Fabrication and characterization of Sm0.2Ce0.8O2−δ-Sm0.5Sr0.5CoO3−δ composite cathode for anode supported solid oxide fuel cell

The Sm_0.5Sr_0.5CoO_3−δ (SSC) with perovskite structure is synthesized by the glycine nitrate process (GNP). The phase evolution of SSC powder with different calcination temperatures is investigated by X-ray diffraction and thermogravimetric analyses. The XRD results show that the single perovskite phase of the SSC is completely formed above 1100 °C. The anode-supported single cell is constructed with a porous Ni-yttria-stabilized zirconia (YSZ) anode substrate, an airtight YSZ electrolyte, a Sm_0.2Ce_0.8O_2−δ (SDC) barrier layer, and a screen-printed SSC-SDC composite cathode. The SEM results show that the dense YSZ electrolyte layer exhibits the good interfacial contact with both the Ni-YSZ and the SDC barrier layer. The porous SSC-SDC cathode shows an excellent adhesion with the SDC barrier layer. For the performance test, the maximum power densities are 464, 351 and 243 mW cm⁻² at 800, 750 and 700 °C, respectively. According to the results of the electrochemical impedance spectroscopy (EIS), the charge-transfer resistances of the electrodes are 0.49 and 1.24 Ω cm², and the non charge-transfer resistances are 0.48 and 0.51 Ω cm² at 800 and 700 °C, respectively. The cathode material of SSC is compatible with the YSZ electrolyte via a delicate scheme employed in the fabrication process of unit cell.     

Cathode reaction mechanism of porous-structured Sm0.5Sr0.5CoO3−δ and Sm0.5Sr0.5CoO3−δ/Sm0.2Ce0.8O1.9 for solid oxide fuel cells

The cathode reaction mechanism of porous Sm_0.5Sr_0.5CoO_3−δ, a mixed ionic and electronic conductor (MIEC), is studied through a comparison with the composite cathode Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9. First, the cathodic behaviour of porous Sm_0.5Sr_0.5CoO_3−δ and Sm_0.5Sr_0.5CoO_3−δ/Sm_0.2Ce_0.8O_1.9 are observed for micro-structure and impedance spectra according to Sm_0.2Ce_0.8O_1.9 addition, thermal cycling and long-term properties. The cathode reaction mechanism is discussed in terms of frequency response, activation energy, reaction order and electrode resistance for different oxygen partial pressures p(O₂) at various temperatures. Three elementary steps are considered to be involved in the cathodic reaction: (i) oxygen ion transfer at the cathode-electrolyte interface; (ii) oxygen ion conduction in the bulk cathode; (iii) gas phase diffusion of oxygen. A reaction model based on the empirical equivalent circuit is introduced and analyzed using the impedance spectra. The electrode resistance at high frequency (R_c,HF) in the impedance spectra represents reaction steps (i), due to its fast reaction rate. The electrode resistance at high frequency is independent of p(O₂) at a constant temperature because the semicircle of R_c,HF in the complex plane of the impedance spectra is held constant for different values of p(O₂). Reaction steps (ii) and (iii) are the dominant processes for a MIEC cathode, according to the analysis results. The proposed cathode reaction model and results for a solid oxide fuel cell (SOFC) well describe a MIEC cathode with high ionic conductivity, and assist the understanding of the MIEC cathode reaction mechanism.     

The synthesis and characterization of the Sm0.5Sr0.5Co1−xCuxO3−δ cathode by the glycine-nitrate process

In this study, a new oxygen-deficient cathode material, Sm_0.5Sr_0.5Co_1−xCu_xO_3−δ (SSCCu) was developed. It is expected to enhance the efficiency of intermediate-temperature solid oxide fuel cells (IT-SOFCs). The structure, conductivity and electrochemical performance of SSCCu were examined as a function of copper content. The structure of Sm_0.5Sr_0.5Co_0.9Cu_0.1O_3−δ and Sm_0.5Sr_0.5Co_0.8Cu_0.2O_3−δ samples was a single orthorhombic perovskite phase. Second phase SrCoO_2.8, however, formed in the Sm_0.5Sr_0.5Co_0.7Cu_0.3O_3−δ and Sm_0.5Sr_0.5Co_0.6Cu_0.4O_3−δ samples. The conductivity of the Sm_0.5Sr_0.5Co_0.7Cu_0.3O_3−δ cathode was higher than that of other samples. However, the Sm_0.5Sr_0.5Co_0.8Cu_0.2O_3−δ electrode exhibited the lowest overpotential of 25 mV at 400 mA cm⁻² and the lowest area special resistance of 0.2 Ω cm² at 700 °C.     

