Performance and stability of (La,Sr)MnO3–Y2O3–ZrO2 composite oxygen electrodes under solid oxide electrolysis cell operation conditions

The electrochemical performance and stability of (La,Sr)MnO₃–Y₂O₃–ZrO₂ (LSM-YSZ) composite oxygen electrodes is studied in detail under solid oxide electrolysis cells (SOECs) operation conditions. The introduction of YSZ electrolyte phase to form an LSM-YSZ composite oxygen electrode substantially enhances the electrocatalytic activity for oxygen oxidation reaction. However, the composite electrode degrades significantly under SOEC mode tested at 500 mA cm⁻² and 800 °C. The electrode degradation is characterized by deteriorated surface diffusion and oxygen ion exchange and migration processes. The degradation in electrode performance and stability is most likely associated with the breakup of LSM grains and formation of LSM nanoparticles at the electrode/electrolyte interface, and the formation of nano-patterns on YSZ electrolyte surface under the electrolysis polarization conditions. The results indicate that it is important to minimize the direct contact of LSM particles and YSZ electrolyte at the interface in order to prevent the detrimental effect of the LSM nanoparticle formation on the performance and stability of LSM-based composite oxygen electrodes.     

Enhanced electrochemical performance and stability of (La,Sr)MnO3–(Gd,Ce)O2 oxygen electrodes of solid oxide electrolysis cells by palladium infiltration

Palladium-impregnated or infiltrated La_0.8Sr_0.2MnO₃–Gd_0.2Ce_0.8O_1.9 (LSM-GDC) composites are studied as the oxygen electrodes (anodes) for the hydrogen production in solid oxide electrolysis cells (SOECs). The incorporation of small amount of Pd nanoparticles leads to a substantial increase in the electrocatalytic activity and stability of the LSM-GDC oxygen electrodes. The electrode polarization resistance (R_E) at 800 °C on a 0.2 mg cm⁻² Pd-infiltrated LSM-GDC electrode is 0.13 Ω cm², significantly smaller than 0.42 Ω cm² for the reaction on the pure LSM-GDC electrodes. The overpotential loss is also substantially reduced after the Pd infiltration; at an anodic overpotential 50 mV and 800 °C, the current increases from 0.15 A cm⁻² for the pure LSM-GDC anode to 0.47 A cm⁻² on a 0.3 mg cm⁻² Pd-infiltrated LSM-GDC. The infiltrated Pd nanoparticles enhance the stability of the LSM-GDC oxygen electrodes and are most effective in the promotion of the diffusion, exchange and combination processes of oxygen species on the surface of LSM-GDC particles, leading to the increase in the oxygen evolution reaction rate.     

Cobalt-free perovskite Ba0.95La0.05FeO3-δ as efficient and durable oxygen electrode for solid oxide electrolysis cells

Solid oxide electrolysis cells (SOECs) have been demonstrated as an efficient technique to improve energy utilization and alleviate the greenhouse effect. The commercialization of SOECs is limited by the oxygen electrodes, whose problems include high costs and unexpected degradation of cobalt/strontium. In this work, we systematically evaluated the oxygen evolution reaction (OER) performance of a cobalt-free and strontium-free material Ba_0.95La–FeO_3-δ (BLF) and the application of BLF as an oxygen electrode of SOECs by combining DFT calculation and experimental. We found that the BLF has excellent OER performance due to its low oxygen vacancy formation energies and oxygen adsorption energies on the surfaces. Under an applied electrolysis voltage of 1.5 V, the current density reaches 3.17 and 1.53 A cm⁻² at 850 °C with 50%H₂–50%H₂O and 50%H₂–50%CO₂, respectively. The superb stability of the electrolysis cell was shown in the 200 h testing, which further demonstrated that BLF is a promising material for oxygen electrodes of SOECs.     

