固体氧化物电池阻隔层致密化对电池性能提升的作用机制

doi:10.15541/jim20260098

摘要/Abstract

摘要： 固体氧化物电池(SOCs)是一种高效的清洁能源技术,在能源转换与氢能制备中具有重要应用前景。然而,在SOCs的制备和运行过程中易发生有害的界面相反应,特别是在Y_0.16Zr_0.84O_2-_δ(YSZ)电解质和SrCo_0.8Nb_0.1Ta_0.1O_3-_δ(SCNT)等锶钴基氧电极组成的电池中,Sr迁移至电解质界面生成的SrZrO₃等高电阻相严重制约了电池的性能。本研究采用磁控溅射技术在YSZ电解质上制备超薄致密的Gd_0.1Ce_0.9O_2-_δ(GDC)阻隔层,系统研究了工艺条件对其微观结构及性能的影响。结果表明,优化后磁控溅射法制备的GDC阻隔层厚度仅约0.5 μm,结构致密且界面结合良好。与传统的丝网印刷法(~5 μm)和喷涂法(~8 μm)相比,厚度显著降低,致密性明显提高。基于该磁控溅射GDC阻隔层的电池在750 ℃燃料电池模式下的最大功率密度达1.762 W·cm^-2,在1.3 V电解电压下的电流密度高达1.921 A·cm^-2,性能显著优于基于丝网印刷法与喷涂法制备的含GDC阻隔层的电池。电化学阻抗分析表明,致密化GDC层有效降低了界面阻抗,优化了氧离子传输。本研究阐明了GDC阻隔层致密化对SOCs性能提升的作用机制,为高性能阻隔层的设计与制备提供了理论依据和技术途径。

关键词: 固体氧化物电池, 阻隔层, 磁控溅射, 锶偏析, 界面相反应

Abstract: Solid oxide cells (SOCs) are highly efficient clean energy technologies that hold significant promise for energy conversion and hydrogen production. However, detrimental interfacial phase reactions tend to occur during the fabrication and operation of the cell. Particularly in cells composed of a Y_0.16Zr_0.84O_2-_δ (YSZ) electrolyte and Sr-Co-based oxygen electrodes like SrCo_0.8Nb_0.1Ta_0.1O_3-_δ (SCNT), the migration of Sr to the electrolyte interface leads to the formation of high-resistivity phases such as SrZrO₃, which severely limits the cell performance. This study employed magnetron sputtering to deposit an ultrathin and dense Gd_0.1Ce_0.9O_2-_δ (GDC) barrier layer onto the YSZ electrolyte, systematically investigating the effects of processing conditions on its microstructure and performance. The results demonstrate that the optimized magnetron-sputtered GDC barrier layer is only about 0.5 μm thick, exhibits a dense microstructure, and forms a good interfacial bonding. Compared with conventional screen-printing (~5 μm) and spray-coating (~8 μm), the magnetron-sputtered GDC layer is significantly thinner and much denser. The single cell incorporating the magnetron-sputtered GDC barrier layer delivers an excellent peak power density of 1.762 W·cm^-2 at 750 ℃ in fuel cell mode, and achieves a high current density of 1.921 A·cm^-2 at an electrolysis voltage of 1.3 V, significantly superior to cells with screen-printed or spray-coated GDC barrier layers. Electrochemical impedance analysis reveals that the densified GDC barrier layer effectively reduces the interfacial resistance and optimizes oxygen ion transport. This study elucidates the mechanism by which GDC barrier layer densification enhances the performance of SOCs, providing both a theoretical foundation and a technical approach for the design and fabrication of high-performance barrier layers.

Key words: solid oxide cell, barrier layer, magnetron sputtering, strontium segregation, interfacial phase reaction

中图分类号:

TM911

徐毅飞, 王子恒, 李永鑫, 李文怀, 王习习, 周川, 周嵬. 固体氧化物电池阻隔层致密化对电池性能提升的作用机制[J]. 无机材料学报, DOI: 10.15541/jim20260098.

XU Yifei, WANG Ziheng, LI Yongxin, LI Wenhuai, WANG Xixi, ZHOU Chuan, ZHOU Wei. Mechanism of Barrier Layer Densification on Performance Enhancement in Solid Oxide Cells[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260098.