A cobalt-free Sm0.5Sr0.5FeO3−δ–BaZr0.1Ce0.7Y0.2O3−δ composite cathode for proton-conducting solid oxide fuel cells

A cobalt-free Sm_0.5Sr_0.5FeO_3−δ–BaZr_0.1Ce_0.7Y_0.2O_3−δ (SSF–BZCY) was developed as a composite cathode material for proton-conducting solid oxide fuel cells (H-SOFC) based on proton-conducting electrolyte of stable BZCY. The button cells of Ni-BZCY/BZCY/SSF–BZCY were fabricated and tested from 550 to 700 °C with humidified H₂ (～3% H₂O) as a fuel and ambient oxygen as oxidant. An open-circuit potential of 1.024 V, maximum power density of 341 mW cm⁻², and a low electrode polarization resistance of 0.1 Ω cm² were achieved at 700 °C. The experimental results indicated that the SSF–BZCY composite cathode is a good candidate for cathode material.     

Performance of SrSc0.2Co0.8O3−δ + Sm0.5Sr0.5CoO3−δ mixed-conducting composite electrodes for oxygen reduction at intermediate temperatures

In order to improve the electrical conductivity of the SrSc_0.2Co_0.8O_3−δ (SrScCo) electrode, a composite of 70 wt% SrSc_0.2Co_0.8O_3−δ and 30 wt% Sm_0.5Sr_0.5CoO_3−δ (SrScCo + SmSrCo) was prepared and investigated for electrochemical oxygen reduction at intermediate temperatures. The phase reaction between SrScCo and SmSrCo and its effect on the electrical conductivity, oxygen vacancy concentration and oxygen mobility were examined by XRD, 4-probe DC conductivity measurement, iodometry titration and O₂-TPD experiment, respectively. The results showed that the composite reached a maximum conductivity around 123 S cm⁻¹ at 600 °C, nearly five times that of SrScCo. AC impedance results showed that the electron charge-transfer process was greatly improved by forming the composite electrode, while the oxygen-ion charge-transfer process was somewhat deteriorated. By firing at 1000 °C for 2 h, a SOFC with the SrScCo + SmSrCo cathode and thin-film SDC electrolyte delivered peak power densities of 1100 and 366 mW cm⁻² at 600 and 500 °C, respectively, which were only modestly lower than those of a similar cell with a pure SrScCo cathode.     

Performance of double-perovskite Sr2−xSmxMgMoO6−δ as solid-oxide fuel-cell anodes

Double-perovskite Sr_2−xSm_xMgMoO_6−δ (SSMM, 0 ≤ x ≤ 0.8) is investigated as a possible anode material for solid-oxide fuel cells on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolytes. Single-phase SSMM samples with 0 ≤ x ≤ 0.4 are prepared. At x ≥ 0.6, a small amount of SrMoO₄ and Sm₂O₃ impurities are observed. The Mg/Mo ordering in SSMM decreases with increasing Sm content. Substitution of Sm for Sr significantly improves the electrical conductivity of SSMM. At x = 0.6, the sample yields the highest conductivity, with values reaching 16 S cm⁻¹ in H₂ at 800 °C. The maximum power densities of single cells achieved with x = 0.0, 0.2, 0.4, 0.6, and 0.8 anodes on a 300 μm-thick LSGM electrolyte are 693, 770, 860, 907, and 672 mW cm⁻², respectively, in H₂ at 850 °C. The SSMM sample with x = 0.4 is considered as the best anode candidate because of the impurity formation seen in x ≥ 0.6 samples. The x = 0.4 sample not only has a thermal-expansion coefficient closer to that of the LSGM electrolyte but also exhibits good electrochemical performance and stability in commercial city gas containing H₂S, where the maximum power density achieved is 726 mW cm⁻² at 850 °C.     