Preparation and characterization of Ce0.8M0.2O2−δ (M = Y,Gd, Sm,Nd, La) solid electrolyte materials for solid oxide fuel cells

Characteristics, such as lattice parameter, theoretical densities, thermal expansion, mechanical properties, microstructure, and ionic conductivities, of Ce_0.8M_0.2O_2−δ (M = Y, Gd, Sm, Nd, La) ceramics prepared by coprecipitation were systematically investigated in this paper. The results revealed that the lattice parameter and density based on the oxygen vacancy radius generally agreed with experimental results. Ce_0.8Sm_0.2O_2−δ ceramic sintered at 1500 °C for 5 h possessed the maximum ionic conductivity, σ_800 °C = 6.54 × 10⁻² S cm⁻¹, with minimum activation energy, E_a = 0.7443 eV, among Ce_0.8M_0.2O_2−δ (M = Y, Gd, Sm, Nd, La) ceramics. The thermal expansion coefficients of Ce_0.8M_0.2O_2−δ (M = Y, Gd, Sm, Nd, La) were in the range of 15.176–15.571 ppm/°C, which indicates that the rare-earth oxide dopants have insignificant influence on the thermal expansion property. Trivalent, rare-earth oxide doped ceria ceramics revealed high fracture toughness, with the fracture toughness in the range of 6.393–7.003 MPa m^1/2. According to SEM observation, the cracks are limited to one grain diameter; therefore, the high fracture toughness of rare-earth oxide doped ceria may be due to the toughness mechanism of crack deflection at the grain boundary. Based on the results of grain size and mechanical properties, one may conclude that there is no significant dependence of fracture toughness and microhardness for Ce_0.8M_0.2O_2−δ ceramics on grain size. Correlation between the grain size of Ce_0.8M_0.2O_2−δ ceramics and the dopant species can be explained on the basis of the concept of the rate of grain growth being proportional to the boundary mobility M_b. This leads to a conclusion that the diffusion coefficient of La in Ce_0.8La_0.2O_2−δ>Nd in Ce_0.8Nd_0.2O_2−δ>Sm in Ce_0.8Sm_0.2O_2−δ>Gd inCe_0.8Gd_0.2O_2−δ>Y in Ce_0.8Y_0.2O_2−δ.     

Performance and durability of an anode-supported solid oxide fuel cell with a PdO/ZrO2 engineered (La0.8Sr0.2)0.95MnO3-δ-(Y2O3)0.08(ZrO2)0.92 composite cathode

PdO/ZrO₂ co-infiltrated (La_0.8Sr_0.2)_0.95MnO_3-δ-(Y₂O₃)_0.08(ZrO₂)_0.92 (LSM-YSZ) composite cathode (PdO/ZrO₂+LSM-YSZ), which adsorbs more oxygen than equal amount of PdO/ZrO₂ and LSM-YSZ, is developed and used in Ni-YSZ anode-supported cells with YSZ electrolyte. The cells are investigated firstly at temperatures between 650 and 750 °C with H₂ as the fuel and air as the oxidant and then polarized at 750 °C under 400 mA cm^?2 for up to 235 h. The initial peak power density of the cell is in the range of 438–1207 mW cm^?2 at temperatures from 650 to 750 °C, corresponding to polarization resistance from 1.04 to 0.35 Ω cm². This result demonstrates a significant performance improvement over the cells with other kinds of LSM based cathode. The cell voltage at 750 °C under 400 mA cm^?2 decreases from initial 0.951 to 0.89 V after 170 h of current polarization and remains essentially stable to the end of current polarization. It is identified that the self-limited growth of PdO particles is responsible for the cell voltage decrease by reducing the length of triple phase boundary affecting the high frequency steps involved in oxygen reduction reaction in the cathode.     

LaNbO4 toughened NiO–Y2O3 stabilized ZrO2 composite for the anode support of planar solid oxide fuel cells

NiO–Y₂O₃ stabilized ZrO₂ (YSZ) composite is the state-of-the-art material for the anode support of planar solid oxide fuel cells (SOFCs). To improve its fracture toughness (K_C), lanthanum orthoniobate LaNbO₄ is synthesized by the method of solid state reaction and added to the mixture of YSZ and NiO at the weight ratio of 47:53. The content of LaNbO₄ in the composite is in the range between 5 and 30 wt%. The microstructure of the composites is examined by scanning electron microscopy (SEM); and the chemical compatibility among the components is evaluated by X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). Vickers hardness test is performed for estimating the K_C of the composites. The results indicate that the K_C increases with the addition of LaNbO₄ in the composites; and the toughening effect is associated with the grain-refinement in the composite and the domain switch in the monoclinic LaNbO₄.     

