Demonstrating the dual functionalities of CeO2–CuO composites in solid oxide fuel cells

Nowadays, lowering the operating temperature of solid oxide fuel cells (SOFCs) is a major challenge towards their widespread application. This has triggered extensive material studies involving the research for new electrolytes and electrodes. Among these works, it has been shown that CeO₂ is not only a promising basis of solid oxide electrolytes, but also capable of serving as a catalytic assistant in anode. In the present work, to develop new electrolytes and electrodes for SOFCs based on these features of CeO₂, a new type of functional composite is developed by introducing semiconductor CuO into CeO₂. The prepared composites with mole ratios of 7:3 (7CeO₂–3CuO) and 3:7 (3CeO₂–7CuO) are assessed as electrolyte and anode in fuel cells, respectively. The cell based on 7CeO₂–3CuO electrolyte reaches a power outputs of 845 mW cm^?2 at 550 °C, superior to that of pure CeO₂ electrolyte fuel cell, while an Ce_0.8Sm_0.2O_2-δ electrolyte SOFC with 3CeO₂–7CuO anode achieves high power density along with open circuit voltage of 1.05 V at 550 °C. In terms of polarization curve and AC impedance analysis, our investigation manifests the developed 7CeO₂–3CuO composite has good electrolyte capability with a hybrid H⁺/O^2? conductivity of 0.1–0.137 S cm^?1 at 500–550 °C, while the 3CeO₂–7CuO composite plays a competent anode role with considerable catalytic activity, indicative of the dual-functionalities of CeO₂–CuO in fuel cell. Furthermore, a bulk heterojunction effect based on CeO₂/CuO pn junction is proposed to interpret the suppressed electrons in 7CeO₂–3CuO electrolyte. Our study thus reveals the great potential of CeO₂–CuO to develop functional materials for SOFCs to enable low-temperature operation.     

Catalytic modification of Ni–Sm-doped ceria anodes with copper for direct utilization of dry methane in low-temperature solid oxide fuel cells

A Cu/Ni/Sm-doped ceria (SDC) anode has been designed for direct utilization of dry methane in low-temperature anode-supported solid oxide fuel cells. The anode is prepared by the impregnation method, whereby a small amount of Cu is incorporated into the previously prepared Ni/SDC porous matrix. After reduction, Cu nanoparticles adhere to and are uniformly distributed on the surface of the Ni/SDC matrix. For the resulting Cu/Ni/SDC anode-supported cell, maximum power density of 317 mW cm⁻² is achieved at 600 °C. The power density shows only ∼2% loss after 12-h operation. The results demonstrate that the Cu/Ni/SDC anode effectively suppresses carbon deposition by decreasing the Ni surface area available and the level of carbon monoxide disproportionation. This combination of effects results in very low-power density loss over the operating time.     

Performance and durability of Ni–Co alloy cermet anodes for solid oxide fuel cells

Ni alloys are examined as redox-resistant alternatives to pure Ni for solid oxide fuel cell (SOFC) anodes. Among the various candidate alloys, Ni–Co alloys are selected due to their thermochemical stability in the SOFC anode environment. Ni–Co alloy cermet anodes are prepared by ammonia co-precipitation, and their electrochemical performance and microstructure are evaluated. Ni–Co alloy anodes exhibit high durability against redox cycling, whilst the current-voltage characteristics are comparable to those of pure Ni cermet anodes. Microstructural observation reveals that cobalt-rich oxide layers on the outer surface of the Ni–Co alloy particles protect against further oxidation within the Ni alloy. In long-term durability tests using highly humidified hydrogen gas, the use of a Ni–Co cermet with Gd-doped CeO₂ suppresses degradation of the power generation performance. It is concluded that Ni–Co alloy cermet anodes are highly attractive for the development of robust SOFCs.     

