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10 pages, 3707 KiB

Open AccessArticle

A Fibrous Perovskite Nanomaterial with Exsolved Ni-Cu Metal Nanoparticles as an Effective Composite Catalyst for External Steam Reforming of Liquid Alcohols

by Tong Wei, Juan Wang, Yangbo Jia and Tatsukuni Harimoto

Crystals 2023, 13(11), 1594; https://doi.org/10.3390/cryst13111594 - 17 Nov 2023

Viewed by 773

Abstract

The conversion of hydrogen to power via combined external reforming of liquid alcohol and solid oxide fuel cell (SOFC) technology is an effective approach to address future energy challenges. In this study, an La_0.8Ba_0.1Mn_0.8Ni_0.1Cu_0.1 [...] Read more.

The conversion of hydrogen to power via combined external reforming of liquid alcohol and solid oxide fuel cell (SOFC) technology is an effective approach to address future energy challenges. In this study, an La_0.8Ba_0.1Mn_0.8Ni_0.1Cu_0.1O₃ (LBMNCu) perovskite nanofiber with high porosity was synthesized with a modified electrostatic spinning method, which acted as an efficient catalyst for steam reforming of liquid alcohols (methanol and ethanol). After reduction, fine metallic Ni-Cu was uniformly distributed throughout the perovskite nanofiber surface. The obtained composite displayed a methanol conversion above 99.9% at 450 °C and an ethanol conversion above 99% at 600 °C, which was highly superior to the common Ni-Cu/Al₂O₃ catalyst. The catalytic performance of our assembled catalysts also remained stable in methanol and ethanol atmospheres for 50 h and no coking was detected. Furthermore, when the reformed gas was fed into a Y_0.08Zr_0.92O₂ (YSZ)-based SOFC system, the open circuit voltage remained around 1.1 V at 700 °C for 50 h accordingly, without coking, and the voltage remained virtually unchanged at 0.7 V for 50 h at 700 °C and 400 mA cm⁻² during galvanostatic discharge mode, indicating that using LBMNCu nanofiber as a catalyst for hydrogen production and utilization is an efficient strategy. The interaction of the in situ exsolved metallic nanoparticles and nanofibrous perovskite could also be a promising approach for designing a highly active catalyst for H₂ generation. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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17 pages, 2769 KiB

Open AccessArticle

Comparison of the Electrochemical Performances of Solid Oxide Fuel Cells with Sputtered Thin Barrier Layers Fueled by Hydrogen or Ammonia

by Nunzia Coppola, Bertrand Morel, Giovanni Carapella, Dario Montinaro, Alice Galdi, Hafiz Sami Ur Rehman, Pierpaolo Polverino, Cesare Pianese, Julie Mougin and Luigi Maritato

Crystals 2023, 13(7), 1040; https://doi.org/10.3390/cryst13071040 - 29 Jun 2023

Cited by 1 | Viewed by 1405

Abstract

We investigated the influence of a fuel change from pure hydrogen to a hydrogen–ammonia mixture at different percentages on the electrochemical behavior of 50 mm in diameter Solid Oxide Fuel Cells (SOFCs) with sputtered thin buffer layers of Gd-doped ceria, varying the working [...] Read more.

We investigated the influence of a fuel change from pure hydrogen to a hydrogen–ammonia mixture at different percentages on the electrochemical behavior of 50 mm in diameter Solid Oxide Fuel Cells (SOFCs) with sputtered thin buffer layers of Gd-doped ceria, varying the working temperatures from 800 °C to 650 °C. The results show that the performances of the cells are not affected by the fuel change for high working temperatures (800 °C and 750 °C). As an example, a power density value of 802 mW∙cm⁻² at 1 A∙cm⁻² is found when directly feeding the cell with 8 NmL∙min⁻¹cm⁻² of ammonia and with an equivalent flowrate of 12 NmL∙min⁻¹cm⁻² of H₂. These power density output values are higher than those obtained in industrial state-of-art (SoA) SOFCs with screen-printed buffer layers fed with equivalent hydrogen flowrates, thanks to the improved electrochemical performances obtained in the case of cells with sputtered thin buffer layers of Gd-doped ceria. At lower working temperatures (700 °C and 650 °C), slight changes in the electrochemical behavior of the cells are observed. Nevertheless, in this temperature range, we also obtain an output current density value of 0.54 A∙cm⁻² in a pure ammonia flowrate of 12 NmL min⁻¹cm⁻² at 800 mV and 700 °C, equal to the value observed in SoA button cells with industrial screen-printed GDC barrier layer fueled with 16 NmL∙min⁻¹cm⁻² of H₂. These results pave the way towards the use of innovative SOFC structures with sputtered thin buffer layers fueled by ammonia. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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15 pages, 7505 KiB