Fabrication and characterization of nanostructured Ni–IrO2 electrodes for water electrolysis

Nanostructured Ni–IrO₂ electrodes were fabricated by electrodeposition in a two-step procedure: first arrays of nickel nanowires (NWs) were electrodeposited within pores of polycarbonate (PC) membranes, then iridium oxide nanoparticles were deposited on the Ni metal after membrane dissolution, for improving the catalytic activity. The aim was to compare performance of these electrodes with traditional ones consisting of Ni film. Different methods of deposition of the IrO₂ electrocatalyst were investigated and the effect on electrodes stability and activity is discussed. Despite a low coverage of Ni NWs by the electrocatalyst, results indicate a faster kinetics of O₂ evolution in 1 M KOH solution and an improvement of performances for electrolysers having a nanostructured anode.     

Investigation of MBH4–VCl2, M = Li,Na or K

Systematic investigations of MBH₄−VCl₂, M = Li, Na, or K, 2:1 or 3:1, samples prepared by mechano-chemistry and different milling time in order to gain insight in the phase stability and search for novel borohydrides. The samples were investigated using powder X-ray diffraction and Raman spectroscopy. Subsequently, the samples were exposed to heat treatment and investigated by in-situ synchrotron radiation powder X-ray diffraction (SR-PXD). These studies reveal formation of numerous compounds during decomposition of the samples, which contrasts with previous investigations. In several cases the formed compounds were in a less well-crystalline state, which did not allow identification. One of the unidentified compounds was observed both in the LiBH₄−VCl₂ and NaBH₄−VCl₂ systems and appeared to decompose at T ∼ 190 °C and is assumed to be a new vanadium borohydride. Crystalline Li₂VCl₄ was observed, but a major fraction of the decomposition products appeared to be amorphous. The KBH₄−VCl₂ system revealed formation of well-crystalline solid solutions of K(BH₄)_1−xCl_x.     

Performance stability of impregnated La0.6Sr0.4Co0.2Fe0.8O3−δ–Y2O3 stabilized ZrO2 cathodes of intermediate temperature solid oxide fuel cells

The stability of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ impregnated Y₂O₃ stabilized ZrO₂ (LSCF–YSZ) cathodes was investigated under the condition of open circuit or current polarization at 750 °C in air. The electrochemical measurement and the microstructure characteristic show that the flattening of LSCF particles has great contribution to the increase of resistance of LSCF–YSZ cathodes after 500 h heat treatment at 750 °C. Microstructure coarsening and the damage of well-connected porous structure are main reasons of the performance degradation for LSCF–YSZ cathodes testing at 200 mA cm⁻² and 750 °C in air. Higher current density of 500 mA cm⁻² applying on cathodes accelerates degradation processes. X-ray photoelectron spectroscopy (XPS) shows that Sr concentration on the cathode surface decreases after current polarization, which plays a main role in performance activation processes observed at the beginning stage. The enhancement of cobalt activity in LSCF lattice by current polarization increases the conductivity and decreases the stability of LSCF–YSZ cathodes.     

A comparative study of Sm0.5Sr0.5MO3−δ (M = Co and Mn) as oxygen reduction electrodes for solid oxide fuel cells