Cathode reaction models and performance analysis of Sm0.5Sr0.5CoO3−δ-BaCe0.8Sm0.2O3−δ composite cathode for solid oxide fuel cells with proton conducting electrolyte

Cathode reaction models for solid oxide fuel cells with proton conducting electrolyte (H-SOFC) are proposed, and the reacting orders for each elementary step with respect to oxygen and water vapor partial pressure are calculated. The limiting steps of cathode reactions are investigated with Sm_0.5Sr_0.5CoO_3−δ (SSC)-BaCe_0.8Sm_0.2O_3−δ (BCS) composite cathodes. The results suggest that the migration of protons to TPBs and the surface diffusion of might be the limiting reactions for SSC-BCS composite cathodes in wet atmosphere, while the oxygen ions transferring into electrolyte, the reducing of O_ad to , and surface diffusion of might be the limiting reactions for SSC-BCS composite cathode in dry atmosphere.     

New SrMo1−xCrxO3−δ perovskites as anodes in solid-oxide fuel cells

Oxides of composition SrMo_1−xCr_xO_3−δ (x = 0.1, 0.2) have been prepared, characterized and tested as anode materials in single solid-oxide fuel cells, yielding output powers higher than 700 mW cm⁻² at 850 °C with pure H₂ as a fuel. All the materials are suggested to present mixed ionic–electronic conductivity (MIEC) from neutron powder diffraction (NPD) experiments, complemented with transport measurements; the presence of a Mo⁴⁺/Mo⁵⁺ mixed valence at room temperature, combined with a huge metal-like electronic conductivity, as high as 340 S cm⁻¹ at T = 50 °C for x = 0.1, could make these oxides good materials for solid-oxide fuel cells. The magnitude of the electronic conductivity decreases with increasing Cr-doping content. The reversibility of the reduction–oxidation between the oxidized Sr(Mo,Cr)O_4−δ scheelite and the reduced Sr(Mo,Cr)O₃ perovskite phases was studied by thermogravimetric analysis, which exhibit the required cyclability for fuel cells. An adequate thermal expansion coefficient, without abrupt changes, and a chemical compatibility with electrolytes make these oxides good candidates for anodes in intermediate-temperature SOFC (IT-SOFCs).     

Novel SrCo1−yNbyO3−δ cathodes for intermediate-temperature solid oxide fuel cells

Perovskite oxides SrCo_1−yNb_yO_3−δ (SCNy, y = 0.00-0.20) are investigated as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) on La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. Compared to the undoped SrCoO_3−δ, the Nb doping significantly improves the thermal stability and enhances the electrical conductivity of the SCNy oxides. The cubic phase of the SCNy oxides with high thermal stability can be totally obtained when the Nb doping content y ≥ 0.10. Among the investigated compositions, the SrCo_0.9Nb_0.1O_3−δ oxide exhibits the highest electrical conductivity of 461-145 S cm⁻¹ over the temperature range of 300-800 °C in air. The SCNy cathode has a good chemical compatibility with the LSGM electrolyte for temperatures up to 1050 °C for 5 h. The area specific resistances of SCNy with y = 0.10, 0.15 and 0.20 cathodes on LSGM electrolyte are 0.083, 0.099 and 0.110 Ω cm² at 700 °C, respectively. At y = 0.10, 0.15 and 0.20, the maximum power densities of a single-cell with SCNy cathodes on 300-μm thick LSGM electrolyte achieve 675, 642 and 625 mW cm⁻² at 800 °C, respectively. These results indicate that SCNy perovskite oxides with cubic phase are potential cathode materials for application in IT-SOFCs.     

