硅酸盐学报

高温质子陶瓷电化学合成氨关键材料的研究进展

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王嘉宾 ¹ , 周露 ¹ , 杨烨 ² , 颜冬 ¹ , 李箭 ¹ , 贾礼超 ¹

硅酸盐学报 | 固体氧化物电池表界面专题—综合评述 2025,53(10): 3056-3068

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硅酸盐学报 |固体氧化物电池表界面专题—综合评述 2025 , 53 (10) : 3056 -3068

高温质子陶瓷电化学合成氨关键材料的研究进展

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王嘉宾¹, 周露¹, 杨烨², 颜冬¹, 李箭¹, 贾礼超¹

作者信息

^1．华中科技大学材料科学与工程学院，材料成形与模具技术全国重点实验室，武汉 430074

^2．科学技术部国际科技合作中心，北京 100084

通讯作者:

贾礼超（1985—），男，博士，教授。

作者简介:

王嘉宾（1998—），男，博士研究生。

Research Progress on Key Materials for High-Temperature Electrochemical Ammonia Synthesis by Proton-Conducting Ceramic

Jiabin WANG¹, Lu ZHOU¹, Ye YANG², Dong YAN¹, Jian LI¹, Lichao JIA¹

Affiliations

^1.School of Materials Science and Engineering, State Key Lab of Material Processing and Die & Mould Technology, Huazhong University of Science and Technology, Wuhan 430074, China

^2.International Cooperation Center for Science and Technology, Ministry of Science and Technology, Beijing 10084, China

Corresponding Author:

JIA Lichao (1985-), male, Ph.D., Professor. E-mail: jialc@hust.edu.cn

WANG Jiabin (1998-), male, Doctoral candidate. E-mail: jiabinwang1022@163.com

出版时间: 2025-10-20 doi: 10.14062/j.issn.0454-5648.20250187

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摘要

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氨（NH₃）是全球第二大化工产品，在全球经济中占有重要地位。传统Haber-Bosch工艺因高能耗和环境污染问题亟待革新，基于高温质子陶瓷电池的电化学合成氨体系以电能驱动突破氮气活化热力学壁垒，在常压条件下实现绿色合成，受到国内外研究者的广泛关注。本文系统总结了高温质子陶瓷电解质与氨电极材料的研究进展，重点分析了电解质质子传导特性与氨电极催化活性协同优化策略，揭示了材料结构-氨合成性能的构效关系，并就材料设计和理论机制研究进行了展望。

关键词

合成氨 / 质子陶瓷电解质 / 氨电极材料 / 钙钛矿 / 电化学

Abstract

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As the second largest chemical product globally, ammonia plays a pivotal role in the economy. The conventional Haber-Bosch process urgently needs innovation due to its high energy consumption and environmental pollution. The high-temperature electrochemical ammonia synthesis system based on protonic ceramic cells, which uses electric energy to overcome the thermodynamic barrier of nitrogen activation and achieves green synthesis under ambient pressure conditions, has attracted much attention.

Proton-conducting ceramic cells consist of an electrolyte and two electrodes (i.e., ammonia electrode and hydrogen electrode). The electrolyte must simultaneously fulfill dual functions, i.e., proton conduction and gas isolation. Its material design requires a) dense microstructure to block gas permeation, b) high proton conductivity and negligible electronic conductivity, c) chemical stability under high-temperature conditions with exposure to H₂O, CO₂, and NH₃, and d) thermal expansion coefficient compatibility with electrode materials to avoid thermomechanical stress-induced damage. This review systematically represents the applications of perovskite, fluorite, and pyrochlore-type electrolytes in ammonia synthesis. SrCeO₃-based oxides are the reported perovskite materials with a proton conductivity, with their proton transport capacity that is enhanced through ionic doping strategies. Compared to other perovskite oxides, BaCeO₃-based perovskites with a higher conductivity are currently among the most extensively studied proton-conducting materials. Doping with rare-earth metals is a common strategy to improve the proton conductivity of BaCeO₃-based oxides. Alkaline-earth zirconate oxides (i.e., CaZrO₃, SrZrO₃, BaZrO₃) exhibit lower proton conductivity than cerium-based oxides but demonstrate superior chemical stability and mechanical strength. LaGaO₃-based oxides achieve a nearly pure proton conductivity in H₂ atmospheres, and LaGaO₃-based electrolytes doped with Ca²⁺, Sr²⁺, or Ba²⁺ demonstrate a good performance in ammonia synthesis. Beyond perovskites, non-perovskite oxides such as fluorite (i.e., AO₂) and pyrochlore (i.e., A₂B₂O₇) also exhibit a notable proton conductivity under high-temperature and hydrogen-containing conditions. Rare-earth-doped CeO₂ fluorite-type electrolytes outperform perovskite counterparts in ammonia generation rates. SDC electrolyte achieves a record-high ammonia formation rate of 8.2×10^-9 mol·s^-1·cm^-2 at 650 ℃ as the maximum reported value based on proton-conducting ceramic. Pyrochlore-structured electrolytes have a proton conductivity comparable to fluorite structures but with enhanced chemical stability.

