质子陶瓷膜反应器的制备及低温氨分解性能研究

doi:10.15541/jim20250057

无机材料学报 ›› 2025, Vol. 40 ›› Issue (11): 1277-1284.DOI: 10.15541/jim20250057

质子陶瓷膜反应器的制备及低温氨分解性能研究

唐阳¹(), 刘立敏¹^,²(), 周晓亮¹^,²^,³, 张搏³, 蒋星洲¹, 贾浩义¹, 罗延麟庆¹

1.西南石油大学化学化工学院, 成都 610500
2.天府永兴实验室, 成都 611130
3.新疆理工学院能源化工工程学院, 阿克苏 843100

收稿日期:2025-02-14 修回日期:2025-04-17 出版日期:2025-11-20 网络出版日期:2025-05-22
通讯作者: 刘立敏, 副教授. E-mail: liulimin_ly@126.com
作者简介:唐阳(2001-), 男, 硕士研究生. E-mail: 2630565355@qq.com
基金资助:
国家重点研发计划(2021YFB4001502);国家自然科学基金(22075231);天府永兴实验室组织研究项目(2023KJGG09)

Proton Ceramic Membrane Reactor: Preparation and Low-temperature Ammonia Decomposition Performance

TANG Yang¹(), LIU Limin¹^,²(), ZHOU Xiaoliang¹^,²^,³, ZHANG Bo³, JIANG Xingzhou¹, JIA Haoyi¹, LUO Yanlinqing¹

1. College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
2. Tianfu Yongxing Laboratory, Chengdu 611130, China
3. College of Energy and Chemical Engineering, Xinjiang Institute of Technology, Akesu 843100, China

Received:2025-02-14 Revised:2025-04-17 Published:2025-11-20 Online:2025-05-22
Contact: LIU Limin, associate professor. E-mail: liulimin_ly@126.com
About author:TANG Yang (2001-), male, Master candidate. E-mail: 2630565355@qq.com
Supported by:
National Key Research and Development Program of China(2021YFB4001502);National Natural Science Foundation of China(22075231);Tianfu Yongxing Laboratory Organized Research Project Funding(2023KJGG09)

摘要/Abstract

摘要：

氨气(NH₃)作为一种储氢材料, 具有高储氢密度、易液化等优点, 因此利用氨分解制氢是一种理想的氢气(H₂)制备方法。但传统氨分解的工作温度过高, 中低温下NH₃转化效率过低且H₂纯度较低, 无法实现H₂的有效制取。本研究通过共压法制备了具有多孔电极Ni-BZCY/BZCY/Ni-BZCY(BZCY: BaZr_0.1Ce_0.7Y_0.2O_3-_δ)对称结构的质子陶瓷膜反应器(PCMR)。在600 ℃时, PCMR在H₂与NH₃气氛下分别实现了0.11和0.23 Ω·cm²的极化阻抗(R_p), 在0.8 V外加电压下其电流密度分别达到1.87和1.56 A·cm^-2; 在300 ℃、0.8 V外加电压下, H₂与NH₃中的电流密度仍能分别达到0.16和0.06 A·cm^-2。通过共压法所制备的PCMR在600 ℃下的NH₃分解转化效率达到80%, 比裸催化剂材料提升了8%, 在350 ℃仍能实现0.3%的提升, 即使在300 ℃下NH₃转化效率也达到约1%。本研究为实现低温氨分解制氢提供了新的思路。

关键词: 制氢, 氨分解, 低温, 质子陶瓷膜反应器, 电化学性能, 质子传输

Abstract:

Ammonia (NH₃) has been considered as a hydrogen storage material due to high hydrogen storage density and ease of liquefaction, thus hydrogen (H₂) production by ammonia decomposition is an ideal method for hydrogen preparation. However, traditional ammonia decomposition technologies face challenges such as high operating temperatures, low efficiency at moderate temperatures, and difficulties in hydrogen purification. In this study, proton ceramic membrane reactor (PCMR) with symmetric structure of porous electrode Ni-BZCY/BZCY/Ni-BZCY (BZCY: BaZr_0.1Ce_0.7Y_0.2O_3-_δ) was prepared by co-pressing method. At 600 ℃, PCMR exhibited polarization resistances (R_p) of 0.11 and 0.23 Ω·cm² in H₂ and NH₃ atmospheres, respectively, with corresponding current densities of 1.87 and 1.56 A·cm^-2 at an applied voltage of 0.8 V. Even at 300 ℃ and 0.8 V, the current densities in H₂ and NH₃ remained at 0.16 and 0.06 A·cm^-2, respectively. The NH₃ conversion efficiency of PCMR reached 80% at 600 ℃, improving by 8% compared to bare catalyst material. Even at 350 ℃, an additional improvement of 0.3% can still be attained, and the NH₃ conversion efficiency of about 1% was demonstrated even at 300 ℃. This study provides a novel approach to low-temperature ammonia decomposition for hydrogen production.