Open AccessArticle

Laser Machining of Nickel Oxide–Yttria Stabilized Zirconia Composite for Surface Modification in Solid Oxide Fuel Cells

by Miguel Morales, Sandra García-González, Michaela Plch, Dario Montinaro and Emilio Jiménez-Piqué

Crystals 2023, 13(7), 1016; https://doi.org/10.3390/cryst13071016 - 26 Jun 2023

Cited by 2 | Viewed by 1005

Abstract

Laser machining of the nickel oxide–yttria-stabilized zirconia (NiO–YSZ) composite in Solid Oxide Fuel Cells (SOFCs) may be an effective approach to enlarge the electrode–electrolyte interface and improve the cell performance. However, laser energy can cause thermal damage to the composite surface during the [...] Read more.

Laser machining of the nickel oxide–yttria-stabilized zirconia (NiO–YSZ) composite in Solid Oxide Fuel Cells (SOFCs) may be an effective approach to enlarge the electrode–electrolyte interface and improve the cell performance. However, laser energy can cause thermal damage to the composite surface during the machined operation. In this work, the microstructure changes and the collateral damage caused by pulsed laser machining on the sintered NiO–YSZ of the state-of-the-art SOFCs were evaluated using complementary analysis techniques. Laser patterns consisting of parallel tracks on sintered NiO–YSZ were processed, varying the laser parameters such as frequency and laser beam energy density. The analyses evidenced a heat-affected zone (HAZ) limited to around 2 µm with microcracking, porosity reduction, and recrystallization. The changes in chemical composition, phase transformation of YSZ and mechanical properties at the machined surface were quite limited. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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19 pages, 10460 KiB

Open AccessArticle

The Effect of Treatment Temperature on Microstructure and Mechanical Behavior of a Fine-Grained YSZ–NiO(Ni) Anode Material

by Bogdan Vasyliv, Volodymyr Kulyk, Zoia Duriagina and Taras Kovbasiuk

Crystals 2023, 13(6), 944; https://doi.org/10.3390/cryst13060944 - 12 Jun 2023

Cited by 1 | Viewed by 1088

Abstract

Reduction–oxidation (redox) cycling of a solid oxide fuel cell (SOFC) due to leakage of a fuel or standby and shutdown cycling is an issue that has attracted the attention of many research groups for a long time. The researchers mainly note the harmful [...] Read more.

Reduction–oxidation (redox) cycling of a solid oxide fuel cell (SOFC) due to leakage of a fuel or standby and shutdown cycling is an issue that has attracted the attention of many research groups for a long time. The researchers mainly note the harmful effects of redox cycling on the microstructure of SOFC constituents and search for ways to mitigate or diminish them. The purpose of this study was to use reduction and oxidation stages in an appropriate mode as a positive preconditioning to improve redox cycling stability of Ni-containing SOFC anode materials. The redox treatment was applied to YSZ–NiO(Ni) anode substrate specimens at 600 °C and 800 °C. The mechanical tests (flexural strength, microhardness, and fracture toughness) were performed on these specimens and the results were compared to those for as-sintered and one-time reduced specimens. Microstructure and fracture surface morphology of material in corresponding modes were analyzed. The main findings were summarized as follows: (i) Redox treatment at 600 °C provides an increase in flexural strength and electrical conductivity of YSZ–NiO(Ni) anode cermets; (ii) the treatment at 800 °C causes formation of a gradient microstructure with lateral cracks that result in a significant decrease in flexural strength; (iii) the mode of redox treatment at 600 °C for 4 h in Ar–5% H₂/air atmosphere provides an increase in flexural strength of YSZ–NiO(Ni) anode cermets (up to 127 ± 4 MPa), while electrical conductivity was provided at a comparatively high level (7 × 10⁵ S/m). Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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12 pages, 2820 KiB