Catalytic activity of Ni–YSZ–CeO2 anode for the steam reforming of methane in a direct internal-reforming solid oxide fuel cell

As one of the key technologies in the development of a direct internal-reforming solid oxide fuel cell, catalytic activity and stability of a Ni–YSZ–CeO₂ anode on a zirconia electrolyte for the steam reforming of methane was investigated by experiments using a differential fuel cell reactor. The effects of the partial pressure of CH₄, H₂O and H₂, and temperature as well as the electrochemical oxidation on the catalytic activity were analyzed. It was found that the catalytic activity of the Ni–YSZ–CeO₂ anode was higher than that of the Ni–YSZ reported especially at low temperature. A deterioration of the catalytic activity of the anode was observed at low P_H2 and high P_H2O atmosphere, and also at high current densities. This might be caused by the oxidation of the Ni surface by H₂O in the reaction gas and that produced by the anodic reaction. A rate equation for a fractional function for the steam reforming on open circuit was also proposed.     

Cu doped Ni–Co spinel protective coatings for solid oxide fuel cell interconnects application

Four different amount of Cu doped Ni–Co alloy coatings were fabricated on SUS430 substrate by electroplating for solid oxide fuel cells (SOFCs) interconnects application. After oxidation at 800 °C, the microstructure and oxide phase of samples were tested by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Our experimental results indicated that the Cu addition improved the electrical behavior of Ni–Co alloy coating. Cu doping reduced the activation energy (Ea) of electrons hopping and inhibited the growth of Cr₂O₃ oxide layer. Furthermore, the oxidation kinetics and electrical properties of the alloy coatings were obtained. These results showed that the 9% Cu doped Ni–Co coated steels achieved the minimum parabolic rate constant (2.05 × 10⁻¹⁴ g²cm⁻⁴s⁻¹) and area specific resistance (14.11 mΩ cm²) after the thermostatic oxidation process.     

Direct reforming of Methane–Ammonia mixed fuel on Ni–YSZ anode of solid oxide fuel cells

To control the temperature distribution in the Ni–YSZ (yttria-stabilized zirconia) anode of solid oxide fuel cells (SOFCs) by efficiently utilizing the heat generated by electrochemical reactions, the supply of methane–ammonia mixed fuel is proposed. The reaction characteristics of reforming/decomposition of the mixed fuel on a Ni–YSZ catalyst are experimentally investigated. A mixture gas of methane, steam, ammonia, and balance argon is supplied to a packed bed catalyst placed in a quartz tube in an electric furnace. The crushed Ni–YSZ anode of SOFCs is used as the catalyst. The exhaust gas composition is analyzed by gas chromatography and the streamwise temperature distribution of the catalyst bed is measured by an infrared camera. It is found that ammonia decomposition preferentially proceeds and steam methane reforming becomes active after sufficient ammonia has been consumed. A low-temperature region is formed by steam methane reforming owing to its strongly endothermic nature. Its position moves downstream while its magnitude decreases as the ammonia concentration in the fuel increases. This shows that the local temperature distribution can be controlled by tuning the ratio of methane to ammonia in the mixed fuel. It is also found that, at a certain mixture ratio, the mixed fuel realizes a hydrogen production rate higher than that for only methane or ammonia.     

Leveraging in-situ formation of Ni–Fe nanoparticles to promote the catalytic performance of Ruddlesden-Popper based electrode for symmetrical solid oxide fuel cells

Ruddlesden?Popper layered oxide, La_0.25Sr_2.75FeNiO_7-δ (LSFN) is evaluated as a potential electrode material for symmetrical solid oxide fuel cells. The in-situ formation of Ni–Fe alloy nanoparticles on the LSFN surface in reducing atmosphere can be believed to enhance the activity towards hydrogen oxidation reaction. LSFN exhibit maximum conductivity of 221.2 S/cm and 0.206 S/cm in air and hydrogen environment. Furthermore, LSFN is mixed with GDC powder to form a composite electrode for symmetric solid oxide fuel cells (SSOFC). Results show that with the combination of GDC, the maximum power density of YSZ-based SSOFC enlarges from 232.3 mW cm^?2 to 348.5 mW cm^?2, and related polarization resistance reduces from 0.359 Ω cm² to 0.108 Ω cm². The improved performance is attributed to the enlarged triple-phase boundary with the mixing of GDC. In addition, YSZ-based SSOFC with the LSFN-GDC composite electrode shows a stable performance in intermediate-temperature SSOFCs within 200 h, which indicates that LSFN-GDC composite material is a prospective symmetrical electrode for SSOFC.     

