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Review Issue
Progress on Sealing Materials for Planar Solid Oxide Fuel Cells
Journal of the Chinese Ceramic Society 2025, 53(7): 2066-2078
Published: 28 May 2025
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Planar solid oxide fuel cells (SOFCs) offer several advantages, i.e., high power density, simplified fabrication processes, and excellent stack compactness, thus making them the predominant architecture in SOFC technology. However, high-temperature sealing remains a major challenge for planar SOFC stacks. Sealing technology is critical in determining the safety, efficiency, and overall stability of SOFC systems. The sealing material as the core component of this technology directly affects the stack hermeticity, thereby impacting its power output and long-term operational reliability.

Planar solid oxide fuel cells (SOFCs) utilize two primary sealing methods, i.e., compressive and rigid sealing, which are distinguished via the application of compressive load during the sealing process. Compressive sealing materials suitable for planar SOFCs include metal, mica-based, and ceramic-based compressive seals, each offering unique properties such as excellent deformability, high stability, and superior high-temperature resistance. 1) Metal Compressive Seals: Silver (Ag) is the most widely used metal compressive sealing material due to its outstanding ductility, chemical stability, and lower cost, compared to platinum and gold. However, Ag also has several drawbacks, including temperature sensitivity, low mechanical strength, and limited chemical stability under both oxidizing and reducing atmospheres, hindering its suitability for commercial SOFC applications. 2) Mica-based Compressive Seals: Mica-based compressive sealing materials feature a distinctive layered structure, with adjacent layers held together by weak K+ interactions. This unique arrangement enables an interlayer sliding under compressive stress, enhancing their adaptability as sealing materials. The main gas leakage pathways in mica-based compressive sealing materials occur through the mica itself and the contact interfaces between mica and adjacent components. These leakage pathways can be mitigated via introducing an intermediate layer or infiltrating with wetting materials. Thermiculite® 866 is one of the most commercially advanced mica-based compressive sealing materials. It is based upon the mineral vermiculite and contains no organic binder or any other organic component. Thermiculite® 866 is soft and highly conformable, allowing for both macro- and micro-sealing to be readily achieved. In addition, it also maintains its sealing properties without relaxation or creep, even under high-temperature conditions. 3) Ceramic-based Compressive Seals: Ceramic-based materials with a great thermal and chemical stability are challenging to use directly as compressive sealing materials for SOFCs, considering their ductility, thermal expansion coefficient (TEC), and chemical compatibility. However, it is feasible to modify the morphology, optimize the manufacturing process or incorporate metallic components to improve their deformability, making them suitable for seals. In summary, the development and optimization of compressive sealing materials are crucial for enhancing the performance and durability of planar SOFCs. Each type of sealing material presents distinct advantages and challenges, necessitating ongoing research to address these issues and improve SOFC technology.

Rigid sealing materials generally provide a superior gas tightness, compared to compressive seals, making them a focal point in the development of planar solid oxide fuel cells (SOFCs). These rigid seals primarily encompass glass, glass-ceramic, and metal brazing techniques. 1) Glass and Glass-ceramic Seals: Glass and glass-ceramic materials are among the most commonly used sealing materials in planar SOFCs. Adjusting the phase composition or controlling the crystallization process of these materials allows for tailoring their TEC, effectively minimizing thermal expansion mismatches with adjacent cell components. However, solely designing the composition of glass sealants to meet comprehensive performance requirements, such as glass transition temperature (Tg), softening temperature (Ts), TEC, thermal stability, and mechanical strength, poses some challenges. Incorporating ceramics, mica, or glass fibers into glass sealants can significantly enhance their overall properties. A research indicates that glasses and particularly glass–ceramics are ideal sealant candidates due to their properties, including thermal expansion, can be tailored to be compatible with other fuel cell materials. 2) Metal Brazing: Brazing is a high-temperature joining technique wherein a molten metal filler material fills the gap between metal and ceramic components, interacting with the substrates and solidifying upon cooling to form a robust, hermetic joint. Brazing techniques are primarily categorized into active metal brazing (AMB) and air reaction brazing (RAB). AMB is typically conducted under vacuum or a protective gas atmosphere, leading to higher production costs, compared to RAB. The Ag-CuO system as one of the most preferred RAB materials faces several challenges, i.e., high TEC, poor chemical stability, and low mechanical strength, significantly hindering its long-term stability in SOFC applications. In summary, while rigid sealing materials offer superior gas tightness essential for the efficient operation of planar SOFCs, some challenges remain in optimizing their properties to ensure long-term stability and compatibility with other cell components. Ongoing research and development efforts focus on addressing these challenges to enhance the performance and durability of SOFC systems.

Solid oxide fuel cells (SOFCs) hold a significant promise for efficient energy conversion, however, some challenges associated with sealing materials impede their widespread commercialization. Two primary causes of sealing failure are identified:

1) Thermal Expansion Mismatch: Differences in the thermal expansion coefficients (TEC) between sealing materials and adjacent SOFC components can induce thermal stresses at high operating temperatures. These stresses may lead to the formation of pores and cracks, compromising the mechanical integrity of the seal and resulting in gas leakage.