Open AccessArticle

Synergistic Electrochemical Properties of Graphene Incorporated LCZ-Oxide Cathode for Low Temperature Solid Oxide Fuel Cell

by Muhammad Ashfaq Ahmad, Khalil Ahmad, Hu Li, Abdelaziz Gassoumi, Rizwan Raza, Muhammad Saleem, Syed Hassan Mujtaba Jafri and Ghazanfar Abbas

Crystals 2023, 13(3), 434; https://doi.org/10.3390/cryst13030434 - 02 Mar 2023

Cited by 1 | Viewed by 1506

Abstract

Mixed metallic oxides are getting increasing attention as novel electrode materials for energy conversion devices. However, low mixed ionic-electronic conductivity and high operating temperature hamper the practical applications of these devices. This study reports an effective strategy to improve the conductivity and performance [...] Read more.

Mixed metallic oxides are getting increasing attention as novel electrode materials for energy conversion devices. However, low mixed ionic-electronic conductivity and high operating temperature hamper the practical applications of these devices. This study reports an effective strategy to improve the conductivity and performance of the fuel cell at low temperature by partially incorporating graphene in the Li_0.1Cu_0.2Zn_0.7-oxide (LCZ) composite. The proposed cathode material is synthesized via the cost effective conventional solid-state route. Graphene incorporated LCZ shows excellent performance, which is attributed to the favorable charge transport paths offering low area-specific resistance. An X-ray diffractometer (XRD) and scanning electron microscope (SEM) are employed for microstructural and surface morphological analyses, respectively. Electrical conductivities of all the materials are determined by the DC four probe method, and interestingly, LCZ-1.5% graphene exhibits an excellent conductivity of 3.5 S/cm in air atmosphere at a temperature of 450 °C with a minimum value of 0.057 Ωcm² area-specific resistance (ASR) that demonstrates significantly good performance. Moreover, the three-layer fuel cell device is fabricated using sodium carbonated Sm_0.2Ce_0.8O (NSDC) as an electrolyte, which can operate at low temperatures exhibiting open circuit voltage 0.95 V and shows a peak power density, i.e., 267.5 mW/cm² with hydrogen as the fuel. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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14 pages, 4566 KiB

Open AccessArticle

Conductivities in Yttrium-Doped Barium Zirconate: A First-Principles Study

by Huijia Hu, Jie Zou, Liang Shan, Xiaoqing Jiang, Yongjian Ni, Xuebin Li, Xianwei Qian, Wenwen Chen, Yucun Zhou, Weifeng Zhang, Shihao Wei and Jiawen Jian

Crystals 2023, 13(3), 401; https://doi.org/10.3390/cryst13030401 - 25 Feb 2023

Cited by 4 | Viewed by 1924

Abstract

Yttrium-doped barium zirconate (BZY) has emerged as an attractive candidate for application as a proton (H⁺)-conducting solid electrolyte due to its high ionic conductivity and excellent chemical stability. In this study, the conductivities of BaZr_(1−x)Y_xO_3−δ (BZY, [...] Read more.

