Addition effects of erbia-stabilized bismuth oxide on ceria-based carbonate composite electrolytes for intermediate temperature-−solid oxide fuel cells

Highly conductive Er_0.2Bi_0.8O_1.5 (ESB) and rare-earth doped ceria solid oxide electrolytes (SOEs) at intermediate temperature (IT) continue to suffer disadvantages in terms of thermodynamic instability and significant electronic conduction, respectively, at low oxygen partial pressure for solid oxide fuel cell (SOFC) operations. It is therefore necessary to improve the low-temperature ionic conductivity in order to enhance the electrolytic domain of these materials and thereby mitigate cell efficiency dissipation by electronic conduction. In this work, an advanced multiphase carbonate composite material based on ceria has been developed to overcome this IT-SOE challenge. This advanced electrolyte is comprise of nanostructured neodymium-doped ceria (NDC) and 38 wt% (Li–0.5Na)₂CO₃ carbonate with a small amount of ESB phase. The addition of 2 wt% ESB in ceria-based materials decreases the grain boundary resistance of the SOEs in the IT range. Further, a small amount of highly conducting ESB phase in the NDC/[(Li–0.5Na)₂CO₃] composite electrolyte increases the overall conductivity of the composite SOEs. The NDC electrolyte containing 38 wt% carbonate shows the highest conductivity of 0.104 Scm⁻¹ at 600 °C, while the conductivity is increased to 0.165 Scm⁻¹ by the addition of 2 wt% ESB. In addition, the activation energy of the multiphase composite electrolytes (0.52 eV) is lower than that of the NDC/carbonates (0.65 eV) in the IT range. This is attributed to the effect of the physical properties of the NDC sample, induced by the light ESB doping, on the ionic conductivity, and this effect is closely associated with the grain boundary property. Furthermore, the interfacial effects of the multiphase materials also contribute to the improved conductivity of this advanced composite electrolyte.     

The development of semiconductor-ionic conductor composite electrolytes for fuel cells with symmetrical electrodes

Lowering the operational temperature of solid oxide fuel cells (SOFCs) is a vital research challenge for achieving broad commercialization of SOFCs. However, there is currently a lack of suitable electrolyte materials with sufficient ionic conductivity. In this review, the recent progress in semiconductor-ionic conductor composite strategies and related key technologies for low temperature SOFCs (LT-SOFCs) applications is highlighted, in particular, emphasizing the demonstration of such composite materials sandwiched between semiconductor electrodes in a symmetrical configuration that has delivered a potent solution. Despite the co-existence of electronic and ionic conduction in the composite membrane, no electronic short-circuiting was displayed, but rather an enhanced device power output was achieved. Here, the recent progresses in the development of SOFCs, from single-layer fuel cells, to two-phase semiconductor-ionic conductor membrane fuel cells with symmetrical electrodes, are discussed. This review will furnish researchers within the SOFC community and beyond with a broader understanding of the theory, development and significance of composite materials for LT-SOFCs.     

Recent progress on solid oxide fuel cell: Lowering temperature and utilizing non-hydrogen fuels

A solid oxide fuel cell (SOFC) is a promising energy conversion device with high efficiency and low pollutant emission. The practical application of the conventional SOFCs is limited mainly because of their high operating temperature and the inconvenience brought by the H₂ fuel utilization. This work reviews the recent progress on intermediate temperature SOFCs especially with non-hydrogen fuels. Composite electrolyte consisting of a solid oxide ionic conducting phase and a molten carbonate phase exhibits sufficient ionic conductivity in the intermediate temperature range, i.e. 500–800 °C, and facilitates the simultaneous conduction of H⁺, O²⁻ and CO₃²⁻ ions. A single cell with the composite electrolyte shows a promising power density, 1700 mW cm⁻² at 650 °C with hydrogen as the fuel. The composite electrolyte has been also employed in a direct carbon fuel cell (DCFC), and the simultaneous conduction of O²⁻ and CO₃²⁻ in the electrolyte has been proposed. Recently, perovskite structured materials are found to have good resistance to coke formation as the anode of the direct hydrocarbon solid oxide fuel cell, and several carbon resistant perovskite anodes are employed in all-perovskite structured SOFCs, which exhibit excellent performance with CH₄ and methanol as the fuel.     