Key words: hydrogen production, ammonia decomposition, low-temperature, proton ceramic membrane reactor, electrochemical property, proton transport

中图分类号:

TK91

唐阳, 刘立敏, 周晓亮, 张搏, 蒋星洲, 贾浩义, 罗延麟庆. 质子陶瓷膜反应器的制备及低温氨分解性能研究[J]. 无机材料学报, 2025, 40(11): 1277-1284.

TANG Yang, LIU Limin, ZHOU Xiaoliang, ZHANG Bo, JIANG Xingzhou, JIA Haoyi, LUO Yanlinqing. Proton Ceramic Membrane Reactor: Preparation and Low-temperature Ammonia Decomposition Performance[J]. Journal of Inorganic Materials, 2025, 40(11): 1277-1284.

图/表 12

图1 PCMR测试装置示意图

Fig. 1 Schematic diagram of the PCMR test setup

图2 样品的XRD图谱

Fig. 2 XRD patterns of samples (a) BZCY calcined at 1000 ℃ for 5 h in air and calcined at 400 and 600 ℃ for 4 h in NH3; (b) NiO-BZCY and Ni-BZCY treated with H2 and NH3 for 4 h at 400 ℃

图3 PCMR (a)截面、(b)电解质、(c, d)两侧电极的SEM照片和(e~j) NiO-BZCY电极的EDS元素分布图

Fig. 3 SEM images of (a) cross-section, (b) electrolyte, and (c, d) electrodes on both sides of PCMR, and (e-j) EDS elemental mappings of NiO-BZCY electrode

图4 PCMR在(a) H2、(b) NH3气氛下的LSV测试结果

Fig. 4 LSV results under (a) H2 and (b) NH3 environments for PCMR

表1 部分对称型PCMR的电流密度

Table 1 Current density of partially symmetrical PCMR

Reactor structure	Temperature/℃, gas environment	Voltage/V	Current density/ (A·cm^-2)	Ref.
Ni-BZCY/BZCY/Ni-BZCY	650, 50% H₂-N₂(measured at only 650 ℃)	0.8	2.0	[18]
LSV-Ce-Pd/BZCYCu/LSV-Ce-Pd	600, H₂(3% H₂O)	1.0	0.92	[31]
Ni-BZCY/BZCY/Ni-BZCY	450, 60% H₂(maximum testing temperature of 450 ℃)	1.0	0.53	[32]
Ni-BZCYYb/BZCYYb/Ni-BZCYYb	600, 50% H₂-N₂	0.8	1.78	[30]
Ni-BZCY/BZCY/Ni-BZCY	600, H₂(3% H₂O)	0.8	1.87	This work
Ni-BZCY/BZCY/Ni-BZCY	600, NH₃	0.8	1.56	This work

图5 PCMR在(a) H2、(b) NH3气氛下的EIS谱图

Fig. 5 EIS plots under (a) H2 and (b) NH3 environments for PCMR

表2 PCMR在H2、NH3气氛下的阻抗(Ω·cm2)

Table 2 Resistances under H2 and NH3 environments for PCMR (Ω·cm2)

Temperature/℃	H₂			NH₃
Temperature/℃	R_total	R_Ω	R_p	R_total	R_Ω	R_p
600	0.48	0.37	0.11	0.67	0.44	0.23
500	0.72	0.47	0.25	1.28	0.61	0.67
400	1.98	0.81	1.17	3.31	1.09	2.22
300	9.23	1.54	7.69	17.31	2.80	14.51

图6 PCMR在(a) H2和(b) NH3气氛下温度与Rp、RΩ以及Rtotal的阿伦尼乌斯曲线

Fig. 6 Arrhenius curves of temperature vs. Rp, RΩ and Rtotal of PCMR under (a) H2 and (b) NH3 environments

