硅酸盐学报

固体氧化物电池空气极材料质子传输过程研究进展

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洪涛 , 夏谦 , 孙颖 , 孙闯 , 程继贵

硅酸盐学报 | 综合评述 2026,54(4): 1426-1438

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硅酸盐学报 | 综合评述 2026, 54(4): 1426-1438

固体氧化物电池空气极材料质子传输过程研究进展

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洪涛, 夏谦, 孙颖, 孙闯, 程继贵

作者信息

合肥工业大学材料科学与工程学院，合肥 230009

洪涛（1989—），男，博士，副教授。

HONG Tao (1989-), male, Associate Professor. E-mail: taoh@hfut.edu.cn

通讯作者:

洪涛（1989—），男，博士，副教授

程继贵（1963—），男，博士，教授。

Research Progress on Proton Uptake/Transport Process in Solid Oxide Fuel Cell Air Electrode Materials

Tao HONG, Qian XIA, Ying SUN, Chuang SUN, Jigui CHENG

Affiliations

School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China

出版时间: 2026-03-12 doi: 10.14062/j.issn.0454-5648.20250704

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摘要

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以质子为传导离子的可逆固体氧化物燃料电池朝着低温化方向的发展对其空气极材料提出了新的要求，同时具有质子、氧离子和电子传导的混合离子导体材料表现出了良好的发展潜力。目前，混合离子导体中与质子相关的各项参数如浓度、扩散速率、表面交换速率的测量仍然存在诸多问题和挑战。本文系统性地讨论了利用热重方法和电导弛豫方法测量混合离子导体中质子相关参数的原理和进展，给出了质子扩散速率等热力学参数。同时分析了具有三重传导的混合离子导体中质子、氧离子和电子在浓度上的耦合关系，最后讨论了由于氧离子和质子在扩散速率上存在巨大差异导致的双重扩散现象。针对未来采用原位光谱，中子衍射和计算方法对混合离子导体中质子输运过程进行了模拟分析。

关键词

混合离子导体 / 质子 / 水捕获 / 质子陶瓷燃料电池

Abstract

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The proton surface uptake and transport properties in air electrode materials can be complex due to the proton could be effective for protonic ceramic fuel/electrolysis cells. This review summaries the proton surface uptake, transport and the coupled properties in mixed conductors. The proton in mixed conductor with hole, oxygen vacancy and proton conductivity can be determined by thermogravimetric investigations, where the water vapor can occur due to acid-base reaction (hydration) or redox reaction (hydrogen uptake), depending on the oxygen partial pressure, i.e., on the material's defect concentrations. In addition, the reaction in hydrogenation reaction can be also determined by electrical conductivity relaxation method due the consumption of hole in proton uptake process, where the proton surface exchange kinetics can be calculated.

Proton conducting perovskites with significant hole and oxygen vacancy conductivity can make it working as cathode materials that suits for fuel cells using proton conducting electrolytes. Based on the existing studies, the proton transport process in mixed conductor is a complicate process where the three majority carriers, i.e., proton, oxygen ion and electron mixed together. And the effective diffusion coefficient of ions (i.e., oxygen ion and proton) can change, and these observed over-shooting relaxation profiles can be explained in terms of defect chemical model and transport equations for materials with three mobile carriers. For the complex transport kinetics, diffusion equations can be derived by the hypothesis of ideally dilute situation.

The two-fold diffusion process can be determined in the water uptake process. The hydration reaction firstly occurs at the consume of oxygen vacancy. However, in the diffusion step where the incorporated proton/oxygen ion diffuse from outer layer to the inner bulk, the highly mobile protons are charge compensated by holes under electric neutrality law. That is because of the much higher diffusion rate of proton rather than oxygen ion, so hole is formed locally instead of waiting for the slowly moved oxygen vacancy. The non-monotonic process can be monitored by an electrical relaxation method, and the optical absorption spectroscopic method can allow for an in-situ detection of such re-dox involved reactions as a function of space and time at high temperatures.

Summary and prospects

A cathode with mixed hole, oxygen vacancy, and proton conductivity extends the reactive zone for the oxygen reduction to water beyond the triple phase boundary, making the whole cathode surface an active electrocatalyst. The defect chemistry (i.e., concentrations and mobilities of point defects) of such materials with three charge carriers is complex, and some of the desired properties for a PCFC cathode material are in mutual conflict (i.e., proton uptake, electronic conductivity, catalytic activity, and long-term chemical stability). And the promising protonic cathode material needs a high catalytic activity for the oxygen reduction reaction to water to improve its performance. Nevertheless, the reactions both require the dissociation of the strong oxygen-oxygen bond.

The mechanism for this reaction is not exactly identical to that in oxide-ion-conducting cells (where the resulting oxide ions are incorporated into the cathode material, while on PCFC cathode, they are desorbed in the form of steam). The dependence of proton uptake on cation composition in cathode perovskites in order to extract the parameters that are most important for a high proton concentration. Regarding the optimization of PCFC cathode materials, refraining from striving for very high electronic conductivities is anticorrelated with proton uptake. It is prospected that the role plays due to oversized dopants in barium ferrate for enhancing the hydration properties. The beneficial effect on protonation is attributed to a higher degree of disorder in the local structure of doped samples, which translates in B-O-B bonds buckling. The B-O-B buckling reduces the Fe-O bond covalency (i.e., less Fe 3d-O 2p orbital overlap), thus decreasing the hole transfer from iron to oxygen. This leaves more negative charge density on the oxide ions, which increases their basicity and propensity for protonation.

In addition, although the existing thermogravimetric and electrical conductivity relaxation methods still have certain limitations in measuring proton concentration in mixed ionic conductors. The in-situ characterization techniques (such as in-situ transmission electron microscopy, in-situ spectroscopy, neutron diffraction, etc.) can be used to analyze the process of proton absorption and transport in mixed ionic conductors. Also, combining multi-scale simulations with experiments can further analyze numerical values such as the binding energy of proton absorption and the activation energy of diffusion. For instance, in-situ transmission electron microscopy is used to directly observe water entering Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ via introducing a small amount of water vapor into the TEM chamber. Electron energy loss spectroscopy is also used to determine the formation of oxygen bubbles on the material surface, while the protons ultimately remain within the material. This result provides the most direct evidence for studying the reactions of water and protons in mixed ionic conductors.

Key words

mixed ionic and electronic conductor / proton / water uptake / protonic ceramic fuel cells

引用本文

洪涛, 夏谦, 孙颖, 孙闯, 程继贵. 固体氧化物电池空气极材料质子传输过程研究进展. 硅酸盐学报, 2026 , 54 (4) : 1426 -1438 . DOI: 10.14062/j.issn.0454-5648.20250704

Tao HONG, Qian XIA, Ying SUN, Chuang SUN, Jigui CHENG. Research Progress on Proton Uptake/Transport Process in Solid Oxide Fuel Cell Air Electrode Materials[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (4) : 1426 -1438 . DOI: 10.14062/j.issn.0454-5648.20250704

基金

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国家自然科学基金青年基金项目(51802065)

参考文献

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2026年第54卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250704

接收时间：2025-09-24
首发时间：2026-05-20
出版时间：2026-03-12

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收稿日期：2025-09-24
修回日期：2025-12-04

基金

国家自然科学基金青年基金项目(51802065)

作者信息

合肥工业大学材料科学与工程学院，合肥 230009

通讯作者:

洪涛（1989—），男，博士，副教授

程继贵（1963—），男，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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