参考文献

[1] FEI M, CAI Z, CHEN P,et al. The interlayer proton capture and transport mechanism in oxygen electrodes boosts proton ceramic electrolysis. Energy & Environmental Science, 2026, 19(1): 349.
[2] ZHANG Y, LIU Z, LI J,et al. Interfacial oxide wedging for mechanical-robust electrode in high-temperature ceramic cells. Nature Communications, 2025, 16(1): 8715.
[3] ZHAO Z, QI H, TANG S,et al. A highly active and stable hybrid oxygen electrode for reversible solid oxide cells. International Journal of Hydrogen Energy, 2021, 46(73): 36012.
[4] TIAN Y, ABHISHEK N, YANG C,et al. Progress and potential for symmetrical solid oxide electrolysis cells. Matter, 2022, 5(2): 482.
[5] 周川, 刘威, 梅伟杰, 等. 钨酸镧系列质子导体的开发及应用. 科学通报, 2022, 67(2): 163.
[6] WANG Z, LI W, LI Y,et al. Patterned electrodes for advanced energy conversion and storage: from precision engineering to practical applications. Journal of Materials Chemistry A, 2025, 13(47): 40553.
[7] DEVELOS-BAGARINAO K, YOKOKAWA H, KISHIMOTO H,et al. Elucidating the origin of oxide ion blocking effects at GDC/SrZr(Y)O₃/YSZ interfaces. Journal of Materials Chemistry A, 2017, 5(18): 8733.
[8] POLITOVA T I, IRVINE J T S. Investigation of scandia-yttria-zirconia system as an electrolyte material for intermediate temperature fuel cells—influence of yttria content in system (Y₂O₃)_x(Sc₂O₃)_(11-x)(ZrO₂)₈₉.Solid State Ionics, 2004, 168(1/2): 153.
[9] KHAN M Z, SONG R H, MEHRAN M T,et al. Controlling cation migration and inter-diffusion across cathode/interlayer/electrolyte interfaces of solid oxide fuel cells: a review. Ceramics International, 2021, 47(5): 5839.
[10] KHAN M Z, MEHRAN M T, SONG R H,et al. Effect of GDC interlayer thickness on durability of solid oxide fuel cell cathode. Ceramics International, 2016, 42(6): 6978.
[11] RAILSBACK J, CHOI S H, BARNETT S A.Effectiveness of dense Gd-doped ceria barrier layers for (La,Sr)(Co,Fe)O₃ cathodes on Yttria-stabilized zirconia electrolytes.Solid State Ionics, 2019, 335: 74.
[12] ZHANG Q, PARK B K, BARNETT S,et al. On the role of the zirconia/ceria interface in the degradation of solid oxide electrolysis cells. Applied Physics Letters, 2020, 117(12): 123906.
[13] RYU S, KIM D, LIU T,et al. Fabrication and performance of solid oxide electrolysis cells with sputtered thin film ceria barrier layers. International Journal of Hydrogen Energy, 2026, 197: 152643.
[14] ZHAO H, LYU Q, WANG Y, et al. Controlled aqueous crystallization of gadolinia doped ceria micron-thick ceramic electrolyte for solid oxide fuel cell. Journal of Power Sources, 2025, 644: 237114.
[15] WANG X, HAN M, HUANG Y,et al. Influences of the thickness and density of the gadolinia doped ceria barrier layer on the performance of the solid oxide fuel cell. International Journal of Hydrogen Energy, 2025, 113: 355.
[16] KIM S J, CHOI M, MEGRA Y T,et al. Precursor‐driven facile densification of Gd_0.1Ce_0.9O₂-_δ interlayer for high‐performance solid oxide fuel cells. International Journal of Energy Research, 2022, 46(12): 17511.
[17] JIANG Z, SARRUF B J M, EL-KHAROUF A,et al. Preparation of gadolinium-doped ceria barrier layer for intermediate temperature solid oxide fuel cells by spin coating and evaluation of performance degradation by impedance analysis. Ceramics International, 2024, 50(13): 23222.
[18] LYU Q, ZHU T, QU H,et al. Lower down both ohmic and cathode polarization resistances of solid oxide fuel cell via hydrothermal modified gadolinia doped ceria barrier layer. Journal of the European Ceramic Society, 2021, 41(12): 5931.
[19] LYU Q, ZHU T, LI Z,et al. Enhancement of the cathode/electrolyte interface by a sintering-active barrier layer for solid oxide fuel cells. International Journal of Hydrogen Energy, 2023, 48(40): 15238.
[20] LIANG F, YANG J, WANG H,et al. Fabrication of Gd₂O₃-doped CeO₂ thin films through DC reactive sputtering and their application in solid oxide fuel cells. International Journal of Minerals, Metallurgy and Materials, 2023, 30(6): 1190.
[21] WANG Y, JIA C, LYU Z,et al. Performance and stability analysis of SOFC containing thin and dense gadolinium-doped ceria interlayer sintered at low temperature. Journal of Materiomics, 2022, 8(2): 347.