2) Decomposition and Interfacial Reactions: Exposure to high temperatures and environments with both oxidizing and reducing conditions can cause decomposition of sealing materials. In addition, chemical reactions at the interfaces between seals and SOFC components can also occur, ultimately leading to a sealing failure.

Addressing these issues is crucial for the commercial application of SOFCs. Future research should focus on:

1) Enhancing high-temperature stability and chemical compatibility: Developing materials that remain stable and chemically inert under SOFC operating conditions.

2) Improving TEC matching: Tailoring the TEC of sealing materials to closely align with those of adjacent components to minimize thermal stresses.

3) Enhancing resistance to chemical corrosion and oxidation: Creating seals that can withstand corrosive environments and resist oxidation over prolonged periods.

4) Optimizing glass-ceramic formulations: Adjusting compositions to reduce crystallization tendencies, thereby improving mechanical properties and durability.

5) Developing self-healing materials: Innovating materials capable of autonomously repairing minor damages, extending the operational lifespan of seals.

6) Advancing cost-effective solutions: Streamlining manufacturing processes to reduce costs without compromising quality.

7) Promoting environmentally friendly technologies: Ensuring that new sealing materials and processes with a minimal environmental impact, aligning with sustainable development goals.

Summary and prospects

Advancements in sealing materials are pivotal for the progression of solid oxide fuel cell (SOFC) technology. These materials must maintain a long-term stability under extreme operating conditions, i.e., high temperatures, elevated pressures, and chemically aggressive environments. In addition, they also require excellent thermal expansion compatibility and gas impermeability to ensure the structural integrity and operational longevity of SOFC stacks. Future developments in SOFC sealing materials should focus on glass-ceramic composites, offering superior chemical stability, tailored thermal expansion behavior, and robust mechanical properties at elevated temperatures. These characteristics make them well-suited for ensuring the long-term stability of SOFC systems. The microstructure of these composites can be engineered to enhance gas tightness, self-healing capabilities, and overall durability via optimizing the composition of glass and ceramic phases, as well as refining heat treatment processes. The development of high-performance glass-ceramic composite sealing materials will address the critical challenges associated with the existing SOFC sealing technologies, providing some essential solutions for the commercialization and large-scale deployment of SOFC systems. Advancements in this field will facilitate a widespread adoption of clean energy technologies, contributing to the global transition toward a low-carbon economy and sustainable energy infrastructure.

Issue
Progress in Mn-based A-site Double Perovskite for Solid Oxide Cell
Journal of Ceramics 2022, 43(5): 816-824
Published: 01 October 2022
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Solid oxide cell (SOC) can convert chemical energy of fuel into electrical energy in fuel cell mode or convert electrical energy into chemical energy in electrolysis cell mode. It has advantages of high conversion efficiency, fuel flexibility, etc., which is very attractive for the storage and conversion of renewable energy. The electrode, where the electrochemical reaction takes place, plays a key role in SOC performance. Compared with the traditional composite electrode materials, perovskite materials have attracted extensive attention because of their simple structure, strong structural tolerance and adjustable electrochemical properties. The Mn-based A-site layered double perovskite (LnBaMn2O5+δ, Ln = lanthanide) has fast oxygen ion migration channel and good catalytic activity for both fuel oxidation and oxygen reduction processes and shows good structural stability under a wide oxygen partial pressure. Therefore, it is widely used as an SOC electrode. The structural characteristics and the formation reasons of the Mn-based A-site double perovskites are introduced, and the modification strategies and the progress are summarized in this work. The prospects of the Mn-based A-site double perovskites are also prospected.

Open Access Research Article Issue
A Scalable and Effective Strategy for Boosting the Initial Coulombic Efficiency of Silicon Suboxide Anode
Energy Material Advances 2024, 5: 0098
Published: 23 July 2024
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Silicon suboxide (SiOx) is one of the most attractive candidates for anode materials for high-energy-density lithium-ion batteries due to its high specific capacity and its relatively lower volume expansion than that of Si. However, its low initial Coulombic efficiency (ICE) seriously affects its practical applications. In this work, we demonstrate a scalable and effective strategy to enable a high ICE of the SiOx electrode through a MnO-assisted disproportionation reaction. The obtained Mn2SiO4–Si–SiOx@C (MSS@C) material shows a reduced lithium irreversible consumption in the first cycle. The Mn2SiO4 phase can store lithium through a conversion reaction with a smaller volume change (33%) than SiOx, which helps to maintain the structural stability of MSS@C during cycling. Meanwhile, the metallic Mn nanoparticles generated from Mn2SiO4 during the lithiation process facilitate electron conduction, thus improving the electrode reaction kinetics. Owing to the synergetic effects, the MSS@C material exhibits a higher ICE (79.51%) compared to 60.91% of pure SiOx, and a superior cyclic performance (832 mAh g−1 at 0.5 A g−1 after 350 cycles with a capacity retention of 90.4%). This work offers a new approach to increase the ICE while improving the electrode reaction kinetics and cycling stability of SiOx-based materials.

