystallization pathways in the Ba–Ca–CO3–H2O system, with a focus on the transformation of amorphous calcium barium carbonate (ACBC) to balcite and subsequent decomposition into the equilibrium calcite (CaCO3) and witherite (BaCO3) phases. Density functional theory calculations show that balcite is an unstable solid solution (Ca1–xBaxCO3, R3̅m) in the range 0.17 < x < 0.5, but is accessible through the amorphous ACBC precursor for x ≲ 0.5, and predict its decomposition into calcite and witherite. We confirm this pathway experimentally but found demixing to proceed slowly and remain incomplete even after 9 months. Nucleation kinetics of balcite from ACBC was assessed using a microfluidic assay, where increasing barium content led to a surprising increase in the balcite nucleation rate, despite decreasing thermodynamic driving force. We attribute crystallization rates that dramatically accelerate with time to changes in interfacial structure and composition during coarsening of the amorphous precipitate. By carefully quantifying the thermodynamic and kinetic contributions in the multistep crystallization of a metastable carbonate, we produce insights that allow us to better interpret the formation and persistence of metastable minerals in natural and synthetic environments.

Survey on electrochemical properties of La2−xSrxNiO4±δ (x = 0.2 and 0.8, δ > 0) cathodes related with structural stability under cathodic polarization conditions

Solid Oxide Fuel Cells (SOFCs) are energy conversion devices known for their significantly higher power density compared to other fuel cell types. However, their high operating temperatures pose challenges related to thermal stability. To address this, research is focusing on Low-Temperature SOFCs (LT-SOFCs), which function at lower temperatures and exhibit enhanced electrochemical performance. While various electrode materials are utilized in SOFCs, platinum (Pt) stands out for its excellent electronic conductivity and catalytic activity. Unfortunately, at the operating temperatures of SOFCs, Pt tends to agglomerate, leading to a rapid reduction in the triple phase boundary (TPB) and a subsequent decline in electrochemical reactions. In this study, LT-SOFCs were fabricated with a Praseodymium Oxide (PrOx) capping layer applied to a porous Pt cathode using sputtering, with various thicknesses achieved by adjusting the deposition time. The electrochemical performance of the LT-SOFCs was measured at 500oC. Additionally, the degradation behavior of the LT-SOFCs was assessed by applying a constant voltage of 0.5 V for 48 hours. Scanning Electron Microscopy (SEM) analysis was also conducted on the PrOx capping layer thin films under the same operating conditions.