[22] KHAN M Z, SONG R H, LEE S B,et al. Effect of GDC interlayer on the degradation of solid oxide fuel cell cathode during accelerated current load cycling. International Journal of Hydrogen Energy, 2014, 39(35): 20799.
[23] KHAN M Z, MEHRAN M T, SONG R H,et al. Effects of applied current density and thermal cycling on the degradation of a solid oxide fuel cell cathode. International Journal of Hydrogen Energy, 2018, 43(27): 12346.
[24] GU B, SUNARSO J, ZHANG Y,et al. A high performance composite cathode with enhanced CO₂ resistance for low and intermediate-temperature solid oxide fuel cells. Journal of Power Sources, 2018, 405: 124.
[25] BUZI F, BERNADET L, ORRIT-PRAT J,et al. Advanced manufacturing for efficient GDC diffusion barrier layer by rapid thermal processing for large-area solid oxide cells. Journal of Power Sources, 2025, 652: 237629.
[26] LEE J H, LEE H, YOON J,et al. High performance TF-SOFCs with defect-free electrolyte manufactured via controlled reactive sputtering. Ceramics International, 2025, 51(23): 40490.
[27] LI S, LIU Y, LIU C,et al. Enhanced performance of solid oxide fuel cells using highly conductive Ca²+ and F- co-doped Gd_0.2Ce_0.8O_1.9 buffer layer. Journal of Power Sources, 2024, 612: 234810.
[28] SUMI H, SHIMADA H, WATANABE K,et al. External current dependence of polarization resistances for reversible solid oxide and protonic ceramic cells with current leakage. ACS Applied Energy Materials, 2023, 6(3): 1853.
[29] ZHOU X D, SCARDINO B, ANDERSON H U.Electrical conductivity and stability of Gd-doped ceria/Y-doped zirconia ceramics and thin films.Solid State Ionics, 2004, 175(1-4): 19.
[30] WILDE V, STURMER H, SZASZ J,et al. Gd_0.2Ce_0.8O₂ diffusion barrier layer between (La_0.58Sr_0.4)(Co_0.2Fe_0.8)O₃-_δ cathode and Y_0.16Zr_0.84O₂ electrolyte for solid oxide fuel cells: effect of barrier layer sintering temperature on microstructure. ACS Applied Energy Materials, 2018, 1(12): 6790.
[31] WU S, YAN W, NI N,et al. Densification of ceria-based barrier layer for solid oxide cells at lower sintering temperatures: a review. Journal of Advanced Ceramics, 2025, 14(1): 9221001.
[32] LYU Q, ZHU T, XU N,et al. High-performance (Ce, Zr)O₂-free solid oxide fuel cell with an active-sintered cathode interface and a low-temperature densified micron-scale barrier layer. ACS Applied Materials & Interfaces, 2023, 15(34): 40588.
[33] HANANTYO M P G, PARK J, NAMGUNG Y,et al. Enhanced densification of screen-printed GDC interlayers for solid oxide fuel cells using nitrate-based precursor in various chelating agents as pore-filling solution. International Journal of Hydrogen Energy, 2024, 88: 760.
[34] LEE S E, WARSHI M K, PARK H J.Fabrication of thin and dense GDC buffer layers: enhancing cathode performance in SOFCs.Journal of Material s Chemistry A, 2025, 13(39): 33136.
[35] PARK J, NAMGUNG Y, SINGH B,et al. Enhanced performance of reversible solid oxide fuel cells by densification of Gd_0.1Ce_0.9O₂-_δ(GDC) barrier layer/La_0.6Sr_0.4Co_0.2Fe_0.8O₃-_δ, 2024, 976: 173296.
[36] LYU Q, ZHAO H, HE J,et al. Interfacial engineering of (Ce, Zr) O₂ composite barrier layers for enhancing the durability of solid oxide fuel cells. Journal of Power Sources, 2024, 622: 235354.
[37] LYU Q, ZHAO H, HE J,et al. An in situ hydrothermally self-crystallized dense ceria-based barrier layer for solid oxide fuel cells. Journal of Materials Chemistry A, 2024, 12(16): 9778.
[38] SONG J H, JUNG M G, PARK H W,et al. The effect of fabrication conditions for GDC buffer layer on electrochemical performance of solid oxide fuel cells. Nano-Micro Letters, 2013, 5(3): 151.
[39] BOILEAU L, COTON N, COQUÍS P,et al. GDC buffer layer synthesized by reactive magnetron sputtering: effect of total pressure and thickness on SOFC performances. Crystals, 2020, 10(9): 759.
[40] BAI Q, DEVELOS-BAGARINAO K, YAMAGUCHI T,et al. Unraveling the pivotal role of heterointerfaces on oxide ion transport in solid oxide fuel cells. Journal of Power Sources, 2024, 593: 233952.
[41] LAURENCIN J, HUBERT M, SANCHEZ D F,et al. Degradation mechanism of La_0.6Sr_0.4Co_0.2Fe_0.8O₃-_δ/Gd_0.1Ce_0.9O_2-δ composite electrode operated under solid oxide electrolysis and fuel cell conditions. Electrochimica Acta, 2017, 241: 459.