Proton-conducting Solid Oxide Fuel Cells Research Articles

A dual modification strategy of highly active catalytic cathode for proton-conducting solid oxide fuel cell with Ni-doped PrBaFe1.9Mo0.1O6-δ

The cathode catalytic activity and stability in a temperature range of 550–700 °C is crucial to the development of proton-conductive solid oxide fuel cells (PCFCs). A facile dual-modification strategy is developed for the design of Ni-doped PrBaFe1.9Mo0.1O6-δ (PBFMN), composed of a major perovskite and a minor NiO phases, as a cobalt-free cathode. The composite cathode PBFMN exhibits high catalytic activity and stability. Computational simulation indicates that the perovskite phase increases the oxygen vacancies and enhances the proton transfer, while nickel oxide nanoparticles improve oxygen adsorption and dissociation. The fuel cell with as-prepared PBFMN reached a peak power density 1.23 W cm−2 at 700 °C. The improved performance of the cell is mainly due to the fast ORR kinetics. This work provides a new insight into the design of cobalt-free cathode for a PCFC.

Towards highly dense electrolytes at lower sintering temperature (∼1200 °C): Optimization strategies for BaCe0.7Zr0.1CuxY0.2-xO3-δ in SOFCs

High-conducting and long-term stable proton-conducting electrolytes are of utmost importance. This study investigates the synthesis and characterization of BaCe0.7Zr0.1CuxY0.2-xO3-δ (BCZCuxY; x = 0, 0.005, 0.01, 0.02, 0.05, and 0.1) electrolytes tailored for proton-conducting solid oxide fuel cells (SOFCs). Through Cu2+ doping at the B-site of BaCe0.7Zr0.1Y0.2O3-δ (BCZY), a successful reduction of the sintering temperature to 1200 °C was achieved. BCZCu0.02Y exhibited a high relative density of approx. 98.1% at this temperature, but beyond 2 mol% Cu doping, the appearance of a BaCuO2 secondary phase adversely impacted conductivity. The electronic properties of BCZY and BCZCuxY are elucidated via partial density of states (PDOS) analysis, revealing optimized crystal structures and band gap reductions (from approx. 1.9 eV–1.1 eV) upon Cu doping. Notably, BCZCu0.02Y demonstrated a commendable conductivity, with values of 3.5 × 10−2 S. cm−1 in air and 4.8 × 10−2 S. cm−1 in a moist atmosphere at 750 °C. Remarkably, excellent electrochemical stability was observed in a moist hydrogen atmosphere for up to 450 h at 600 °C. Single cells incorporating BCZCu0.02Y electrolytes exhibited peak power densities of 380 mW/cm2 at 750 °C. The incorporation of 2 mol% Cu2+ in the BCZY lattice holds promise for achieving low-temperature sintering and high-performance proton-conducting SOFCs.

A novel platinum modified barium zirconate-based electrolyte for enhanced solid oxide fuel cell performance

Pt modified BaZr0.76Y0.2Ni0.04O3 (BZYN) is fabricated and characterized as a stable electrolyte for proton-conducting solid oxide fuel cell (H-SOFC). The utilization of X-ray diffraction method (XRD) and transmission electron microscopy (TEM) enables the identification of the presence of platinum (Pt) in both the crystal lattice sites and the grain interface. This occurrence contributes to a reduction in grain boundary resistance. Consequently, this phenomenon improves the conductivity of the electrolyte. The electrochemical performance of the single cell with Pt-modified BZY electrolyte is improved by the reduction of ohmic resistance and enhancement of ion migration. This signifies a noteworthy advancement in the creation of more efficient and durable proton-conducting SOFCs.

Recent Novel Fabrication Techniques for Proton-Conducting Solid Oxide Fuel Cells

Research has been conducted on solid oxide fuel cells (SOFCs) for their fuel flexibility, modularity, high efficiency, and power density. However, the high working temperature leads to the deterioration of materials and increased operating costs. Considering the high protonic conductivity and low activation energy, the proton conducting SOFC, i.e., the protonic ceramic fuel cell (PCFC), working at a low temperature, has been wildly investigated. The PCFC is a promising state-of-the-art electrochemical energy conversion system for ecological energy; it is characterized by near zero carbon emissions and high efficiency, and it is environment-friendly. The PCFC can be applied for the direct conversion of various renewable fuels into electricity at intermediate temperatures (400–650 °C). The construction of the PCFC directly affect its properties; therefore, manufacturing technology is the crucial factor that determines the performance. As a thinner electrolyte layer will lead to a lower polarization resistance, a uniformly constructed and crack-free layer which can perfectly bond to electrodes with a large effective area is challenging to achieve. In this work, different fabrication methods are investigated, and their effect on the overall performance of PCFCs is evaluated. This article reviews the recent preparation methods of PCFCs, including common methods, 3D printing methods, and other advanced methods, with summarized respective features, and their testing and characterization results.