Enhanced ionic conductivity in calcium doped ceria – Carbonate electrolyte: A composite effect

Recently, ceria-based nanocomposites, as a proton and oxygen ion conductor, has been developed as promising electrolyte candidates for low-temperature solid oxide fuel cells (LTSOFCs). Up to now, samarium doped ceria (SDC) was studied as a main oxide for nanocomposite electrolyte; while calcium doped ceria (CDC) is considered as a good alternative from both material performance and economical aspects. Yet the conduction behavior of CDC-based composite has not been reported. In the present study, calcium doped ceria was prepared by oxalate co-precipitation method, and used for the fabrication of CDC/Na₂CO₃ composite. The thermal decomposition process, structure and morphology of the samples were characterized by TGA, XRD, SEM, etc. The oxygen ion conductivity of single phase CDC sample was measured by electrochemical impedance spectroscopy (EIS), while the proton and oxygen ion conductivity of CDC/Na₂CO₃ nanocomposite sample were determined by four-probe d.c. measurements. The CDC/Na₂CO₃ samples show significantly enhanced overall ionic conductivity compared to that of single phase CDC samples, demonstrating pronounced composite effect. This confirms that the use of nanocomposite as electrolyte can effectively lower the operation temperature of SOFC due to improved ionic conductivity.     

State of the art ceria-carbonate composites (3C) electrolyte for advanced low temperature ceramic fuel cells (LTCFCs)

Solid oxide fuel cells (SOFCs) are considered as one of the most promising power-generation technologies. However, the current high operation temperature (800–1000 °C) of SOFCs impedes their commercialization significantly. A key requirement for reducing the operation temperature of SOFCs is to improve the performance of the electrolyte at such low temperature. Recently, ceria-based composite materials, especially ceria-carbonate composites (3C), have been developed as competitive electrolyte candidates for SOFCs operated below 600 °C, which resulted in an emerging R & D upsurge followed up by worldwide activities. This report gives a short review on current worldwide activities on 3C for advanced low temperature ceramic fuel cells (LTCFCs), which mainly based on recent more than 70 publications since 2010. It gives an overview of materials composition and microstructure, multi-ion conduction effects, durability of the 3C materials in the areas of LTCFC or joint SOFC/MCFC filed, as well as some other novel applications of the 3C materials.     

Revisiting ionic conductivity of rare earth doped ceria: Dependency on different factors

The rare–earth–doped ceria overcomes the difficulties of yttria–stabilized zirconia (YSZ) as an electrolyte in Solid Oxide Fuel Cells (SOFCs) due to its superior ionic conductivity in the intermediate temperature range. However, several factors such as synthesis process, sintering condition, dopant concentration, co–doping mechanism, dopant vacancy interaction, ionic radius of dopants, grain boundary, grain size, affect the ionic conductivity of the rare earth doped ceria. It is difficult to explain the ionic conductivity of rare–earth–doped ceria in terms of a single factor because there is a complex correlation among these factors. This review tries to find the complicated relationship between these factors. This work also reviews different opinions regarding the effect of these factors on ionic conductivity. The knowledge about the factors is vital to develop a better solid electrolyte for SOFCs. This work is an overview of the ionic conductivity of rare–earth–doped ceria in terms of the several affecting factors.     

