图形电极在固体氧化物燃料电池中的应用

doi:10.11949/0438-1157.20241401

摘要/Abstract

摘要：

固体氧化物燃料电池（SOFC）以其高效、低排放特性成为可持续能源的关键，但电极反应机理的复杂性制约着其性能提升。图形电极作为一种新兴的电极结构，因其可精确调控电极的几何形状，显著提升了三相边界（TPB）的长度和反应表面积，极大促进了SOFC电化学反应速率，并为反应机理的深入研究提供了理想平台。综述了图形电极在SOFC反应机理研究中的应用及其制备技术。图形电极通过微纳加工实现了电极-电解质界面的精确结构控制，显著增加了TPB的长度和反应活性面积，从而提升了电池的电化学性能和长期稳定性。详细探讨了图形电极在SOFC反应机理研究中的独特优势，包括其在电化学反应动力学、物质传输机制以及电荷传输耦合研究中的应用。通过对TPB反应、气体扩散、电流分布等关键过程的精确控制，图形电极能够简化复杂的多孔电极结构，提供了深入分析电极反应过程的理想平台。最后展望了其未来发展方向及面临的挑战，特别是在规模化应用和新型材料探索方面的潜力。

关键词: 燃料电池, 电化学, 微尺度, 图形电极, 三相边界, 反应机理

Abstract:

Solid oxide fuel cells (SOFCs) have become the key to sustainable energy with their high efficiency and low emission characteristics, but the complexity of the electrode reaction mechanism restricts their performance improvement. The patterned electrode, as a new type of electrode structure, can precisely control the geometric shape of the electrode, significantly increase the length and reaction surface area of the triple phase boundary (TPB), greatly promote the electrochemical reaction rate of SOFC, and provide an ideal platform for in-depth research on reaction mechanisms. This paper reviews the application and preparation technology of patterned electrodes in the study of SOFC reaction mechanisms. Patterned electrodes realize the precise structural control of the electrode-electrolyte interface through micro-nano processing, significantly increase the length and reaction active area of TPB, thereby enhancing the electrochemical performance and long-term stability of the battery. The unique advantages of patterned electrodes in the study of SOFC reaction mechanisms are discussed in detail, including their application in the study of electrochemical reaction dynamics, material transfer mechanisms, and charge transfer coupling. Through precise control of key processes such as TPB reaction, gas diffusion, and current distribution, patterned electrodes can simplify complex porous electrode structures, providing an ideal platform for in-depth analysis of electrode reaction processes. Finally, the future development direction and challenges faced are looked forward to, especially the potential in large-scale applications and exploration of new materials.

Key words: fuel cells, electrochemistry, microscale, patterned electrodes, triple phase boundary, reaction mechanism

中图分类号:

TM 911.4

王子恒, 李文怀, 周嵬. 图形电极在固体氧化物燃料电池中的应用[J]. 化工学报, 2025, 76(7): 3153-3171.

Ziheng WANG, Wenhuai LI, Wei ZHOU. Application of patterned electrodes in solid oxide fuel cell[J]. CIESC Journal, 2025, 76(7): 3153-3171.

图/表 20

图1 阳极支撑SOFC的结构[30]

Fig.1 Schematic images of the proposed configuration of patterned anode-supported SOFC[30]

图2 激光烧蚀过程及机理示意图[32]

Fig.2 Schematic illustration of the laser ablating process and mechanism[32]

图3 主模加工工艺：(a) SU8旋转涂层；(b)预烘烤；(c)光掩膜紫外曝光；(d)烘烤；(e)在PGMEA中显影；(f)冲洗；(g)烘烤使SU8完全固化；(h)得到主柱图案[34]

Fig.3 Fabrication process of the master mold: (a) SU8 spin coating; (b) pre-baking; (c) UV exposure through the photomask; (d) baking; (e) developing in PGMEA; (f) rinsing; (g) baking to cure SU8 completely; (h) master pillar pattern was obtained[34]

图4 微挤压打印工艺示意图[36]

Fig.4 Schematic view of the microextrusion printing process[36]

图5 （a）层状材料压印工艺示意图；（b）两张叠片在加热下压紧；（c）在板材表面和板材之间的界面上都有微图案[42]