Carbon Deposition Mitigation Strategies in Proton-Conducting Solid Oxide Fuel Cells: A Case Study with Biomass Fuels.

Methanol and ethanol, when used as biomass fuels, demonstrate distinct benefits compared to hydrogen in proton-conducting solid oxide fuel cells (PCFCs) applications. Nevertheless, employing these biomass fuels in PCFCs encounters a significant obstacle due to carbon deposition, adversely affecting the cells' longevity. To mitigate this issue, a dendritic pore channel anode design was implemented to optimize the fuel distribution and utilization efficiency. Additionally, the approach incorporates a co-reforming strategy of fuel and steam, operating the cell under stable output current conditions to mitigate carbon deposition in the cell. Furthermore, the integration of Ru-GDC nanofiber catalysts enhanced the cell's resistance to carbon deposition and improved its stability. Techniques such as argon and oxygen purging, along with thermal regeneration, were investigated for carbon removal. These approaches have proven to be effective in diminishing carbon buildup and restoring cell functionality. Applying these strategies, PCFCs equipped with Ru-GDC fiber catalysts, operating at a stable 700 °C current, demonstrated prolonged stability for 117 h with methanol and 96 h with ethanol, markedly surpassing the performance of untreated cells. These advancements not only alleviate carbon deposition issues in PCFCs utilizing methanol and ethanol but also enhance the potential of biomass fuels in PCFC applications.

Nickel-Regulated Composite Cathode with Balanced Triple Conductivity for Proton-Conducting Solid Oxide Fuel Cells.

Proton-conducting solid oxide fuel cells (H-SOFCs) have the potential to be a promising technology for energy conversion and storage. To achieve high chemical compatibility and catalytic activity, nickel-doped barium ferrate with triple conducting ability is developed as cathodes for H-SOFCs, presenting an impressive electrochemical performance at intermediate temperatures. The cell performance with the optimized BaCe0.26 Ni0.1 Fe0.64 O3 -δ (BCNF10) composite cathode reaches an outstanding performance of 1.04Wcm-2 at 600°C. The high electrocatalytic capacity of the nickel-doped barium ferrate cathode can be attributed to its significant proton conductivity which is confirmed through hydrogen permeation experiments. Density functional theory (DFT) calculations are further conducted to reveal that the presence of nickel can enhance processes of hydration formation and proton migration, leading to improve proton conductivity and electro-catalytic activity.

Local Structure and Mixed Proton-Hole Conduction in Y and Al-Doped BaZrO3

A mixed proton-hole conductor is expected to be an excellent cathode material for proton-conducting solid oxide fuel cells (PCFCs). Accepter-doped BaZrO3 has oxygen vacancies that can be either proton defects in wet or holes in oxidizing conditions. When both proton and hole concentrations are high enough, mixed proton-hole conduction is achieved. Our group has investigated the relationship between local structural distortion and hydration energy of accepter-doped BaZrO3. It was suggested that large Y3+ prefers the compensation by protonic defects; on the other hand, small Al3+ does holes or oxygen vacancies. Thus, by doping Y and Al into BaZrO3 simultaneously, high mixed proton-hole conduction is expected without transition metals. This study focuses on the local structure around dopants, especially around Al, which can be observed by nuclear magnetic resonance (NMR) spectroscopy. The coordination number of oxygen around Al can be converted to the number of oxygen vacancies. Based on the local structural analysis, the defect equilibrium and mixed conductivity of Y and Al co-doped BaZrO3 can be discussed. BaZr0.8Y0.2-xAlxO3-δ (BZYA) was prepared by solid-state reaction method. Proton concentration was evaluated by thermogravimetric analysis at 350 ºC. AC impedance measurement was performed to evaluate the electrical conductivity of BAYA in dry or wet Ar. The proton transport number was measured at 600 ºC using a water-vapor concentration cell. 27Al Magic-Angle Spinning (MAS) NMR was performed to investigate the configuration around Al. The proton concentration of BZY10A10 and BZY15A5 was 0.6 mol%, 1.8 mol%, respectively. These proton concentrations were much smaller than that of BZY20, 18.6 mol%. This indicates that Al substitution led to a decrease in proton concentration. Meanwhile, those BZYAs showed a relatively high proton transport number, 0.84. This was found to be due to the unique oxygen configuration around Al. The local structure around Al and its effect on proton concentration and mixed conduction will be discussed in the presentation.