Sm_0.5Sr_0.5MO_3−δ (M = Co and Mn) materials are synthesized, and their properties and performance as cathodes for solid oxide fuel cells (SOFCs) on Sm_0.2Ce_0.8O_1.9 (SDC) and Y_0.16Zr_0.92O_2.08 (YSZ) electrolytes are comparatively studied. The phase structure, thermal expansion behavior, oxygen mobility, oxygen vacancy concentration and electrical conductivity of the oxides are systematically investigated. Sm_0.5Sr_0.5CoO_3−δ (SSC) has a much larger oxygen vacancy concentration, electrical conductivity and TEC than Sm_0.5Sr_0.5MnO_3−δ (SSM). A powder reaction demonstrates that SSM is more chemically compatible with the YSZ electrolyte than SSC, while both are compatible with the SDC electrolyte. EIS results indicate that the performances of SSC and SSM electrodes depend on the electrolyte that they are deposited on. SSC is suitable for the SDC electrolyte, while SSM is preferred for the YSZ electrolyte. A peak power density as high as 690 mW cm⁻² at 600 °C is observed for a thin-film SDC electrolyte with SSC cathode, while a similar cell with YSZ electrolyte performs poorly. However, SSM performs well on YSZ electrolyte at an operation temperature of higher than 700 °C, and a fuel cell with SSM cathode and a thin-film YSZ electrolyte delivers a peak power density of ∼590 mW cm⁻² at 800 °C. The poor performances of SSM cathode on both YSZ and SDC electrolytes are obtained at a temperature of lower than 650 °C.     

Mixed ionic-electronic conductivity,phase stability and electrochemical activity of Gd-substituted La2NiO4+δ as oxygen electrode material for solid oxide fuel/electrolysis cells

Ruddlesden-Popper La_2-xGd_xNiO_4+δ (x = 0–0.4) nickelates were synthesized by glycerol-nitrate combustion technique and explored as potential oxygen electrode materials for solid oxide fuel/electrolysis cells. Similar to the parent La₂NiO_4+δ, the metastability of RP-type n = 1 structure limits the applicability of La_2-xGd_xNiO_4+δ to temperatures below 900 °C. These solid solutions are mixed conductors with predominantly p-type electronic conductivity that exceeds 50 S/cm at 500–800 °C in air. Substitution by gadolinium does not change the overstoichiometric oxygen content in air but has a negative impact on the mobility of interstitial oxygen, most likely, due to steric effects associated with the lattice shrinkage on doping. The electrochemical activity of bilayer electrodes comprising functional La_2-xGd_xNiO_4+δ and current collecting LaNi_0.6Fe_0.4O_3-δ + 3 wt% CuO layers in contact with Ce_0.8Gd_0.2O_1.9 electrolyte was studied in air at 550–850 °C. Analysis of electrochemical impedance spectroscopy data employing the ALS (Adler-Lane-Steele) model revealed the limiting role of oxygen-ionic conductivity of functional La_2-xGd_xNiO_4+δ materials in overall electrode performance.     

CO2 dry-reforming of methane over La0.8Sr0.2Ni0.8M0.2O3 perovskite (M = Bi,Co, Cr,Cu, Fe): Roles of lattice oxygen on C–H activation and carbon suppression

La_0.8Sr_0.2Ni_0.8M_0.2O₃ (LSNMO) (where M = Bi, Co, Cr, Cu and Fe) perovskite catalyst precursors have been successfully developed for CO₂ dry-reforming of methane (DRM). Among all the catalysts, Cu-substituted Ni catalyst precursor showed the highest initial catalytic activity due to the highest amount of accessible Ni and the presence of mobile lattice oxygen species which can activate C–H bond, resulting in a significant improvement of catalytic activity even at the initial stage of reaction. However, these Ni particles can agglomerate to form bigger Ni particle size, thereby causing lower catalytic stability. As compared to Cu-substituted Ni catalyst, Fe-substituted Ni catalyst has low initial activity due to the lower reducibility of Ni–Fe and the less mobility of lattice oxygen species. However, Fe-substituted Ni catalyst showed the highest catalytic stability due to: (1) strong metal–support interaction which hinders thermal agglomeration of the Ni particles; and (2) the presence of the abundant lattice oxygen species which are not very active for C–H bond activation but active to react with CO₂ to form La₂O₂CO₃, hence minimizing carbon formation by reacting with surface carbon to form CO.     