Fig.5 (a) Schematic of the imprint process for layered material; (b) Two stacked sheets are pressed under heating; (c) Micro patterns are made on both surface and interface between sheets[42]

图6 使用µCP和选择性ALD制备图像化铂薄膜的过程示意图[45]

Fig.6 Schematic outline of the procedure to fabricate patterned Pt thin films using microcontact printing and selective atomic layer deposition[45]

图7 电池制造过程和实验装置的示意图：(a)第一次溅射；(b)第二次溅射；(c) Pt阴极制作；(d)电池尺寸调整；(e)共聚焦激光显微镜实验设置；(f)高温室；(g)图像化电池结构；(h)图像化阳极的SEM图像[49]

Fig.7 Schematic representations of the cell fabrication process and the experimental setup: (a) first sputtering; (b) second sputtering; (c) Pt cathode fabrication; (d) size adjustment of the cell; (e) experimental set-up with a confocal laser microscope; (f) high temperature chamber; (g) patterned cell configuration; (h) SEM image of the patterned anode[49]

表1 在不同压力下烧结的对称电池在不同温度下的极化电阻测量［31］

Table 1 Polarisation resistance measured at different temperatures on symmetrical cells sintered with different pressures［31］

温度/℃	极化电阻/(Ω·cm²)
温度/℃	空白无压力	空白 P=4.9 kPa	点阵28 µm 无压力	点阵28 µm P=2.45 kPa	点阵28 µm P=4.90 kPa
700	2.47	2.61	5.05	2.09	1.70
750	1.17	1.27	2.92	1.00	0.91
800	0.54	0.55	1.87	0.43	0.41
850	0.28	0.25	1.31	0.19	0.18
900	0.14	0.13	1.03	0.10	0.10
平均变化	—	-0.36%	+301%	-22.2%	-28.4%

图8 平面电池和3D电池的电化学性能：平面电池(a)和3D电池(b)在不同工作温度下的电流密度-电压-功率密度曲线；平面电池(c)和3D电池(d)在0.75 V电压及不同工作温度下的Nyquist图（插图为低电阻区域的放大图）[52]

Fig.8 Electrochemical performance of planar- and 3D-cells: Current density-voltage-power density curves for the planar-cell (a) and 3D-cell (b) at different operating temperatures; The Nyquist plots for the planar-cell (c) and 3D-cell (d) under the voltage of 0.75 V and different operating temperatures (The insets are magnified views of the low-resistance region)[52]

图9 Y2O3多孔条纹电池在运行前后镍形貌的光学显微镜图像（Ni的初始边缘由红色虚线标示，迁移后的Ni前沿由黄色虚线标示）[60]

Fig.9 Optical microscopy images of Ni morphology on the Y2O3 porous stripe cells (The initial edge of Ni is indicated by the red dashed line, and the migrated Ni front is indicated by the yellow dashed line)[60]

图10 在近乎干燥的CH4气氛下的性能与稳定性：(a)在550℃、3% H2O/CH4气氛下，未经电化学沉积(CELD)处理的对称模型Ni-YSZ（图案化Ni‖YSZ‖图案化Ni）和12%（原子分数） Ni NP-SDC阴极电解质层时的典型阻抗谱；(b)裸Ni和12%（原子分数）Ni NP-SDC在3% H2O/CH4气氛下的低频电阻（RLF）随温度的变化情况；(c)在650℃、3% H2O/CH4气氛下，裸Ni和12%（原子分数）Ni NP-SDC的RLF的降解速率；(d)在650℃、3% H2O/CH4气氛下进行90 h电化学阻抗谱测试后，12%（原子分数）Ni NP-SDC的扫描电子显微镜图像[68]

Fig.10 Performance and stability under a nearly dry CH4 atmosphere: (a) Typical impedance spectra of the symmetric model Ni-YSZ (patterned Ni‖YSZ‖patterned Ni) without CELD and with 12% (atom) Ni NP-SDC CELD obtained under a 3%H2O/CH4 atmosphere at 550℃; (b) Temperature dependence of the RLF of bare Ni and 12% (atom) Ni NP-SDC under a 3%H2O/CH4 atmosphere; (c) Degradation rate of the RLF of bare Ni and 12% (atom) Ni NP-SDC under a 3% H2O/CH4 atmosphere at 650℃; (d) SEM image of the 12% (atom) Ni NP-SDC after the EIS test under 3% H2O/CH4 at 650℃ for 90 h[68]