Sintering of Protonic Ceramics for Tubular Solid Oxide Fuel Cells

Protonic ceramics are considered to be the most promising candidates for intermediate-temperature solid oxide fuel cells (SOFCs) owing to their high proton conductivity and competitive electrochemical performance at intermediate temperatures (typically 500–700 °C). However, the fabrication of proton-conducting SOFCs has been challenging mainly due to the poor sinterability of common proton-conducting electrolyte materials. Significantly high sintering temperatures (1500–1600 °C) and long sintering times (up to 24 h) have been reported for obtaining dense, gas-tight proton-conducting electrolytes. These sintering conditions may lead to undesirable interfacial reactions and dense electrode microstructures, thereby limiting the cell performance. The present work focuses on optimizing the co-sintering temperature of tubular SOFCs with a traditional Ni–yttria-stabilized zirconia (YSZ) anode support and proton-conducting functional layers. BaZr0.3Ce0.5Y0.2O3 (BZCY), Ni–BZCY, and BZCY–BaCo0.4Fe0.4Ce0.1Y0.1O3 were used as the electrolyte, anode functional layer, and cathode, respectively. Various approaches to lowering the co-sintering temperature and resulting cell performances will be discussed. We will also examine the thermal cycling behavior and durability of the fabricated protonic SOFCs.

Modifying La0.5Sr0.5MnO3 with the U element leads to the formation of nanocomposites as a cathode for proton-conducting SOFCs

Sr-doped LaMnO3 (LSM) is a conventional cathode material for traditional solid oxide fuel cells (SOFCs), but its application in proton-conducting SOFCs is unsatisfactory due to the lack of catalytic activity of LSM at intermediate temperatures. Various strategies have been employed to optimize LSM performance, but no radiative element has been utilized. In this study, uranium was used to modify LSM. The U-doped LSM (LSMU) was not a pure phase but rather a mixture of LSM and SrUO4. The formation of oxygen vacancy was promoted at the LSM/SrUO4 interface, as indicated by first-principles calculations and experimental studies, potentially enhancing the oxygen reduction reaction (ORR) activity of the material. Using LSMU as the cathode, the proton-conducting SOFC (H–SOFC) reaches a peak power density of 1206 mW cm−2 at 700 °C, significantly greater than the LSM cell, which reached only 522 mW cm−2 under the same testing conditions. In addition, the current LSMU cell demonstrated the highest power output for LSM-based H–SOFCs to date, proving the LSUM to be an effective cathode for H–SOFCs. This study demonstrated a potential method for immobilizing uranium in a perovskite cathode oxide with improved performance for H–SOFCs.

Application of Ba0.5Sr0.5FeO3−δ-NdMnO3−δ Composite Cathode in Proton-Conducting Solid Oxide Fuel Cells

Ba0.5Sr0.5FeO3−δ (BSF) nanofibers are prepared via electrospinning and sintering at a temperature of 800 °C for 2 h to produce a pure cubic perovskite phase, with the aim of finding a high-performance cathode material suitable for proton-conducting solid oxide fuel cells (PCFCs) operating at medium temperatures. The results of SEM analysis showed that the BSF nanofibers are alternately stacked, presenting fluffy and uniform high porosity, which is favorable to the cathode polarization reaction of PCFCs. To balance the excessive coefficient of thermal expansion of the BSF cathode, it is combined with a negative thermal expansion (NTE) material NdMnO3−δ (NM). At 700 °C, the peak power density (PPD) of the BSF–NM cathode cell is 1170 mW cm−2, and the open-circuit voltage (OCV) of the single cell is 1.04 V. The corresponding polarization impedance (Rp) of the BSF–NM is 0.037 Ω cm2. This result is significantly better than the previously reported powder cathode BSF, indicating that the performance of PCFC can be further optimized by transforming the BSF cathode into a nanofiber state and compounding it with the NTE material NM.