Electrochemical properties and durability of in-situ composite cathodes with SmBa0.5Sr0.5Co2O5+δ for metal supported solid oxide fuel cells

The electrochemical properties and long-term performance of an in-situ composite cathode comprised of SmBa_0.5Sr_0.5Co₂O_5+δ (SBSCO) and Ce_0.9Gd_0.1O_2?δ (CGO91) are investigated for metal supported solid oxide fuel cell (MS-SOFC) application.The Area Specific Resistance (ASR) of an in-situ composite cathode comprised of 50 wt% of SBSCO and 50 wt% of CGO91 (SBSCO:50) is 0.031 Ω cm² in the first stage of measurement at 700 °C; this value of ASR increases to 0.138 Ω cm² after 1000 h. The ASR of SBSCO:50 (in-situ sample at 750 °C) is 0.014 Ω cm² at the initial stage of measurement; the increase of ASR after 1000 h at 750 °C is only 0.067 Ω cm². These results suggest that the optimum temperature for in-situ firing of an SBSCO:50 cathode sample of MS-SOFC is higher than 700 °C, ideally around 750 °C.     

Anode performance of LST–xCeO2 for solid oxide fuel cells

La-doped SrTiO₃ (LST)–xCeO₂ (x = 0, 30, 40, 50) composites were evaluated as anode materials for solid oxide fuel cells in terms of chemical compatibility, electrical conductivity and fuel cell performance in H₂ and CH₄. Although the conductivity of LST–xCeO₂ composite slightly decreased from 4.6 to 3.9 S cm⁻¹ in H₂ at 900 °C as the content of CeO₂ increased, the fuel cell performance improved from 75.8 to 172.3 mW cm⁻² in H₂ and 54.5 to 139.6 mW cm⁻² in CH₄ at 900 °C. Electrochemical impedance spectra (EIS) indicated that the addition of CeO₂ into LST can significantly reduce the fuel cells polarization thus leading to a higher performance. The result demonstrated the potential ability of LST–xCeO₂ to be used as SOFCs anode.     

Development of trimetallic Ni–Cu–Zn anode for low temperature solid oxide fuel cells with composite electrolyte

Trimetallic alloys of Ni_0.6Cu_0.4−xZn_x (x = 0, 0.1, 0.2, 0.3, 0.4) have been investigated as promising anode materials for low temperature solid oxide fuel cells (SOFCs) with composite electrolyte. The alloys have been obtained by reduction of Ni_0.6Cu_0.4−xZn_xO oxides, which are synthesized by using the glycine–nitrate process. Increasing the Zn content x decreases the particle sizes of the oxides at a given sintering temperature. Fuel cells have been constructed using lithiated NiO as cathode and as-prepared alloys as anodes based on the composite electrolyte. Peak power densities are observed to increase with the increasing Zn addition concentration into the anode. The maximum power density of 624 mW cm⁻² at 600 °C, 375 mW cm⁻² at 500 °C has been achieved for the fuel cell equipped with Ni_0.6Zn_0.4 anode. A.c. impedance results show that the resistances dramatically decrease with increasing temperatures under open circuit voltage state. Both cathodic and anodic interfacial polarization resistances increase with the amplitude of applied DC voltage. Possible reaction process for H₂ oxidation reaction at anode based on composite electrolyte has been proposed for the first time. The stability of the fuel cell with Ni_0.6Cu_0.2Zn_0.2 composite anode has been investigated. The results indicate that the trimetallic Ni_0.6Cu_0.4−xZn_x anodes are considerable for low temperature SOFCs.     