Electrochemical properties of ceramic membranes based on SrTi0.5Fe0.5O3−δ in reduced atmosphere

The present work aims at the investigation of the electrochemical properties of SrTi_0.5Fe_0.5O_3−δ as a membrane material for hydrogen production via electrochemical reforming. The dependence of the electrical conductivity on the oxygen partial pressure, as well as the oxygen permeability in the range of 10⁻²⁰ atm ≤ pO₂$p_{{\text{O}}_2}$ ≤ 10⁻¹⁴ atm is examined. The oxygen permeability is measured by an electrochemical method. The dependences of ion current as a function of the electromotive force (EMF) at various temperatures, oxygen partial pressures and the membrane surface conditions (rough and activated by PrO_x) are studied. Finally, the values of hydrogen flux at different temperatures are calculated and a long term investigation during 600 h at pO₂$p_{{\text{O}}_2}$ = 10⁻¹⁹ atm, T = 1173 K is carried out. According to the present results, the permeation current increases with the increase of temperature, oxygen partial pressure gradient and activation by PrO_x. The long term investigation shows that the electrical resistance of the SrTi_0.5Fe_0.5O_3−δ ceramic membrane increases by 10%, possibly due to the formation of micro-domains into the material's volume and the decrease in the grain boundary conductivity, because of the segregation of dopant-rich layers near the grain boundaries.     

Synthesis and electrochemical properties of (Pr–Nd)1−ySryMnO3−δ and (Pr1−xNdx)0.7Sr0.3MnO3−δ as cathode materials for IT-SOFC

(Pr–Nd)_1−ySr_yMnO_3−δ (P-NSM, y = 0.2, 0.25, 0.3, 0.35) powders made from commercial Pr–Nd mixed oxide, as well as (Pr_1−xNd_x)_0.7Sr_0.3MnO_3−δ (PN3SM, x = 0, 0.5, 0.7, 1) were synthesized by a glycine-nitrate process and characterized as cathode materials for intermediate temperature solid oxide fuel cell (IT-SOFC). XRD patterns showed the powders had formed pure perovskite phase after being calcined at 800 °C for 2 h. (Pr–Nd)_0.7Sr_0.3MnO_3−δ (P-N3SM) achieved a high conductivity of 194 S cm⁻¹ at 500 °C and showed a good chemical stability against YSZ at 1150 °C. And the thermal expansion coefficient of P-N3SM/YSZ cathode was 11.1 × 10⁻⁶ K⁻¹, which well matched YSZ electrolyte film. The tubular SOFC with P-N3SM/YSZ cathode exhibited the maximum power densities of 415, 367, 327 and 282 mW cm⁻² at 850, 800, 750 and 700 °C, respectively, which indicated P-N3SM was potentially applied in SOFC for low cost.     

Phase stability and conductivity of Ba1−ySryCe1−xYxO3−δ solid oxide fuel cell electrolyte

The structure, phase stability, and electrical properties of BaCe_1−xY_xO_3−δ (x = 0-0.4) in humidity air and CO₂ atmosphere are investigated. XRD results indicate that the BaCe_0.9Y_0.1O_3−δ sample has a symmetric cubic structure, and its phase changes to tetragonal as the Y³⁺ doping amount increases to 20 mol%. The conductivity of BaCe_1−xY_xO_3−δ increases with temperature, and it depends on the amount of yttrium doping and the atmosphere. BaCe_0.8Y_0.2O_3−δ exhibits the highest conductivity of 0.026 S cm⁻¹ at 750 °C. The activation energy for conductivity depends on yttrium doping amount and temperature. The conductivity of BaCe_0.8Y_0.2O_3−δ is 0.025 S cm⁻¹ in CO₂ atmosphere at 750 °C which is 3.8% lower than that in air due to reactions with CO₂ and BaCO₃ and the CeO₂ impure phases formed. The structure of BaCe_0.8Y_0.2O_3−δ is unstable in water and decomposes to Ba(OH)₂ and CeO₂ phases. It is found that the activation energy of samples in CO₂ atmosphere is higher than that of sample in air. Sr-doped Ba_1−ySr_yCe_0.8Y_0.2O_3−δ (y = 0-0.2) is prepared to improve the phase stability of BaCe_0.8Y_0.2O_3−δ in water. The conductivity of Ba_0.9Sr_0.1Ce_0.8Y_0.2O_3−δ is 0.023 S cm⁻¹ at 750 °C which was 11% lower than that of BaCe_0.8Y_0.2O_3−δ, however, the phase stability of Ba_0.9Sr_0.1Ce_0.8Y_0.2O_3−δ is much better than that of BaCe_0.8Y_0.2O_3−δ in water.     