Sintering of Protonic Ceramics for Tubular Solid Oxide Fuel Cells

The fabrication of proton-conducting solid oxide fuel cells (PC-SOFCs) has been challenging mainly due to the poor sinterability of common proton-conducting electrolyte materials. Extremely high sintering temperatures (up to 1600 °C) and long sintering times (>10 h) are typical for obtaining dense, gas-tight proton-conducting electrolytes. Apart from the high energy cost and long production cycle time, the high sintering temperature leads to several other issues, including chemical stability of the electrolyte and its compatibility with the electrodes. In the present work, we focused on optimizing the co-sintering temperature of tubular PC-SOFCs using a freeze-cast anode support. The densification of the BaZr0.3Ce0.5Y0.2O3 (BZCY) electrolyte was greatly facilitated by the sintering shrinkage of the NiO-BZCY anode support, which was as high as 35%. Preliminary electrochemical testing of the fabricated cells was also conducted.

Implications of Cation Interdiffusion between Double Perovskite Cathode and Proton-Conducting Electrolyte for Performance of Solid Oxide Fuel Cells

Chemical compatibility and cation interdiffusion between the double perovskite cobaltites RBaCo2O6−δ (R = Gd, Pr) and proton-conducting electrolyte BaZr0.8Y0.2O3−δ were studied. Chemical interaction was found to occur already at 1100 °C as a result of the partial dissolution of RBaCo2O6−δ (R = Gd, Pr) in BaZr0.8Y0.2O3−δ. Analysis of the element distribution along the cross sections of diffusion couples RBaCo2O6−δ(R = Gd, Pr)|BaZr0.8Y0.2O3−δ showed strong interdiffusion of cations, with cobalt being the most mobile one. Its diffusion depth in the electrolyte reaches up to several hundreds of micrometers. The addition of NiO as a sintering aid to BaZr0.8Y0.2O3−δ promotes cation diffusion especially through the grain boundary mechanism, increasing the diffusion depth of Co. The possible implications of cation interdiffusion on the performance of proton-conducting SOFCs are discussed based on the results obtained.

Anodic Reaction in Syngas-Fueled Proton-Conducting Solid Oxide Fuel Cells

Anode-supported proton-conducting solid oxide fuel cells (PC-SOFCs) fabricated with two representative proton-conducting oxides, BaCe0.7Zr0.1Y0.1Yb0.1O3-δ (BCZYYb) and BaZr0.8Y0.2O3-δ (BZY), were compared to obtain the insight into the electrochemical performances when fueled with syngas at 700°C and the correlation between the anode thickness (0.4, 0.8, and 1.6 mm) and operational stability. We have demonstrated that, in stability tests, the BCZYYb cells exhibited significantly higher maximum power density (MPD) than the BZY cells when operating on H2, 1.22 and 0.48 W/cm2 for the BCZYYb and BZY cells, but the BCZYYb cells degraded more rapidly than the BZY cells when operating on syngas. In addition, decreasing the anode thickness significantly enhanced the stability of BCZYYb cells operating on syngas, a reduction of 81, 76, and 71% in MPD for 1.6, 0.8, and 0.4 mm anode after 30 min. The electrochemical impedance spectra and X-ray diffraction patterns indicated that the rapid degradation of cerate-based cells with syngas could be mainly attributed to the considerable increase in polarization resistance due to the phase decomposition of the electrolyte powder in the anode. Heterogeneous catalysis was performed to study the catalytic reaction of the H2–CO mixture over anode powders prepared with the two proton-conducting oxides (Ni-BCZYYb and Ni-BZY) in a fixed bed reactor, and the CO conversion and selectivity to CO2 and CH4 were determined. For all anode powders, continuous CO2 production was initially observed with CH4 formation, and no significant difference in catalytic activity trends was observed between both anode powders. An increased residence time substantially decreased the normalized CO2 yield, which was associated with the potential secondary reaction of CO2 with H2, CH4, or perovskite oxide. Based on the results of heterogeneous catalysis with both anode powders, the observed cell degradation on both cells during operation with syngas may be primarily attributed to carbon coking due to CO disproportionation; however, more than 4 times rapid degradation of the cerate-based cell when operating with syngas was clearly demonstrated to be attributed to the decomposition of the electrolyte powder in anode by the resulting CO2 from the catalytic reaction of the H2–CO mixture.

Revealing and Quantifying the Role of Oxygen-Ionic Current in Proton-Conducting Solid Oxide Fuel Cells: A Modeling Study

Revealing and Quantifying the Role of Oxygen-Ionic Current in Proton-Conducting Solid Oxide Fuel Cells: A Modeling Study

Self-assembled triple-conductive La2Ni1 − xCe2xO4+δ cathodes for proton-conducting solid oxide fuel cells

A novel composite cathode with triple conductivity and excellent stability is prepared for proton-conducting SOFCs using one-step combustion method. The dual phase composite cathode presents an excellent performance of 1516 mW cm−2 at 700 °C.