Performance of large-scale anode-supported solid oxide fuel cells with impregnated La0.6Sr0.4Co0.2Fe0.8O3−δ+Y2O3 stabilized ZrO2 composite cathodes

Anode-supported planar solid oxide fuel cells (SOFCs) with an active area of 81 cm² (9 cm × 9 cm) and nano-structured La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ + Y₂O₃ stabilized ZrO₂ (LSCF + YSZ) composite cathodes are successfully fabricated by tape casting, screen printing, co-firing and solution impregnation, and tested using H₂ fuel and air oxidant at various flow rates. Maximum power densities of 437 and 473 mW cm⁻² are achieved at 750 °C by loading 0.6 and 1.3 mg cm⁻² of LSCF in the composite cathodes, respectively. The gas flow rates, particularly the air, have a significant effect on the cell performance. Cell performance degradation with time is also observed, which is considered to be associated with the growth and coalescence of the nanosized LSCF particles in the composite cathode. The use of the LSCF cathode in combination with YSZ electrolyte without a Gd-doped CeO₂ (GDC) buffer layer is proved to be applicable in large cells, even though the thermal stability of the nanosized LSCF needs to be further improved.     

Oxidative steam reforming of ethanol over Ni/Al2O3 catalysts promoted by CeO2, ZrO2 and CeO2–ZrO2

Oxidative steam reforming of ethanol at low oxygen to ethanol ratios was investigated over nickel catalysts on Al₂O₃ supports that were either unpromoted or promoted with CeO₂, ZrO₂ and CeO₂–ZrO₂. The promoted catalysts showed greater activity and a higher hydrogen yield than the unpromoted catalyst. The characterization of the Ni-based catalysts promoted with CeO₂ and/or ZrO₂ showed that the variations induced in the Al₂O₃ by the addition of CeO₂ and/or ZrO₂ alter the catalyst's properties by enhancing Ni dispersion and reducing Ni particle size. The promoters, especially CeO₂–ZrO₂, improved catalytic activity by increasing the H₂ yield and the CO₂/CO and the H₂/CO values while decreasing coke formation. This results from the addition of ZrO₂ into CeO₂. This promoter highlights the advantages of oxygen storage capacity and of mobile oxygen vacancies that increase the number of surface oxygen species. The addition of oxygen facilitates the reaction by regenerating the surface oxygenation of the promoters and by oxidizing surface carbon species and carbon-containing products.     

Performance of solid oxide electrolysis cells based on composite La0.8Sr0.2MnO3−δ – yttria stabilized zirconia and Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen electrodes

The electrochemical performance of solid oxide electrolysis cells (SOECs) having barium strontium cobalt ferrite (Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ) and composite lanthanum strontium manganite–yttria stabilized zirconia (La_0.8Sr_0.2MnO_3−δ–YSZ) oxygen electrodes has been studied over a range of operating conditions. Increasing the operating temperature (973 K to 1173 K) significantly increased electrochemical performance and hydrogen generation efficiency for both systems. The presence of water in the hydrogen electrode was found to have a marked positive effect on the EIS response of solid oxide cell (SOC) under open circuit voltage (OCV). The difference in operation between electrolytic and galvanic modes was investigated. Cells having BSCF oxygen electrodes (Ni–YSZ/YSZ/BSCF) showed greater performance than LSM-YSZ-based cells (Ni–YSZ/YSZ/LSM-YSZ) over the range of temperatures, in both galvanic and electrolytic regimes of operation. The area specific resistance (ASR) of the LSM-YSZ-based cells remained unchanged when transitioning between electrolyser and fuel cell modes; however, the BSCF cells exhibited an overall increase in cell ASR of ∼2.5 times when entering electrolysis mode.     

Hydrogen production from oxidative steam-reforming of n-propanol over Ni/Y2O3–ZrO2 catalysts

Oxidative steam reforming (OSR) of n-propanol was studied over new Ni catalysts (ca. 7% Ni wt/wt) supported on Y₂O₃–ZrO₂ oxides with different yttrium content (2–41 % Y₂O₃ wt/wt). Materials were characterized by X-ray diffraction, temperature-programmed reduction, X-ray photoelectron and Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray analysis and high resolution transmission electron microscopy. Samples were used in calcined form and tested in the temperature range 673–773 K using a reactant feed of n-propanol/water/O₂ at a molar ratio 1/9/0.5. Hydrogen production is related with the support composition and Ni dispersion.     