图7 PCMR在400 ℃、0.6 V不同气氛下的稳定性测试

Fig. 7 Stability testing in different gas environments at 400 ℃ and 0.6 V for PCMR

图8 PCMR在NH3气氛下稳定性测试前后的阻抗变化

Fig. 8 Variation in impedance before and after stability testing under NH3 environment for PCMR

图9 PCMR在NH3气氛下稳定性测试前后的DRT曲线

Fig. 9 DRT curves before and after stability testing under NH3 environment for PCMR

图10 Ni-BZCY粉体与在0.8 V电压下工作的PCMR的NH3转化效率

Fig. 10 NH3 conversion efficiency of Ni-BZCY powder and PCMR operated at 0.8 V

参考文献 12

[13]	LI Y F, ZHANG W S, REN J, et al. Ammonia decomposition for carbon-free hydrogen production over Ni/Al-Ce catalysts: synergistic effect between Al and Ce. Fuel, 2024, 358: 130176. DOI URL
[14]	BUONOMENNA M G. Proton-conducting ceramic membranes for the production of hydrogen via decarbonized heat: overview and prospects. Hydrogen, 2023, 4(4): 807. DOI URL
[15]	WANG H N, WANG X B, MENG B, et al. Perovskite-based mixed protonic-electronic conducting membranes for hydrogen separation: recent status and advances. Journal of Industrial and Engineering Chemistry, 2018, 60: 297. DOI URL
[16]	LI N N, ZARKADOULAS A, KYRIAKOU V. Opportunities and challenges for direct electrification of chemical processes with protonic ceramic membrane reactors. Progress in Energy, 2024, 6(4): 043007. DOI
[17]	LI F R, DUAN G X, WANG Z G, et al. Highly efficient recovery of hydrogen from dilute H₂-streams using BaCe_0.7Zr_0.1Y_0.2O_3-_δ/ Ni-BaCe_0.7Zr_0.1Y_0.2O_3-_δ dual-layer hollow fiber membrane. Separation and Purification Technology, 2022, 287: 120602. DOI URL
[18]	WANG Q J, LUO T, TONG Y C, et al. Large-area protonic ceramic cells for hydrogen purification. Separation and Purification Technology, 2022, 295: 121301. DOI URL
[19]	TONG Y C, WANG Y, CUI C S, et al. Preparation and characterization of symmetrical protonic ceramic fuel cells as electrochemical hydrogen pumps. Journal of Power Sources, 2020, 457: 228036. DOI URL
[20]	LIANG M Z, SONG Y F, XIONG B C, et al. In situ exsolved CoFeRu alloy decorated perovskite as an anode catalyst layer for high-performance direct-ammonia protonic ceramic fuel cells. Advanced Functional Materials, 2024, 34(48): 2408756. DOI URL
[21]	曹希文, 罗凌虹, 曾小军, 等. 固体氧化物燃料电池Ni基阳极抗积碳的研究进展. 陶瓷学报, 2024, 45(1): 72.
[22]	蓝海洋, 陈星余, 张博, 等. 固体氧化物直接氨燃料电池阳极材料的研究进展. 陶瓷学报, 2023, 44(6): 1078.
[23]	PENG C X, ZHAO B X, MENG X, et al. Effect of NiO addition on the sintering and electrochemical properties of BaCe_0.55Zr_0.35Y_0.1O_3-_δ proton-conducting ceramic electrolyte. Membranes, 2024, 14(3): 61. DOI URL
[24]	DANILOV N A, STAROSTINA I A, STAROSTIN G N, et al. Fundamental understanding and applications of protonic Y- and Yb-coped Ba(Ce, Zr)O₃ perovskites: state-of-the-art and perspectives. Advanced Energy Materials, 2023, 13(47): 2302175. DOI URL
[25]	YANG Y M, LU J C, ZHANG X Y, et al. Symmetry-induced modulation of proton conductivity in Y-doped Ba(Zr, Ce)O₃: insights from Raman spectroscopy. Journal of Materials Chemistry A, 2024, 12(21): 12599. DOI URL
[26]	ZHANG J H, LU X T, MAO H Y, et al. Effect of sintering additives on sintering behavior and conductivity of BaZr_0.1Ce_0.7Y_0.2O_3-_δ electrolytes. Journal of Inorganic Materials, 2025, 40(1): 84. DOI URL
[27]	ZHU D C, LIU Z Q, ZHU C J, et al. Construction of a novel BaZr_0.1Ce_0.7Y_0.2O_3-_δ-SnO₂ heterojunction composite electrolyte for advanced semiconductor ion fuel cells operating at lower temperature down to 350 ℃. Chemical Engineering Journal, 2025, 505: 159368. DOI URL
[28]	HOU J, GONG J Y, BI L. Advancing cathodic electrocatalysis via an in situ generated dense active interlayer based on CuO₅ pyramid-structured Sm₂Ba_1.33Ce_0.67Cu₃O₉. Journal of Materials Chemistry A, 2022, 10(30): 15949. DOI URL