Synthesis of Yttrium Doped Barium Zirconate/Cerate Electrolyte Materials and Densification Using Conventional and Cold-Sintering Processes

Compared to high temperature SOEC usually based on Yttrium stabilized Zirconia electrolytes, intermediate temperature PCEC allows the production of water free hydrogen and a better chemical stability. Proton conducting perovskite specific materials, such as Barium Indates1, Zirconate or Cerates2 are nearly commercial electrolytes for such devices.This study focuses on the synthesis the characterization and the densification of the BaZr1-xCexY0.1O3- δ 3 powder. At intermediate temperature and under humid atmosphere, hydration process allows diffusion of protonic charges. Such electrolyte material combines a low thermal expansion coefficient and a high protonic conductivity. Two specific stoichiometry’s have been studied, Cerium rich BaZr 0.3 Ce 0.6 Y0.1O3- δ (BZCY361) and Zirconium rich BaZr 0.7 Ce 0.2 Y0.1O3- δ (BZCY721). BZCY361 shows at 550°C, a conductivity level of 2.10- 2 S.cm- 1. However, despite its high protonic conductivity, the cerium rich phase is not stable at high temperature and is torn apart in presence of carbon dioxide.BaZr1-xCexY0.1O3- δ powder has been synthetized by combustion reaction based on nitrate precursors and glycine as organic complexing/fuel agent. The fuel/oxidizer (nitrates) ratio, which is a key parameter4, has been optimized in order to obtain the best purity and crystallinity. The powder is then milled and calcined. The single-phase electrolyte powder is conventionally shaped into pellets and densified A minimal temperature of 1600°C is necessary to obtained a density of 90-95%. In order to reduce the sintering temperature, an intermediate sintering step called "Cold Sintering Process"5 (CSP) has been investigated. In this technic, derived from the hydrothermal method, BCZY powder mixed with a small volume of liquid phase (3-30 wt%) is simultaneously pressed (at 50 to 500 MPa) and heated during a short time period (1-60 min) at low temperatures (100-200°C), leading to dense pellets.In regards to design a complete cell based on this electrolyte, EIS has been performed under hydrogen and air atmosphere. The electrochemical measurements of the samples provided by the different protocols and stoichiometry’s have been compared in order to determine the impact of the CSP and stoichiometry parameters on the ionic conductivity of the material.Acknowledgment: This study, included in the PhD of P. Castellani, was made possible with support from the Franco German ANR-BMBF project (Grant No. ANR-19-ENER-0003-12 [1] Quarez, Eric, Samuel Noirault, Annie Le Gal La Salle, Philippe Stevens, et Olivier Joubert. « Evaluation of Ba2(In0.8Ti0.2)2O5.2−n(OH)2n as a Potential Electrolyte Material for Proton-Conducting Solid Oxide Fuel Cell ». Journal of Power Sources 195 (15), 4923-27 (2010) [2] Thabet, K., Le Gal La Salle, A., Quarez, E., and Joubert, O. “Protonic-Based Ceramics for Fuel Cells and Electrolyzers,” Solid Oxide-Based Electrochemical Devices, Elsevier, pp. 91–122 (2020) [3] Thabet, K., Devisse, M., Quarez, E., Joubert, O., and Le Gal La Salle, A. “Influence of the Autocombustion Synthesis Conditions and the Calcination Temperature on the Microstructure and Electrochemical Properties of BaCe0.8Zr0.1Y0.1O3− δ Electrolyte Material,” Solid State Ionics, 325, pp. 48–56, (2018) [4] Varma, A., Mukasyan, A. S., Rogachev, A. S., and Manukyan, K. V., “Solution Combustion Synthesis of Nanoscale Materials,” Chem. Rev., 116(23), pp. 14493–14586 (2016) [5] Guo, H., Baker, A., Guo, J., and Randall, C. A., “Cold Sintering Process: A Novel Technique for Low‐Temperature Ceramic Processing of Ferroelectrics,” J. Am. Ceram. Soc., 99(11), pp. 3489–3507 (2016) Figure 1

Evaluation of La2-x(Ca/Sr)xNi1-yFeyO4+δ (x = 0.5, 0.6; y = 0.4, 0.5) as cathodes for proton-conducting SOFC based on lanthanum tungstate