Study on charge transportation in the layer-structured oxide composite of SOFCs

In the past few years, triple (H⁺/O^2?/e^?) conducting materials have been regarded as one of the most promising electrode categories for solid oxide fuel cells (SOFCs). In this work, a layer-structured LiNi_0.8Co_0.15Al_0.05O_2-δ (LNCA) with triple conduction has been studied. The semiconductor-ionic conductor (SIC) LNCA-SDC composite has been fabricated by compositing the LNCA material with ionic conductor, i.e., samarium doped ceria (SDC). The electrochemical performance of the LNCA-SDC composite was studied by electrochemical impedance spectroscopy, while its electronic conductivity was confirmed by d.c. polarization method. It is found that the ionic conductivity of the composite is higher than the electronic conductivity by several orders of magnitude. The charge carriers and transportation properties of LNCA-SDC were studied using H⁺ and O^2? blocking layer cells respectively. Results prove that the LNCA-SDC composite is a hybrid oxygen ion-proton conducting material. The oxygen ion conduction is dominated at low temperature (425–500 °C), however, it is comparable with H⁺ conduction at high temperature (550 °C). Additionally, the formation of Li₂CO₃ under fuel cell operation environment was observed and the mechanism of the hybrid conductivity of LNCA-SDC was studied.     

Study on GDC-KZnAl composite electrolytes for low-temperature solid oxide fuel cells

Development of low-temperature solid oxide fuel cells (LTSOFC) is now becoming a mainstream research direction worldwide. The advancement in the effective electrolyte materials has been one of the major challenges for LTSOFC development. To further improve the performance of electrolyte, composite approaches are considered as common strategies. The enhancement on ionic conductivity or sintering behavior ceria-based electrolyte can either be done by adding a carbonate phase to facilitate the utilization of the ionic-conducting interfaces, or by addition of alumina as insulator to reduce the electronic conduction of ceria. Thus the present report aims to design a composite electrolyte materials by combining the above two composite approaches, in order to enhance the ionic conductivity and to improve the long-term stability simultaneously. Here we report the preparation and investigation of GDC-KAlZn materials with composition of Gd doped ceria, K₂CO₃, ZnO and Al₂O₃. The structure and morphology of the samples were characterized by XRD, SEM, etc. The ionic conductivity of GDC-KAlZn sample was determined by impedance spectroscopy. The composite samples with various weight ratio of GDC and KAlZn were used as electrolyte material to fabricate and evaluate fuel cells as well as investigate the composition dependent properties. The good ionic conductivity and notable fuel cell performance of 480 mW cm⁻² at 550 °C has demonstrated that GDC-KAlZn composite electrolyte can be regarded as a potential electrolyte material for LTSOFCs.     

Electrochemical impact of the carbonate in ceria-carbonate composite for low temperature solid oxide fuel cell

Ceria-carbonate composite has been suggested as a promising electrolyte for solid oxide fuel cells operating at low temperatures. However, the roles of carbonate in the enhancement of the superionic conductivity and fuel cell performance of ceria-carbonate composite electrolytes are not yet confirmed. In this work, we look into the chemical and ionic state, transmission and segregation of carbonate and alkali cations under normal and electrochemical conditions. The XRD measurement confirms that there are not any carbonate crystals in the sample electrolyte. It is interesting to see that part of the carbonate and alkali ions are not formed into the stoichiometric carbonate in sample materials under the typical electrical field condition from the EDS and XPS analysis. Instead, carbonate (CO₃^2?) and alkali ions accumulate in the cathode side, which we believe, was caused by the electrochemical “catalyst” of CO₂ and alkali ions that accelerated the electrochemical oxygen reduction reaction, while the CO₃^2? ions as one of the charge carriers which diffuse from fuel cell cathode to anode are on account of the concentration gradient. Those together contribute to the excellent electrochemical performances of ceria-carbonate composite electrolyte for low temperature solid oxide fuel cell.     

Next generation fuel cell R&D

The material innovations and developments can play a key role in realizing solid oxide fuel cell (SOFC) commercialization. However, it seems missing in the long SOFC R&D strategy. Recent R&D on innovative ceria‐based composites (CBCs) make a breakthrough and open a new research subject on low‐temperature (300–600°C) SOFCs. Low temperatures create many freedoms to develop next generation fuel cell technology for commercialization. Copyright © 2006 John Wiley & Sons, Ltd.     