Yttrium-doped barium zirconate (BZY) has emerged as an attractive candidate for application as a proton (H⁺)-conducting solid electrolyte due to its high ionic conductivity and excellent chemical stability. In this study, the conductivities of BaZr_(1−x)Y_xO_3−δ (BZY, x = 0, 0.037, 0.074, 0.148, and 0.22) with different carriers were studied based on density functional theory (DFT) and experiments. The results revealed that yttrium doping can effectively reduce the energy barrier for the migration of protons and oxygen ions (O²⁻). When comparing the energy barriers for protons and oxygen ions, the energy barriers for proton migration were found to be lower than those for oxygen ion migration, which indicates that a proton conductor can offer the advantages of lower activation energy and, possibly, higher conductivity. An analysis of the electronic structure of the BZYs found that the top of the valence band exceeded the Fermi energy level following yttrium doping. As a result, the electron conductivity increased as the yttrium content increased. Furthermore, this study also tested the total conductivity of BaZr_(1−x)Y_xO_3−δ (BZY, x = 0.1, 0.2, 0.3, and 0.4) and found the trend of the total conductivity to be consistent with the results of the DFT calculations. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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13 pages, 3730 KiB

Open AccessArticle

Evaluation of La_1−xSr_xNi_0.4Fe_0.6O_3-δ as Electrode Materials for Direct Methane Symmetrical Solid Oxide Fuel Cells

by Caixia Shi, Ting Chen, Dongyang Fang and Shaorong Wang

Crystals 2023, 13(1), 152; https://doi.org/10.3390/cryst13010152 - 15 Jan 2023

Viewed by 1576

Abstract

In this work, La_1−xSr_xNi_0.4Fe_0.6O_3-δ (0 ≤ x ≤ 0.2) oxides were synthesized and employed as the identical electrode of direct methane symmetrical solid oxide fuel cell (SSOFC). In addition, the phase structure, redox stability, [...] Read more.

In this work, La_1−xSr_xNi_0.4Fe_0.6O_3-δ (0 ≤ x ≤ 0.2) oxides were synthesized and employed as the identical electrode of direct methane symmetrical solid oxide fuel cell (SSOFC). In addition, the phase structure, redox stability, electrical conductivity, chemical compatibility, and thermal expansion of La_1−xSr_xNi_0.4Fe_0.6O_3-δ oxides were evaluated. The La₂NiO₄ phase occurs when the amount of doped Sr rises to 0.2. The composition of La_0.9Sr_0.1Ni_0.4Fe_0.6O_3-δ (LSNF9146) boasts the highest conductivity of 463 S cm⁻¹ with lowest activation energy of 0.066 eV as well as a relatively large thermal expansion coefficient. After treatment in methane for 10 h, the LSNF9146 oxide exhibits 33% lower carbon deposition than the LaNi_0.4Fe_0.6O_3-δ (LNF46) oxide. Moreover, the impregnated LSNF9146 electrode demonstrates lower polarization resistance in both air and methane atmospheres. SSOFCs with impregnated LSNF9146 and LNF46 identical composite electrodes have the maximum power densities of 233 and 170 mW cm⁻² at 850 °C in methane, respectively. These results prove that LSNF9146 is a promising symmetrical electrode with high catalytic activity, good redox stability, and coking resistance to direct methane SSOFCs. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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9 pages, 3175 KiB

Open AccessArticle

Study of the La_1−xSr_xMnO₃ Cathode Film Prepared by a Low Power Plasma Spray Method with Liquid Solution Precursor for a Solid Oxide Fuel Cell

by Chih-Hao Lee, Bing-Syun Yeh and Tsun-Neng Yang

Crystals 2022, 12(11), 1633; https://doi.org/10.3390/cryst12111633 - 14 Nov 2022

Cited by 1 | Viewed by 1268

Abstract

A perovskite La_1−xSr_xMnO₃ cathode thin film for an oxygen ion conducting solid oxide fuel cell was prepared using a low power (8.8 kW) liquid solution plasma spray method. Usually, a 30–50 kW Ar plasma torch with temperature higher [...] Read more.