Electrical properties of SDC–BCY composite electrolytes for intermediate temperature solid oxide fuel cell

The electrolyte material Ce_0.85Sm_0.15O_1.92 (SDC) powders are synthesized by glycine–nitrate processes and BaCe_0.83Y_0.17O_3−δ (BCY) powders are synthesized by sol–gel processes, respectively. Then SDC–BCY composite electrolytes are prepared by mixing SDC and BCY. The SDC and BCY powders are mixed in the weight ratio of 95:5, 90:10 and 85:15 and named as SB95, SB90 and SB85, respectively. The electrical properties of SDC and SDC–BCY composites are investigated. The experimental results show that SDC–BCY composites exhibit the excellent conductivity and could significantly enhance the fuel cell performances. The behavior that SDC–BCY composites display hybrid proton and oxygen ion conduction is substantiated. Among these electrolytes, the maximum power density reaches as high as 159 mW cm⁻² for the fuel cell based on SB90 composite electrolyte at 600 °C.     

Interaction between electrode materials Sr2FeCo0.5Mo0.5O6−δ and hydrogen sulfide in symmetrical solid oxide fuel cells

Symmetrical Solid Oxide Fuel Cells (SSFCs) are highly competitive options for a sustainable energy future, however, its application is hindered by the development of more surfer tolerance and highly efficient electrodes. Sr₂FeCo_0.5Mo_0.5O_6?δ (SFCM) was investigated as potential electrode materials for SSFCs using H₂S as a fuel directly. SFCM powders, before and after exposure to 0.05% H₂S/N₂, were carried out to analyze the structure and morphology by X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM). A maximum power density of 45.69 mW cm^?2 was obtained in the configuration of SSFC (SFCM/LSGM/SFCM) in 0.05% H₂S/N₂ at 800 °C. SFCM had high catalytic activity in converting H₂S into SO₂ without obviously deactivation. After cell test, X-ray photoelectron spectroscopy (XPS) was used to reveal the distribution of valence state of sulfur. There founding demonstrated that the SSCM has a certain surfer tolerance ability, and that understanding how the electrodes works and impact the cell performance is critical to the design of highly stable double perovskite electrodes.     

High-performance La0.5(Ba0.75Ca0.25)0.5Co0.8Fe0.2O3-δ cathode for proton-conducting solid oxide fuel cells

La_0.5(Ba_0.75Ca_0.25)_0.5Co_0.8Fe_0.2O_3-δ, a simple perovskite cathode material with high electrical conductivity (940 S cm^?1 at 600 °C) and impressive surface catalytic activity, was prepared and used in proton-conducting solid oxide fuel cells. As its thermal expansion coefficient is higher than that of the electrolyte material BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ, they were combined and used as a composite cathode. The crystal structure, chemical compatibility, electrical conductivity, cell performance, and the oxygen reduction reaction of the cathode material were explored, and we found that the single fuel cell developed with the composite cathode achieved excellent electrochemical performance, with both a low polarization resistance and high peak power density (0.044 Ω cm² and 1102 mW cm^?2 at 750 °C, respectively). Outstanding stability was also achieved, as indicated by a long-term 100-h test. Additionally, the rate-limiting steps of the oxygen reduction reaction were the oxygen adsorption, dissociation, and diffusion processes.     