[29]	HOU J, DONG K, MIAO L N, et al. Rationally structuring proton-conducting solid oxide fuel cell anode with Ni metal catalyst and porous skeleton. Ceramics International, 2020, 46(15): 24038. DOI URL
[30]	ZHANG G J, CHEN T, GUO Z Z, et al. A 10 × 10 cm² protonic ceramic electrochemical hydrogen pump for efficient and durable hydrogen purification. Chemical Engineering Journal, 2024, 495: 153521. DOI URL
[31]	CHOI J, SHIN M, KIM B, et al. High-performance ceramic composite electrodes for electrochemical hydrogen pump using protonic ceramics. International Journal of Hydrogen Energy, 2017, 42(18): 13092. DOI URL
[32]	MUSHTAQ U, WELZEL S, SHARMA R K, et al. Development of electrode-supported proton conducting solid oxide cells and their evaluation as electrochemical hydrogen pumps. ACS Applied Materials & Interfaces, 2022, 14(34): 38938.
[1]	SADEQ A M, HOMOD R Z, HUSSEIN A K, et al. Hydrogen energy systems: technologies, trends, and future prospects. Science of the Total Environment, 2024, 939: 173622. DOI URL
[2]	YUE M L, LAMBERT H, PAHON E, et al. Hydrogen energy systems: a critical review of technologies, applications, trends and challenges. Renewable and Sustainable Energy Reviews, 2021, 146: 111180. DOI URL
[3]	AGYEKUM E B, ODOI-YORKE F, ABBEY A A, et al. A review of the trends, evolution, and future research prospects of hydrogen fuel cells-a focus on vehicles. International Journal of Hydrogen Energy, 2024, 72: 918. DOI URL
[4]	LI N, ZHANG C, LI D, et al. Review of reactor systems for hydrogen production via ammonia decomposition. Chemical Engineering Journal, 2024, 495: 153125. DOI URL
[5]	ZAINAL N A, ZULKIFLI N W M, GULZAR M, et al. A review on the chemistry, production, and technological potential of bio-based lubricants. Renewable and Sustainable Energy Reviews, 2018, 82: 80. DOI URL
[6]	LIANG D T, FENG C, XU L, et al. Promotion effects of different methods in CO_x-free hydrogen production from ammonia decomposition. Catalysis Science & Technology, 2023, 13(12): 3614.
[7]	ZHANG X S, LIU Y T, WANG Y Y, et al. Self-assembled platinum-iridium alloy aerogels and their efficient electrocatalytic ammonia oxidation performance. Journal of Inorganic Materials, 2023, 38(5): 511. DOI
[8]	MUKHERJEE S, DEVAGUPTAPU S V, SVIRIPA A, et al. Low-temperature ammonia decomposition catalysts for hydrogen generation. Applied Catalysis B: Environmental, 2018, 226: 162. DOI URL
[9]	LIAN M L, SU J X, HUANG H Y, et al. Supported Ni catalysts from Ni-Mg-Al hydrotalcite-like compounds: preparation and catalytic performance for ammonia decomposition. Journal of Inorganic Materials, 2025, 40(1): 53. DOI URL
[10]	SUN S C, JIANG Q Q, ZHAO D Y, et al. Ammonia as hydrogen carrier: advances in ammonia decomposition catalysts for promising hydrogen production. Renewable and Sustainable Energy Reviews, 2022, 169: 112918. DOI URL
[33]	YUN J, XIONG G, KIM S, et al. Understanding direct-ammonia protonic ceramic fuel cells: high-performance in the absence of precious metal catalysts. ACS Energy Letters, 2024, 9(11): 5520. DOI URL
[34]	ZHOU Y C, LIU E Z, CHEN Y, et al. An active and robust air electrode for reversible protonic ceramic electrochemical cells. ACS Energy Letters, 2021, 6(4): 1511.
[11]	CECHETTO V, DI FELICE L, MARTINEZ G R, et al. Ultra-pure hydrogen production via ammonia decomposition in a catalytic membrane reactor. International Journal of Hydrogen Energy, 2022, 47(49): 21220. DOI URL
[12]	SHEN M H, AI F J, MA H L, et al. Progress and prospects of reversible solid oxide fuel cell materials. iScience, 2021, 24(12): 103464. DOI URL