A perovskite La_1−xSr_xMnO₃ cathode thin film for an oxygen ion conducting solid oxide fuel cell was prepared using a low power (8.8 kW) liquid solution plasma spray method. Usually, a 30–50 kW Ar plasma torch with temperature higher than all the melting points of solid precursors is essential to synthesis oxides thin film. However, using the liquid precursors as the feeding materials, the required power can be reduced and save a lot of thermal budget. The precursors are water solutions of lanthanum nitrate hexahydrate, manganese(II) nitrate tetrahydrate, and strontium nitrate. The atomic percentage of La in the plasma sprayed La_1−xSr_xMnO₃ cathode film is lower than that of La in the feeding precursor into the torch, which is due to the low boiling temperature of La(NO₃)₃ precursor. The oxygen stoichiometry of La_1−xSr_xMnO_3−δ deduced from the valence state of Mn measured by X-ray absorption spectroscopy shows an oxygen deficit structure. The measured low resistivity of 0.07–0.09 Ωcm at room temperature for this La_1−xSr_xMnO_3−δ is essential for oxygen ion transport in the cathode thin film of a solid-state fuel cell. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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12 pages, 3197 KiB

Open AccessArticle

Nanofiber Sr₂Fe_1.5Mo_0.5O_6-δ Electrodes Fabricated by the Electrospinning Method for Solid-Oxide Cells

by Bo Zhang, Zhizhong Leng, Yihan Ling, Hu Bai, Sha Li, Juan Zhou and Shaorong Wang

Crystals 2022, 12(11), 1624; https://doi.org/10.3390/cryst12111624 - 12 Nov 2022

Cited by 3 | Viewed by 1671

Abstract

Solid oxide cells (SOCs) are attracting much more attention as promising energy conversion and storage devices. One of the challenges of optimizing of solid-oxide cells’ performance is that there are not enough triple-phase boundaries (TPB) in the electrode bulk. To enhance the reaction [...] Read more.

Solid oxide cells (SOCs) are attracting much more attention as promising energy conversion and storage devices. One of the challenges of optimizing of solid-oxide cells’ performance is that there are not enough triple-phase boundaries (TPB) in the electrode bulk. To enhance the reaction area for SOCs, Sr₂Fe_1.5Mo_0.5O_6-δ nanofibers are synthesized by electrospinning with metal nitrate precursors and used for SOC electrodes operated in both humidified air and a hydrogen atmosphere. SFMO nanofibers display a highly porous and crystallized perovskite structure and continuous pathways by XRD analysis and SEM observation. The average diameter of the SFMO nanofibers after sintering is about 100 nm. The La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-δ(LSGM) electrolyte-supported symmetrical cell with the SFMO nanofiber electrode exhibits enhanced electrochemical performance in humidified air and an H₂ atmosphere. Moreover, a distribution of the relaxation time method is used to analyze the impedance spectra, and the polarization peaks observed are assigned to correspond different electrochemical processes. The results indicate that the SFMO nanofiber with an improved nanostructure can be the potential material for the SOC electrode. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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17 pages, 4117 KiB

Open AccessArticle

Effects of Methane Pre-Reforming Percentage and Flow Arrangement on the Distribution of Temperature and Thermal Stress in Solid Oxide Fuel Cell

by Weiqiang Cai, Qingrong Zheng, Wanneng Yu, Zibin Yin, Jinliang Yuan, Zhonggang Zhang and Yuyao Pei

Crystals 2022, 12(7), 953; https://doi.org/10.3390/cryst12070953 - 07 Jul 2022

Cited by 6 | Viewed by 1766

Abstract

To obtain detailed information on the temperature field and thermal stress field inside the solid oxide fuel cell (SOFC) fueled with partially pre-reformed methane. A three-dimensional geometric and mathematical model of the SOFC is implemented by using the finite element method in the [...] Read more.

To obtain detailed information on the temperature field and thermal stress field inside the solid oxide fuel cell (SOFC) fueled with partially pre-reformed methane. A three-dimensional geometric and mathematical model of the SOFC is implemented by using the finite element method in the commercial software COMSOL Multiphysics^®. The coupling characteristics were analyzed for electrode chemical reaction, multi-component mass transfer, and heat transfer process under typical operating conditions, which was further applied for predicting and analyzing the thermal stress distribution. After model validation, parametric simulations are conducted to investigate how the methane pre-reforming percentage and flow arrangement affect the temperature and the thermal stress of SOFC. The simulated results show that reducing the methane pre-reforming percentages can decrease the temperature maximum and the variation range of the first principal stress, but will increase the possibility of carbon deposition. The maximum temperature of the counter-flow is about 20 K lower than that of the co-flow, and the first principal stress variation range of the counter-flow is 8.6 Mpa lower than that of the co-flow. The methane pre-reforming percentages have a significant effect on the heat transfer and the thermal stress, and the counter-flow can improve the temperature uniformity and reduce the thermal stress variation range. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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Review