Pd-substituted (La,Sr)CrO3−δ-Ce0.9Gd0.1O2−δ solid oxide fuel cell anodes exhibiting regenerative behavior

Composite anodes consisting of Pd-substituted (La,Sr)CrO_3−δ mixed with 50 wt% Ce_0.9Gd_0.1O_2−δ were tested in La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ-electrolyte supported fuel cells at 800 °C with humidified H₂ fuel. Low anode polarization resistance was observed during the first several hours of operation, explained by the nucleation of Pd nano-particles on perovskite particle surfaces. Anode performance then degraded gradually before stabilizing. Redox cycling repeatedly restored the anodes to their initial peak performance, followed again by degradation. This regenerative behavior was explained by the observation that the Pd nano-particles were removed by oxidation, and then re-nucleated upon reduction.     

La0.9−xCaxCe0.1CrO3−δ as potential anode materials for solid oxide fuel cells

LaCrO₃ doped with calcium and cerium on the A-site in the series of La_0.9−xCa_xCe_0.1CrO_3−δ (LCCC3060, LCCC4050, LCCC5040, LCCC6030 corresponding to x = 0.6, 0.5, 0.4, and 0.3 respectively), is synthesized by a sol–gel combustion method and evaluated as anode material for solid oxide fuel cells (SOFCs). Relatively higher Ca-doping on La in LaCrO₃ is found to improve both electronic and ionic conductivity. LCCC compositions have demonstrated good chemical stability in reducing atmospheres. Evaluation of the LCCC material as anode in symmetrical cell configuration shows that the highest Ca-doping composition results in the lowest activation energy and the lowest polarization resistance. La_0.8Sr_0.2Ga_0.83Mg_0.17O_3−δ (LSGM) electrolyte-supported single cells with LCCC3060 as the anode and La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) as the cathode show that LCCC3060 can be a potential anode material for H₂, but not for CH₄.     

Structure, chemical stability and mixed proton-electron conductivity in BaZr0.9−xPrxGd0.1O3−δ

BaZr_0.9−xPr_xGd_0.1O_3−δ (x = 0.3 and 0.6) was prepared by combustion synthesis and characterised with respect to conductivity and stability in an attempt to combine the desirable properties of the end members. The polycrystalline materials exhibit a cubic or pseudo-cubic structure as determined by X-ray synchrotron radiation and transmission electron microscopy. The chemical stability of the compositions is strongly dependent on the praseodymium content, the materials with more Pr present lower stability. Electron holes dominate the conductivity under oxidising atmospheres in BaZr_0.3Pr_0.6Gd_0.1O_3−δ, while BaZr_0.6Pr_0.3Gd_0.1O_3−δ exhibits a mixed electron hole-proton conducting behaviour. Substitution of Zr by Pr in acceptor-doped BaZrO₃ decreases the sintering temperature and increases the grain growth rate.     

SrCo1−xSbxO3−δ perovskite oxides as cathode materials in solid oxide fuel cells

The SrCo_1−xSb_xO_3−δ (x = 0.05, 0.1, 0.15 and 0.2) system was tested as possible cathode for solid oxide fuel cells (SOFCs). X-ray diffraction results show the stabilization of a tetragonal P4/mmm structure with Sb contents between x = 0.05 and x = 0.15. At x = 0.2 a phase transition takes place and the material is defined in the cubic Pm-3m space group. In comparison with the undoped hexagonal SrCoO₃ phase, the obtained compounds present high thermal stability without abrupt changes in the expansion coefficient. In addition, a great enhancement of the electrical conductivity was observed at low and intermediate temperatures (T ≤ 800 °C). The sample with x = 0.05 displays the highest conductivity value that reaches 500 S cm⁻¹ at 400 °C and is over 160 S cm⁻¹ in the usual working conditions of a cathode in SOFC (650-900 °C). Moreover, the impedance spectra of the SrCo_1−xSb_xO_3−δ/Ce_0.8Nd_0.2O_2−δ/SrCo_1−xSb_xO_3−δ (x ≥ 0.05) symmetrical cells reveal polarization resistances below 0.09 Ω cm² at 750 °C which are much smaller than that displayed by the pristine SrCoO_3−δ sample. The composition with x = 0.05 shows the lowest ASR values ranging from 0.009 to 0.23 Ω cm² in the 900-600 °C temperature interval with an activation energy of 0.82 eV.     