The catalytic activity and stability of the ammonia electrode directly affect the rate of ammonia synthesis. Electrode materials require superior nitrogen adsorption/dissociation capabilities coupled with a high NH₃ selectivity. Also, ammonia electrodes must demonstrate adequate electronic/protonic conductivity and chemical stability. Noble metals are widely used in early-stage proton-conducting ceramic electrochemical ammonia synthesis due to their high electronic conductivity and catalytic activity. Ag-Pd bimetallic alloys are the most common electrode materials. Pd exhibits a high catalytic activity for NRR, enabling N≡N bond dissociation at elevated temperatures. However, Pd preferentially adsorbs H atoms over N atoms, leading to dominant HER over NRR. Ag-Pd alloy partially suppresses HER, while enhancing ammonia production rates and faradaic efficiency. Perovskite materials become promising alternatives for ammonia electrodes due to their tunable structure, high thermal stability and low cost. Cobalt-based perovskites possess a superior catalytic activity, and they are extensively studied for electrochemical ammonia synthesis. However, some challenges such as cobalt reduction/volatilization, high thermal expansion coefficients, and elevated costs restrict their practical application. Ru-doped perovskites are particularly attractive due to the superior catalytic activity for N₂ activation. Iron-containing perovskites have attracted much attention as cathode materials for protonic ceramic ammonia synthesis. The multivalent characteristics of Fe confer dual advantages in vacancy regulation and electronic structure optimization.

Summary and prospects

High-temperature proton-conducting ceramic ammonia synthesis remains in the fundamental research stage, requiring further studies in proton source optimization, material development, and reaction mechanism elucidation. For proton source exploration, previous studies predominantly used high-cost pure H₂ as a proton source. Recent research has confirmed the feasibility of H₂O as a proton source, but this imposes stringent requirements on electrode stability under steam exposure. Hydrogen derived from steam methane reforming or water-gas shift reactions offers an alternative strategy, enabling potential reductions in energy consumption and CO₂ emissions. Future work should systematically evaluate the protonation efficiency of H₂O, CH₄, and other candidates, establishing a matching mechanism among hydrogen sources, electrolytes, and electrodes. Compared to conventional metal electrodes, perovskite electrodes exhibit unique advantages in cost-effectiveness and performance tunability. However, their catalytic activity and long-term operational stability require an enhancement. Strategies such as ionic doping, defect engineering, in-situ exsolution, and advanced synthesis techniques can optimize crystal structures, enabling electrodes with high activity and durability. The reaction mechanism of protonic ceramic ammonia synthesis remains unclear. In-depth studies on catalytic pathways and degradation mechanisms at ammonia electrodes are urgently needed. The density functional theory should be used to calculate N₂ adsorption/activation energy barriers and proton transport pathways, establishing structure-activity relationships between catalyst electronic structures and NRR performance. In-situ X-ray photoelectron spectroscopy and in-situ transmission electron microscopy are used to analyze the proton migration process at the hydrogen electrode and N₂ activation process at the ammonia electrode, and the DRT analysis is used to reveal the velocity determination steps under multi-field coupling conditions. These studies will provide a theoretical support for the construction of efficient and stable proton ceramic ammonia synthesis system.

Key words

synthesis of ammonia / proton ceramic electrolyte / ammonia electrode material / perovskite / electrochemistry

引用本文

王嘉宾, 周露, 杨烨, 颜冬, 李箭, 贾礼超. 高温质子陶瓷电化学合成氨关键材料的研究进展. 硅酸盐学报, 2025 , 53 (10) : 3056 -3068 . DOI: 10.14062/j.issn.0454-5648.20250187

Jiabin WANG, Lu ZHOU, Ye YANG, Dong YAN, Jian LI, Lichao JIA. Research Progress on Key Materials for High-Temperature Electrochemical Ammonia Synthesis by Proton-Conducting Ceramic[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (10) : 3056 -3068 . DOI: 10.14062/j.issn.0454-5648.20250187

基金

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国家自然科学基金(52472202)

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2025年第53卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250187

接收时间：2025-03-19
首发时间：2026-10-21
出版时间：2025-10-20

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收稿日期：2025-03-19
修回日期：2025-04-17

基金

国家自然科学基金(52472202)

作者信息

^1．华中科技大学材料科学与工程学院，材料成形与模具技术全国重点实验室，武汉 430074

^2．科学技术部国际科技合作中心，北京 100084

通讯作者:

贾礼超（1985—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250187

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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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