Open Access Review Article Issue
Limitations and Strategies toward High-Performance Red Phosphorus Materials for Li/Na-Ion Batteries
Energy Material Advances 2024, 5: 0086
Published: 15 March 2024
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Downloads:49

Phosphorus, particularly the red phosphorus (RP) allotrope, has been extensively studied as an anode material in both lithium-ion batteries (LIBs) and emerging sodium-ion batteries (SIBs). RP is featured with high theoretical capacity (2,596 mA h g−1), suitable low redox potential (~0.7/0.4 V for LIBs/SIBs), abundant resources, and environmental friendliness. Despite its promises, the inherent poor electrical conductivity of RP (~10−14 S cm−1) and significant volume changes during charge/discharge processes (>300%) compromise its cycling stability. In order to address these issues, various countermeasures have been proposed, focusing on the incorporation of materials that provide high conductivity and mechanical strength in composite-type anodes. In addition, the interfacial instability, oxidation, and safety concerns and the low mass ratio of active material in the electrode need to be addressed. Herein, this review summarizes the up-to-date development in RP materials, outlines the challenges, and presents corresponding countermeasures aimed to enhance the electrochemical performance. It covers aspects such as the structural design of RP, the choice of the additive materials and electrolytes, rational electrode construction, etc. The review also discusses the future prospects of RP for LIBs/SIBs and aims to provide a different perspective on the challenges that must be overcome to fully exploit the potential of RP and meet commercial application requirements.

Research Article Issue
Rational structure design to realize high-performance SiOx@C anode material for lithium ion batteries
Nano Research 2020, 13(2): 527-532
Published: 23 January 2020
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Downloads:88

Silicon suboxide (SiOx) is considered to be one of the most promising materials for next-generation anode due to its high energy density. For its preparation, the wet-chemistry method is a cost-effective and readily scalable route, while the so-derived SiOx usually shows lower capacity compared with that prepared by high temperature-vacuum evaporation route. Herein, we present an elaborate particle structure design to realize the wet-chemistry preparation of a high-performance SiOx/C nanocomposite. Dandelion-like highly porous SiOx particle coated with conformal carbon layer is designed and prepared. The highly-porous SiOx skeleton provides plenty specific surface for intimate contact with carbon layer to allow a deep reduction of SiOx to a low O/Si ratio at relatively low temperature (700 °C), enabling a high specific capacity. The abundant mesoscale voids effectively accommodate the volume variation of SiOx skeleton, ensuring the high structural stability of SiOx@C during lithiation/delithiation process. Meanwhile, the three-dimensional (3D) conformal carbon layer provides a fast electron/ion transportation, allowing an enhanced electrode reaction kinetics. Owing to the optimized O/Si ratio and well-engineered structure, the prepared SiOx@C electrode delivers an ultra-high capacity (1,115.8 mAh·g-1 at 0.1 A·g-1 after 200 cycles) and ultra-long lifespan (635 mAh·g-1 at 2 A·g-1 after 1,000 cycles). To the best of our knowledge, the achieved combination of ultra-high specific capacity and ultra-long cycling life is unprecedented.

Open Access Research Article Issue
High-performance oxygen permeation membranes: Cobalt-free Ba0.975La0.025Fe1-xCuxO3-δ ceramics
Journal of Materiomics 2019, 5(2): 264-272
Published: 02 February 2019
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A new group of cobalt-free perovskite oxides, Ba0.975La0.025FeCuO3-δ (BLFC, x = 0.05–0.15), was designed, characterized and applied as oxygen permeation membranes. It was found that BLFC oxides with Cu doping range of 0.075–0.15 maintain cubic perovskite phase in a wide range of temperatures. More Cu introduced at the B-site results in a gradual increase of the electrical conductivity, which is attributed to the denser overlapping of electron clouds of Cu–O bonds. With increasing Cu content, the oxygen vacancy concentration increases and the oxygen ion migration energy decreases, leading to the highest oxygen permeation flux of 1.59 mL cm−2 min−1 recorded for Ba0.975La0.025Fe0.9Cu0.1O3-δ 1 mm thick membrane at 950 °C. However, the oxygen permeability decreases with further Cu doping, which may be correspond to a presence of defect association. Ba0.975La0.025Fe0.9Cu0.10O3-δ membrane with 0.7 mm thickness delivers stable oxygen permeation flux of 1.57 mL cm−2 min−1 for 200 h at 900 °C. All of the obtained results indicate that the developed BLFC with optimized Cu content (i.e. x = 0.1) is a very promising material for usage in oxygen separation applications.

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