A new solid-state process for synthesis of LiMn1.5Ni0.5O4−δ spinel

A new two-step solid-state process was developed for synthesis of a pure phase 4.7 V LiMn_1.5Ni_0.5O_4−δ (LMNO) spinel of good electrochemical properties. This process which was based on formation of stable Ni_1−xMn₂O_4−δ (x ≤ 0.33) spinel followed by subsequent lithiation, demonstrated the emerging of LiMn_1.5Ni_0.5O_4−δ frame work at temperatures of as low as 350 °C. During this lithiation process, migration of metal ions (Ni/Mn) from partially occupied tetrahedral 8a sites (in Ni_0.67Mn₂O_4−δ) toward octahedral 16d site occurred. The resultant spinel material displayed low irreversible loss, a 97% columbic efficiency and 6% loss in discharge capacity after 100 cycles at 60 °C.     

SrCo1−yTiyO3−δ as potential cathode materials for intermediate-temperature solid oxide fuel cells

The perovskites SrCo_1−yTi_yO_3−δ (SCTy, y = 0.00-0.20) are synthesized and assessed as potential cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) based on the La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) electrolyte. SCTy composites with y ≥ 0.05 adopt a cubic perovskite structure with thermal stability between 30 °C and 1000 °C in air. Substitution of Ti significantly enhances the electrical conductivity of the SCTy composites relative to the undoped SrCoO_3−δ. The highest electrical conductivity of the sample with y = 0.05 varied from 430 S cm⁻¹ to 160 S cm⁻¹ between 300 °C to 800 °C in air. The area-specific resistances of the SCTy cathodes on the LSGM electrolyte gradually increase from 0.084 Ω cm² at y = 0.05 to 0.091 Ω cm² at y = 0.20 with increasing Ti content at 750 °C. Single-cells that used SCTy cathodes with y = 0.05, 0.10, 0.15, and 0.20 on a 300 μm-thick LSGM electrolyte achieve peak power densities of 793, 608, 525, and 425 mW cm⁻² at 800 °C, respectively. These novel SCTy cubic perovskites demonstrate considerable potential for application in IT-SOFC cathodes.     

Electrical performance and structural analysis of La1−xBaxGa0.8Mg0.2O3−δ solid electrolyte

The aim of this study was to develop La_1−xBa_xGa_1−yMg_yO_3−δ (x = 0.03–0.1, y = 0.2–0.25) (LBGM) electrolytes for intermediate-temperature solid-oxide fuel cells (SOFCs); these electrolytes were synthesized via a solid-state reaction. In the study, the La_1−xBa_xGa_1−yMg_yO_3−δ samples crystallized in an orthorhombic (Imma) structure, and a BaLaGa₃O₇ phase was detected for x ≥ 0.08 at a fixed y = 0.2. The solubility limit of the Ba ions increased with an increase in the Mg content in the matrix. Two active Raman bands at ca. 677 and 739 cm⁻¹ were observed, and they were attributed to the oxygen vacancies. The La_0.95Ba_0.05Ga_0.75Mg_0.25O_3−δ sample had a higher conductivity ca. 0.1 S/cm at 800 °C, and an activation energy of ca. 0.83–1.27 eV at 500–800 °C. The thermal expansion coefficient (TEC) of the LBGM samples at 200–800 °C was in the range of 10 × 10⁻⁶ to 14 × 10⁻⁶/°C.     

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.