Ceria-carbonate composite for low temperature solid oxide fuel cell: Sintering aid and composite effect

In this study, the effect of carbonate content on microstructure, relative density, ionic conductivity and fuel cell performance of Ce_0.8Sm_0.2O_1.9-(Li/Na)₂CO₃ (SDC-carbonate, abbr. SCC) composites is systematically investigated. With the addition of carbonate, the nano-particles of ceria are well preserved after heat-treatment. The relative densities of SCC pellets increase as the carbonate content increases or sintering temperature rises. Especially, the relative density of SCC2 sintered at 900 °C is higher than that of pure SDC sintered at 1350 °C. Both the AC conductivity and DC oxygen ionic conductivity are visibly improved compared with the single phase SDC electrolyte. Among the composites, SDC-20 wt% (Li/Na)₂CO₃ (SCC20) presents high dispersion, relative small particle size, and the dense microstructure. The optimized microstructure brings the best ionic conductivity and fuel cell performance. It is hoped that the results can contribute the understanding of the role of carbonate in the composite materials and highlight their prospective application.     

A direct carbon fuel cell with (molten carbonate)/(doped ceria) composite electrolyte

A composite electrolyte containing a Li/Na carbonate eutectic and a doped ceria phase is employed in a direct carbon fuel cell (DCFC). A four-layer pellet cell, viz. cathode current collector (silver powder), cathode (lithiated NiO/electrolyte), electrolyte and anode current collector layers (silver powder), is fabricated by a co-pressing and sintering technique. Activated carbon powder is mixed with the composite electrolyte and is retained in the anode cavity above the anode current collector. The performance of the single cell with variation of cathode gas and temperature is examined. With a suitable CO₂/O₂ ratio of the cathode gas, an operating temperature of 700 °C, a power output of 100 mW cm⁻² at a current density of 200 mA cm⁻² is obtained. A mechanism of O²⁻ and CO₃²⁻ binary ionic conduction and the anode electrochemical process is discussed.     

Improved ceria–carbonate composite electrolytes

It has been successfully demonstrated that the fuel cells using the ceria–carbonate composite as electrolytes have achieved excellent performances of 200–1150 W/cm² at 300–600 °C. Previously it was reported these ceria–carbonate composite electrolytes have been prepared with two-step processes: step 1, prepare ion-doped ceria which was prepared usually through the wet-chemical co-precipitation process; step 2, mixing the doped ceria with carbonates in various compositions. We first report here to prepare the SDC–carbonate composites within one-step chemical co-precipitation process, i.e. mixing carbonates and preparing the SDC in the same process. The one-step process has provided a number of advantages: (i) to reduce the involved preparation processes to enhance the production, to make the produced materials in good quality control, more homogenous composites microstructure; (ii) as results, these composites showed also different micro-structures and electrical properties. It has significantly improved the ceria–carbonate conductivities and cause the superionic conduction at much lower temperatures; (iii) to reduce manufacturing costs also.     

A review on recent status and challenges of yttria stabilized zirconia modification to lowering the temperature of solid oxide fuel cells operation

Solid Oxide Fuel Cells (SOFCs) are an electrochemical energy converter that receives the world's attention as a power generation system of the future owing to its flexibility to consume various types of fuels, low emission of greenhouses gases, and having high efficiency reaching over 70%. A conventional SOFCs operates at high temperature, typically ranges between 800 to 1000°C. SOFCs use yttria-stabilized zirconia (YSZ) as the electrolyte, which exhibits excellent oxide ion conductivity in this temperature range. However, this temperature range poses an issue to SOFCs durability, as it leads to the degradation of the cell components. In addition, SOFCs application is limited and difficult to implement for the transportation sector and portable appliance. A viable solution is to lower the SOFCs operating temperature to intermediate (600 to 800°C) or low (<600°C) operating temperature. The benefit of this way, cell durability will improve, as well as other advantages such as facilitates handling, assembling, dismantling, cost reduction, and expanded the SOFCs application. Nonetheless, the key challenge for the issue is finding suitable electrolyte, as YSZ have lower ionic conductivity at low and intermediate temperature range. The aim of this paper is to review the status and challenges in the attempts made to modify YSZ electrolyte within the past decade. The resulting ionic conductivity, microstructure, and densification, mechanical and thermal properties of these 'new' electrolytes critically reviewed. The targeted conductivity of modification of YSZ electrolyte must be exceeded >0.1 S cm^–1 to enable high performance of SOFCs power generation systems to be realized for transportation and portable applications. Based on our knowledge, this paper is the first review which focused on the recent status and challenges of YSZ electrolyte towards lowering the operating temperature.     