图11 在800℃、含5%水蒸气的氢气气氛下，阳极与参比电极之间的电流-电压特性：(a)溅射法制备的Ni-YSZ；(b)丝网印刷法制备的Ni-YSZ；(c)溅射法制备的Ni；(d)丝网印刷法制备的Ni[69]

Fig.11 Current-voltage characteristics between the anode and reference electrodes under a 5% humidified hydrogen atmosphere at 800℃: (a) Ni-YSZ by sputtering; (b) Ni-YSZ by screen printing; (c) Ni by sputtering; (d) Ni by screen printing[69]

图12 (a)无量纲交换电流密度（iex/i0）和无量纲电位（Fϕ0/RT）对无量纲平均电流密度（iav/i0）的综合影响；(b)基于图(a)生成的相图（用于设计和操作嵌入离子导体中的半圆柱形电子导体条图案化阳极，其中最大面积、过渡面积和最小面积分别对应于图(a)中虚点线划分的底部、中部和上部区域）[76]

Fig.12 (a) Combined effect of dimensionless exchange current density (iex/i0) and dimensionless potential (Fϕ0/ RT) on dimensionless average current density (iav/i0); (b) Phase map generated based on Fig.(a) for rational design and operation of patterned anode with semi-cylinder electronic conductor strips embedded in ionic conductor, in which the maximum area, the transition area and the minimum area correspond to the bottom, middle and upper areas of Fig.(a) divided by dash dot line[76]

图13 Cu10/CeO2(111)表面H2氧化的TPB (a)和氢溢流(b)途径示意图[86]

Fig.13 Schematic of TPB (a) and H-spillover (b) pathways for H2 oxidation on the Cu10/CeO2(111) surface[86]

图14 H2氧化反应能量对比（黑线和紫线分别为H2在化学计量学CeO2(111)和Cu10/CeO2(111)的TPB途径上的氧化反应；ΔEx 表示相邻两个反应步骤间结构的能量差，即第x步的能量减去第x-1步的能量；ΔETS表示过渡态的能垒；Rx对应图13）[86]

Fig.14 Comparison of reaction energy profiles for H2 oxidation (The black line and the purple line refer to H2 oxidation on the stoichiometric CeO2(111) and the TPB pathway of the Cu10/CeO2(111), respectively; ΔEx represents the energy difference of structures between two neighboring reaction steps, which is the energy of the xth minus the energy of the (x-1) th; ΔETS represents the energy barrier of the transition state; Rx corresponds to Fig.13)[86]

图15 H2氧化途径示意图[85]

Fig.15 The schematic of H2 oxidation pathways[85]

图16 在(a) 2.5 h、 (b) 5 h和(c) 20 h VW-R = 0.7 V下的Ni膜电极截面的SEM图像；(d)工作20 h后电极微观结构的FIB-SEM重建[89]

Fig.16 SEM images of Ni film electrode cross-sections after (a) 2.5 h, (b) 5 h and (c) 20 h operations at VW-R = 0.7 V; (d) The FIB-SEM reconstruction of the electrode microstructure corresponding to Fig.(c) after 20 h operation[89]

图17 在800℃工作温度下，电池(a) C1-A~C4-A以及(b)C1-C~C4-C的性能和(c)最佳情况[97]

Fig.17 Performances of (a) C1-A—C4-A and (b) C1-C—C4-C and (c) the best cases at 800℃ operating temperature[97]

图18 RSOC在阳极极化条件下的原位观测结果(a)~(h)（其中白色线条表示活性TPB）；(i)电流密度和活性TPB长度随时间的变化情况[图(a)~(h)是图(i)中蓝色点处的俯视图][103]

Fig.18 Operando observation of RSOC cell under anodic polarization (a)—(h) (white line indicates active TPB); (i) Developments of current density and active TPB length over time [Figs.(a)—(h) are the top views at the blue points in Fig.(i)][103]

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