H2 and CH4 oxidation on Gd0.2Ce0.8O1.9 infiltrated SrMoO3–yttria-stabilized zirconia anode for solid oxide fuel cells

Strontium molybdate (SrMoO₃) as an electronic conductor was incorporated with yttria-stabilized zirconia (YSZ) to form an anode scaffold for solid oxide fuel cells. Gd_0.2Ce_0.8O_1.9 (GDC) nanoparticles were introduced by wet impregnation to complete the Ni-free GDC infiltrated SrMoO₃–YSZ anode fabrication. The effects of SrMoO₃ on the electrode conductivity and GDC infiltration on the catalytic activity were examined. A pronounced performance improvement was observed both on wet H₂ and CH₄ oxidation for the 56 wt.% GDC infiltrated SrMoO₃–YSZ. In particular, the polarization resistance decreased from 8 Ω cm² to 0.5 Ω cm² under wet H₂ (3% H₂O) at 800 °C with the introduction of GDC. Under wet CH₄ at 900 °C, a maximum power density of 160 mW cm⁻² was obtained and no carbon deposition was observed on the anode. It was found that the addition of H₂O in the anode caused an increase of electrode ohmic resistance and a decrease of open circuit voltage. Redox cycling stability was investigated and only a slight drop in cell performance was observed after 5 cycles. These results suggest that GDC infiltrated SrMoO₃–YSZ is a promising anode material for solid oxide fuel cells.     

Investigation of cobalt-free perovskite Ba0.95La0.05FeO3−δ as a cathode for proton-conducting solid oxide fuel cells

Cobalt-free perovskite Ba_0.95La_0.05FeO_3−δ (BLF) was synthesized. The conductivity of BLF was measured with a DC four-point technique. The thermal expansion coefficient of the BLF was measured using a dilatometer. The BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7) electrolyte based proton conducting solid oxide fuel cells (SOFCs) were fabricated. A composite cathode with BLF + BZCY7 was used to mitigate the thermal expansion mismatch with the BZCY7 electrolyte. The polarization processes of the button cell NiO-BZCY7/BZCY7/BLF + BZCY7 were characterized using the complicated electrochemical impedance spectroscopy technique. The open circuit voltage of 0.982 V, 1.004 V, and 1.027 V was obtained at 700 °C, 650 °C, and 600 °C, respectively, while the peak power density of 325 mW cm⁻², 240 mW cm⁻², and 152 mW cm⁻², was achieved accordingly.     

SiO2–Al2O3–Y2O3–ZnO glass sealants for intermediate temperature solid oxide fuel cell applications

In this study, eleven alkaline earth metal and B₂O₃-free SiO₂–Al₂O₃–Y₂O₃–ZnO glass sealants were prepared. The thermal stability, adhesion, and sealing properties of the glass systems with respect to SUS430 stainless steel (SUS430) were assessed for use in intermediate temperature solid oxide fuel cells (ITSOFCs). The glass transition points fell in the range of 694 °C and 833 °C, while the glass softening points, varying from 725 °C to 885 °C, decreased linearly with the ZnO/SiO₂ ratio. Among the glasses evaluated, the YAS1-50, YAS4-50, YAS5-50, and YAS5-90 glasses coupled with SUS430 showed fine adhesion and no detectable inter-diffusion across the interface. The coefficient of thermal expansion (CTE) of the YAS5-50 glass escalated from 7.01 to 9.30 × 10⁻⁶/K with 50 wt% Bi_1.5Y_0.5O₃ (BYO) fillers. The leak rates of the composite seals comprising the YAS5-50 glass and 50 wt% BYO fillers were measured at 700 °C after joining at 850 °C. The measurement used helium with a pressure at 1 psi across the glass seals and a slight load of 1.0 psi to minimize compressive seal effect on the glass. It appeared that a low leak rate of 0.052 sccm/cm was obtained and stayed unchanged as the system was soaked at 700 °C for 500 h, indicating a fine thermal stability against the extended duration benefited from the limited crystallization of the YAS5-50 glass. This promising long-term stability qualified the glass for use as SOFC seal.