Validation of H/O conduction in doped ceria–carbonate composite material using an electrochemical pumping method

A hydrogen and oxygen electrochemical pump technique has been employed to elucidate the conduction of proton and oxygen ion in a doped ceria–carbonate composite electrolyte for intermediate temperature solid oxide fuel cells. The composite material shows efficient conductivities of both of the two ions at 650 °C. The molten carbonate phase is important for the migration of both of the two ions. The mechanism of the conduction of proton and oxygen ion is also discussed.     

Development of lanthanum strontium cobalt ferrite perovskite electrodes of solid oxide fuel cells – A review

There is an enormous driving force in solid oxide fuel cells (SOFCs) to reduce the operating temperatures from high temperatures (800–1000 °C) to intermediate and low temperatures (400–800 °C) in order to increase the durability, improve thermal compatibility and thermal cycle capability, and reduce the fabrication and materials costs. One of the grand challenges is the development of cathode materials for intermediate and low temperature SOFCs with high activity and stability for the O₂ reduction reaction (ORR), high structural stability as well as high tolerance toward contaminants like chromium, sulfur and boron. Lanthanum strontium cobalt ferrite (LSCF) perovskite is the most popular and representative mixed ionic and electronic conducting (MIEC) electrode material for SOFCs. LSCF-based materials are characterized by high MIEC properties, good structural stability and high electrochemical activity for ORR, and have played a unique role in the development of SOFCs technologies. However, there appears no comprehensive review on the development and understanding of this most important MIEC electrode material in SOFCs despite its unique position in SOFCs. The objective of this article is to provide a critical and comprehensive review in the structure and defect chemistry, the electrical and ionic conductivity, and relationship between the performance, intrinsic and extrinsic factors of LSCF-based electrode materials in SOFCs. The challenges, strategies and prospect of LSCF-based electrodes for intermediate and low temperature SOFCs are discussed. Finally, the development of LSCF-based electrodes for metal-supported SOFCs and solid oxide electrolysis cells (SOECs) is also briefly reviewed.     

Effects of P-N and N-N heterostructures and band alignment on the performance of low-temperature solid oxide fuel cells

Reducing the operating temperature of solid oxide fuel cells (SOFCs) has attracted worldwide attention in recent years. This has prompted massive efforts in developing new electrolyte materials for low-temperature SOFCs, typically including heterostructure materials consisting of semiconductors and ionic conductors. In this study, a p-n heterostructure (LiZnO–SnO₂) and an n-n heterostructure (ZnO–SnO₂) are proposed and evaluated in SOFCs to tap further the potential of a heterostructure for low-temperature electrolyte use. The results show that the developed LiZnO–SnO₂ and ZnO–SnO₂ both capably play competent electrolyte roles in SOFCs with high ionic conductivities and promising fuel cell performance, achieving peak power outputs of 376 and 255 mW cm^?2 at 530 °C, respectively. To interpret the good performance of the two heterostructure electrolytes, energy band alignment mechanisms based on p-n hetero-junction and n-n heterostructure are employed to illustrate the ionic enhancement and electronic suppression processes of the materials. These findings reveal new insight into developing heterostructure electrolytes for low-temperature SOFCs.     