Synthesis and electrical properties of Al-doped Sr2MgMoO6-δ as an anode material for solid oxide fuel cells

Aluminum doped Sr₂MgMoO_6-δ (SMMO) was synthesized via citrate-nitrate route. Dense samples of Sr₂Mg_1-xAl_xMoO_6−δ (0 ≤ x ≤ 0.05) were prepared by sintering the pellets at 1500 °C in air and then reducing at 1300 °C in 5%H₂/Ar. The electrical conductivity strongly depended on the preparing atmosphere, samples reduced in 5%H₂/Ar exhibited higher conductivity than those unreduced. Al-doping increased remarkably the electrical conductivity of Sr₂Mg_1-xAl_xMoO_6−δ. The reduced samples displayed a relatively stable electrical conductivity under oxygen partial pressure (Po₂) from 10⁻¹⁹ to 10⁻¹⁴ atm at 800 °C, and exhibited an excellent recoverability in electrical conductivity when cycled in alternative air and 5%H₂/Ar atmospheres. Sr₂Mg_0.95Al_0.05MoO_6−δ material showed a good chemical compatibility with LSGM and GDC electrolytes below 1000 °C, while there was an obvious reaction with YSZ. Al-doping improves the anode performance of SMMO in half-cell of Pt/Sr₂Mg_1-xAl_xMoO_6−δ∣GDC∣Pt in H₂ fuel. The present results demonstrate that Sr₂Mg_1-xAl_xMoO_6−δ is a potential anode material for intermediate temperature-Solid Oxide Fuel Cells (IT-SOFCs).     

Fe doped Ni–Co alloy by electroplating as protective coating for solid oxide fuel cell interconnect application

To obtain higher electrical conductivity and lower area specific resistance (ASR), the 10% Fe doped Ni–Co (NCF) alloy was prepared on SUS 430 steel substrate by electroplating for solid oxide fuel cells (SOFCs) interconnects application. Then, the SUS 430 steels and NCF coated steels were oxidized at 800 °C. The microstructure and oxide phase of samples were tested by scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). These results proved that the NCF coated steel achieved the lower oxidation rate of 9.28 × 10⁻¹⁴ g²cm⁻⁴s⁻¹ and ASR of 14.72 mΩ cm².     

Control-oriented thermal management of solid oxide fuel cells based on a modified Takagi–Sugeno fuzzy model

Thermal management for a solid oxide fuel cell (SOFC) is actually temperature control, due to the importance of cell temperature for the performance of an SOFC. An SOFC stack is a nonlinear and multi-variable system which is difficult to model by traditional methods. A modified Takagi–Sugeno (T–S) fuzzy model that is suitable for nonlinear systems is built to model the SOFC stack. The model parameters are initialized by the fuzzy c-means clustering method, and learned using an off-line back-propagation algorithm. In order to obtain the training data to identify the modified T–S model, a SOFC physical model via MATLAB is established. The temperature model is the center of the physical model and is developed by enthalpy-balance equations. It is shown that the modified T–S fuzzy model is sufficiently accurate to follow the temperature response of the stack, and can be conveniently utilized to design temperature control strategies.     

A novel system for the production of pure hydrogen from natural gas based on solid oxide fuel cell–solid oxide electrolyzer

In this paper, a novel process for the production of pure hydrogen from natural gas based on the integration of solid oxide fuel cells (SOFCs) and solid oxide electrolyzer cells (SOECs) is presented. In this configuration, the SOFC is fed by natural gas and provides electricity and heat to the SOEC, which carries out the separation of steam into hydrogen and oxygen. Depending on the system layout considered, the oxygen available at the SOEC anode outlet can be either mixed with the SOFC cathode stream in order to improve the SOFC performance or regarded as a co-product. Two configurations of the cell stack are studied. The first consists of a stack with the same number of SOFCs and SOECs working at the same current density. In this case, since in typical operating conditions the voltage delivered by the SOFC is lower than the one required by the SOEC, the required additional power is supplied by means of an electric grid connection. In the second case, the electricity balance is compensated by providing additional SOFCs to the stack, which are fed by a supplementary natural gas feed. Simulations carried out with Aspen Plus show that pure hydrogen can be produced with a natural gas to hydrogen LHV-efficiency that is about twice the value of a typical water electrolyzer and comparable to that of medium-scale reformers.     