La2NiO4+δ, La1.4Ca0.6Ni0.6Fe0.4O4+δ (LCNF0604), La1.4Sr0.6Ni0.6Fe0.4O4+δ (LSNF0604), La1.4Sr0.6Ni0.5Fe0.5O4+δ (LSNF0605) and La1.5Sr0.5Ni0.6Fe0.4O4+δ (LSNF0504) were synthesized by the citrate-nitrate technique with the following four annealing steps at 950 °C in air (La2NiO4+δ, LCNF0604, LSNF0604) or in atmosphere with the reduced (10−5 atm) oxygen partial pressure (LSNF0605, LSNF0504). Phase purity of the samples is confirmed by the X-ray powder diffraction (XRPD). Electrochemical impedance spectroscopy studies of the symmetrical cells based on the proton-conducting La28−zW4+zO54+1.5z (z = 0.85, LWO85) electrolyte reveal that the polarization resistance (Rp) decreases in the row LCNF0604>La2NiO4+δ>LSNF0504>LSNF0604>LSNF0605 in the temperature interval of 600–800 °C in wet air. The process at low frequencies related to the surface exchange, provides the most significant contribution to the polarization resistance of the studied cells. Higher polarization resistance for the La2NiO4+δ/LWO85 cell can be associated with blocking of protons/protonic species. The minimal Rp value of 1 Ω cm2 at 800 °C in wet air is demonstrated by the LSNF0605/LWO85 symmetrical cell. The maximal power density for the anode-supported LSNF0605/LWO85/Ni-LWO85 single fuel cell is equal to 55 mW cm−2 at 750 °C. The performance of the fuel cell is limited by the formation of La2O3 at the LWO85/Ni-LWO85 interface due to chemical interaction between NiO and LWO85. To improve the performance of the studied fuel cell the development of new proton-conducting buffer layer stable to LWO85 is required.

Nanofibrous La0.7sr0.3feo3-Δ-Sdc Cobalt-Free Composite Cathode for Proton-Conducting Solid Oxide Fuel Cell

Nanofibrous La0.7sr0.3feo3-Δ-Sdc Cobalt-Free Composite Cathode for Proton-Conducting Solid Oxide Fuel Cell

Analysis of symmetry variation as a function of rare earth dopant concentration in proton conducting solid oxide fuel cells

Compositional induced phase transition in proton conducting solid oxide fuel cells (PC-SOFC) is activated due to vacancy generation and dopant substitution altering proton conductivity are of prime concern. In the present work symmetry variations from single phase orthorhombic (Pnma) (BaCeO3) to rhombohedral (R3c) (BaCe0.75Y0.25O3−δ (BCY_25)) and finally to monoclinic (I12/m1) (BaCe0.50Y0.50O3−δ (BCY_50)) through multi-phase coexistence at intermediate Y3+ doping concentrations (BaCe0.875Y0.125O3−δ (BCY_12.5) and (BaCe0.625Y0.375O3−δ (BCY_37.5)) has been affirmed through DFT-VASP simulated XRD and neutron diffraction profile. Lattice contraction due to oxygen vacancy dominance alongside threshold for oxygen vacancy generation between BCY_37.5 and BCY_50 has been demonstrated.

New Insights on the Nickel State Deposited by Hydrazine Wet-Chemical Synthesis Route in the Ni/BCY15 Proton-Conducting SOFC Anode.

Yttrium-doped barium cerate (BCY15) was used as an anode ceramic matrix for synthesis of the Ni-based cermet anode with application in proton-conducting solid oxide fuel cells (pSOFC). The hydrazine wet-chemical synthesis was developed as an alternative low-cost energy-efficient route that promotes ‘in situ’ introduction of metallic Ni particles in the BCY15 matrix. The focus of this study is a detailed comparative characterization of the nickel state in the Ni/BCY15 cermets obtained in two types of medium, aqueous and anhydrous ethylene glycol environment, performed by a combination of XRD, N2 physisorption, SEM, EPR, XPS, and electrochemical impedance spectroscopy. Obtained results on the effect of the working medium show that ethylene glycol ensures active Ni cermet preparation with well-dispersed nanoscale metal Ni particles and provides a strong interaction between hydrazine-originating metallic Ni and cerium from the BCY15 matrix. The metallic Ni phase in the pSOFC anode is more stable during reoxidation compared to the Ni cermet prepared by the commercial mechanical mixing procedure. These factors contribute toward improvement of the anode’s electrochemical performance in pSOFC, enhanced stability, and a lower degradation rate during operation.