Physicochemical properties of Ba(Zr,Ce)O3-δ-based proton-conducting electrolytes for solid oxide fuel cells in terms of chemical stability and electrochemical performance

To enhance the power generation efficiency of solid oxide fuel cells (SOFCs), the use of proton-conducting solid solutions of doped BaCeO₃ and doped BaZrO₃, with formulas of the Ba(Zr_0.1Ce_0.7Y_0.1X_0.1)O_3-δ (X = Ga, Sc, In, Yb, Gd), was investigated as SOFCs electrolyte materials with respect to both chemical stability and electrical conductivity. Regarding chemical stability, the weight changes of each material were measured under a CO₂ atmosphere in a temperature range of 1200 °C–600 °C.Higher chemical stability was observed for dopant ions with smaller radii. Regarding conductivity, the dependences of the total conductivities on the oxygen partial pressure and temperature were measured in the temperature range of 600 °C–900 °C. In each material, the total conductivity was proportional to the oxygen partial pressure to the 1/4 power at high oxygen partial pressures, as previously observed for accepter-doped proton-conducting perovskite-type oxides. The derived conductivities for each type of charge carrier showed that the hole conductivity increased with the ionic conductivity. Based on the measured data, the leakage current densities were calculated for SOFCs with each of the investigated electrolyte materials and an area-specific resistance of 0.383 Ωcm². BZCYSc showed the minimum leakage current density, with a value of 3.7% of the external current density at 600 °C. Therefore, this study indicates that BZCYSc is the most desirable among the materials investigated for use as SOFCs electrolyte. However, for BZCYSc to be used as SOFCs electrolyte material, a protective layer is needed to ensure its chemical stability.     

Compositing protonic conductor BaZr0.5Y0.5O3 (BZY) with triple conductor BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) as electrolyte for advanced solid oxide fuel cell

BaZr_0.5Y_0.5O₃(BZY) electrolyte exhibited enormous potential for low temperature solid oxide fuel cell (SOFC) due to its proton dominant mobile carriers rather than oxygen ions during the electrochemical process. In order to enhance the ionic conductivity, triple conductor BaCo_0.4Fe_0.4Zr_0.1Y_0.1O_3-δ (BCFZY) was composited with proton conductor BZY to form semiconductor-ionic conductor composite (SIM), which was applied as electrolyte to fabricate symmetrical fuel cell. The microstructural and electrochemical properties for BZY, BCFZY and BZY-BCFZY composites were studied. After optimizing the weight ratio of composite content, the ionic conductivity and electronic conductivity reached an equilibrium state to obtain the maximum cell performance, namely the highest output of 902.5 mW cm^?2 and an open circuit voltage (OCV) of 1.043 V at 550 °C. The BZY-BCFZY cell also presented decent power output at low temperature, a power density of 265.625 mW cm^?2 was received even at 500 °C, demonstrating that the BZY-BCFZY composite was a potential electrolyte for low temperature SOFCs.     

Effects of salt composition on the electrical properties of samaria-doped ceria/carbonate composite electrolytes for low-temperature SOFCs

Samaria-doped ceria (SDC)/carbonate composite electrolytes were developed for low-temperature solid oxide fuel cells (SOFCs). SDC powders were prepared by oxalate co-precipitation method and used as the matrix phase. Binary alkaline carbonates were selected as the second phase, including (Li–Na)₂CO₃, (Li–K)₂CO₃ and (Na–K)₂CO₃. AC conductivity measurements showed that the conductivities in air atmosphere depended on the salt composition. A sharp conductivity jump appeared at 475 °C and 450 °C for SDC/(Li–Na)₂CO₃ and SDC/(Li–K)₂CO₃, respectively. However, the conductivities of SDC/(Na–K)₂CO₃ increase linearly with temperature. Single cells based on above composite electrolytes were fabricated by dry-pressing and tested in hydrogen/air at 500–600 °C. A maximum power density of 600, 550 and 550 mW cm⁻² at 600 °C was achieved with SDC/(Li–Na)₂CO₃, SDC/(Li–K)₂CO₃ and SDC/(Na–K)₂CO₃ composite electrolyte, respectively, which we attribute to high ionic conductivities of these composite electrolytes in fuel cell atmosphere. We discuss the conduction mechanisms of SDC/carbonate composite electrolytes in different atmospheres according to defect chemistry theory.