Electroplated Ni–Fe2O3 composite coating for solid oxide fuel cell interconnect application

Ni–Fe₂O₃ composite coating was applied onto ferritic stainless steel using the cost-effective method of electroplating for intermediate temperature solid oxide fuel cell (SOFC) interconnects application. By comparison, the coated and bare steels were evaluated at 800 °C in air corresponding to the cathode environment of SOFC. The oxidation investigations indicated that the oxidation rate of the coated steel was close to that of the bare steel after initially rapid mass gain. The mass gain of the coated steel was higher than that of the bare steel owing to the formation of double-layer oxide structure with an outer layer of (Ni,Fe)₃O₄/NiO atop an inner layer of Cr₂O₃. The area specific resistance (ASR) of the double-layer oxide scale was lower than that of the Cr₂O₃ scale thermally grown on the bare steel.     

Performance of Pd-impregnated Sr1.9FeNb0.9Mo0.1O6-δ double perovskites as symmetrical electrodes for direct hydrocarbon solid oxide fuel cells

Symmetrical solid oxide fuel cell (SSOFC) is one of efficient ways to simplify preparation process, reduce manufacturing cost, and improve redox stability and reliability. Here, we report the performance of Sr-deficient Sr_1.9FeNb_0.9Mo_0.1O_6-δ (SFNM) double perovskites as symmetrical electrodes for direct-hydrocarbon solid oxide fuel cells and significant improvement of electrochemical performance. The SFNM exhibits good structural stability, suitable thermal expansion coefficient and highly chemical compatibility with Sm_0.2Ce_0.8O_1.9 (SDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3–δ (LSGM) electrolytes in both air and 5% H₂/Ar atmospheres. The area specific resistance of SFNM electrode is decreased by 3.6 and 8.4 times at 800 °C in air and H₂, respectively, as compared to the pristine Sr₂FeNbO_6-δ electrode. The electrochemical performance is further improved by introducing a small amount of Pd to form Pd-impregnated SFNM composite electrode (Pd-SFNM). The SSOFCs with Pd-SFNM after two-time impregnation treatments as the electrodes achieve impressive electrochemical performances in different fuels. The Pd-SFNM symmetrical electrode reveals good electrochemical stability operating on CH₄–CO₂ mixed gas.     

Electrochemical performance of Sr1.9La0.1Fe1.5Mo0.5O6-δ symmetric electrode for solid oxide fuel cells with carbon-based fuels

La-doped Sr_2-xLa_xFe_1.5Mo_0.5O_6-δ perovskite oxides are synthesized and used as a symmetric electrode to evaluate the effect of La on the crystal structure, conductivity, and catalytic activity for O₂ reduction and H₂ oxidation reaction. The electronic doping effect dominates the oversize effect in Sr_2-xLa_xFe_1.5Mo_0.5O_6-δ oxide, resulting in unit cell volume expansion and decreased conductivity in air. In addition, the introduction of La increases the chemical structural stability of Sr₂Fe_1.5Mo_0.5O_6-δ in reducing condition due to the higher La–O bond compared with Sr–O bond, leading to high catalytic activity for the H₂ oxidation reaction. At 800 °C, the R_p values of Sr_1.9La_0.1Fe_1.5Mo_0.5O_6-δ symmetric cell in air and wet H₂ are as low as 0.075 and 0.21 Ω cm², respectively. Moreover, the peak power densities of 769, 561, 439, and 653 mW cm^?2 at 850 °C are obtained when wet H₂, CO, CH_4, and C₃H₈ are used as fuels on Sr_1.9La_0.1Fe_1.5Mo_0.5O_6-δ/LSGM/Sr_1.9La_0.1Fe_1.5Mo_0.5O_6-δ cell. The symmetric cell also shows excellent stability (>100 h) in wet H₂/air, implying Sr_1.9La_0.1Fe_1.5Mo_0.5O_6-δ oxide is a promising symmetric electrode material.