Jump to: Research

26 pages, 3846 KiB

Open AccessReview

Nanostructured Materials for Enhanced Performance of Solid Oxide Fuel Cells: A Comprehensive Review

by Hicham Helal, Mohammadi Ahrouch, Abdelaziz Rabehi, Dario Zappa and Elisabetta Comini

Crystals 2024, 14(4), 306; https://doi.org/10.3390/cryst14040306 - 26 Mar 2024

Viewed by 686

Abstract

Solid oxide fuel cells (SOFCs) have emerged as promising candidates for efficient and environmentally friendly energy conversion technologies. Their high energy conversion efficiency and fuel flexibility make them particularly attractive for various applications, ranging from stationary power generation to portable electronic devices. Recently, [...] Read more.

Solid oxide fuel cells (SOFCs) have emerged as promising candidates for efficient and environmentally friendly energy conversion technologies. Their high energy conversion efficiency and fuel flexibility make them particularly attractive for various applications, ranging from stationary power generation to portable electronic devices. Recently, research has focused on utilizing nanostructured materials to enhance the performance of SOFCs. This comprehensive review summarizes the latest advancements in the design, fabrication, and characterization of nanostructured materials integrated in SOFC. The review begins by elucidating the fundamental principles underlying SOFC operation, emphasizing the critical role of electrode materials, electrolytes, and interfacial interactions in overall cell performance, and the importance of nanostructured materials in addressing key challenges. It provides an in-depth analysis of various types of nanostructures, highlighting their roles in improving the electrochemical performance, stability, and durability of SOFCs. Furthermore, this review delves into the fabrication techniques that enable precise control over nanostructure morphology, composition, and architecture. The influence of nanoscale effects on ionic and electronic transport within the electrolyte and electrodes is thoroughly explored, shedding light on the mechanisms behind enhanced performance. By providing a comprehensive overview of the current state of research on nanostructured materials for SOFCs, this review aims to guide researchers, engineers, and policymakers toward the development of high-performance, cost-effective, and sustainable energy conversion systems. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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65 pages, 6260 KiB

Open AccessReview

Recent Advances and Challenges in Thin-Film Fabrication Techniques for Low-Temperature Solid Oxide Fuel Cells

by Mohammadmehdi Choolaei, Mohsen Fallah Vostakola and Bahman Amini Horri

Crystals 2023, 13(7), 1008; https://doi.org/10.3390/cryst13071008 - 25 Jun 2023

Cited by 10 | Viewed by 2211

Abstract

Solid oxide fuel cells (SOFCs) are amongst the most widely used renewable alternative energy systems with near-zero carbon emission, high efficiency, and environment-friendly features. However, the high operating temperature of SOFCs is still considered a major challenge due to several issues regarding the [...] Read more.

Solid oxide fuel cells (SOFCs) are amongst the most widely used renewable alternative energy systems with near-zero carbon emission, high efficiency, and environment-friendly features. However, the high operating temperature of SOFCs is still considered a major challenge due to several issues regarding the materials’ corrosion, unwanted reactions between layers, etc. Thus, low-temperature SOFCs (LT-SOFCs) have gained significant interest during the past decades. Despite the numerous advantages of LT-SOFCs, material selection for each layer is of great importance as the common materials have not shown a desirable performance so far. In addition to the selection of the materials, fabrication techniques have a great influence on the properties of the SOFCs. As SOFCs with thinner layers showed lower polarisation resistance, especially in the electrolyte layer, different thin-film fabrication methods have been employed, and their effect on the overall performance of SOFCs has been evaluated. In this review, we aim to discuss the past and recent progress on the materials and thin-film fabrication techniques used in LT-SOFCs. Full article

(This article belongs to the Special Issue Advances of Solid Oxide Fuel Cells)

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