质子陶瓷膜反应器的制备及低温氨分解性能研究

Proton Ceramic Membrane Reactor: Preparation and Low-temperature Ammonia Decomposition Performance

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 12

相关文章 15

编辑推荐

Metrics

本文评价

[1]	闫共芹, 王晨, 蓝春波, 洪雨昕, 叶维超, 付向辉. Al掺杂P2型Na_0.8Ni_0.33Mn_0.67-_xAl_xO₂钠离子电池正极材料的制备与电化学性能[J]. 无机材料学报, 2025, 40(9): 1005-1012.
[2]	李汶金, 娄程广, 张帅, 苏兴华. 金属Cu和5YSZ陶瓷的“闪连”研究[J]. 无机材料学报, 2025, 40(9): 957-963.
[3]	杨燕, 张发强, 马名生, 王墉哲, 欧阳琪, 刘志甫. 基于CuO-TiO₂-Nb₂O₅复合氧化物烧结助剂的ZnAl₂O₄陶瓷低温烧结研究[J]. 无机材料学报, 2025, 40(6): 711-718.
[4]	姜昆, 李乐天, 郑木鹏, 胡永明, 潘勤学, 吴超峰, 王轲. PZT陶瓷的低温烧结研究进展[J]. 无机材料学报, 2025, 40(6): 627-638.
[5]	尹长志, 成名飞, 雷微程, 蔡弋炀, 宋小强, 付明, 吕文中, 雷文. Ga³⁺掺杂对SrAl₂Si₂O₈陶瓷晶体结构及微波介电性能的影响[J]. 无机材料学报, 2025, 40(6): 704-710.
[6]	陈莉波, 盛盈, 伍明, 宋季岭, 蹇建, 宋二红. Na和O元素共掺杂氮化碳高效光催化制氢[J]. 无机材料学报, 2025, 40(5): 552-562.
[7]	万俊池, 杜路路, 张永上, 李琳, 刘建德, 张林森. Na₄Fe_xP₄O₁₂₊_x/C钠离子电池正极材料的结构演变及其电化学性能[J]. 无机材料学报, 2025, 40(5): 497-503.
[8]	薛柯, 蔡长焜, 谢满意, 李舒婷, 安胜利. 固体氧化物燃料电池Pr₁₊_xBa_1-_xFe₂O₅₊_δ阴极材料的制备及电化学性能研究[J]. 无机材料学报, 2025, 40(4): 363-371.
[9]	张宇婷, 李晓斌, 刘尊义, 李宁, 赵鹬. 复合蛋黄壳型NiCo₂V₂O₈@TiO₂@NC材料用作锂离子电池负极研究[J]. 无机材料学报, 2025, 40(11): 1221-1228.
[10]	连敏丽, 苏佳欣, 黄鸿杨, 嵇玉寅, 邓海帆, 张彤, 陈崇启, 李达林. Ni-Mg-Al类水滑石衍生镍基催化剂的制备及其氨分解性能[J]. 无机材料学报, 2025, 40(1): 53-60.
[11]	陈正鹏, 金芳军, 李明飞, 董江波, 许仁辞, 徐韩昭, 熊凯, 饶睦敏, 陈创庭, 李晓伟, 凌意瀚. 双钙钛矿Sr₂CoFeO₅₊_δ阴极材料的制备及其中温固体氧化物燃料电池性能研究[J]. 无机材料学报, 2024, 39(3): 337-344.
[12]	江强, 施立志, 陈政燃, 周志勇, 梁瑞虹. 高于居里温度极化的硬性PZT压电陶瓷的制备及叠层驱动器性能研究[J]. 无机材料学报, 2024, 39(10): 1091-1099.
[13]	彭萍, 谭礼涛. CuO掺杂(Ba,Ca)(Ti,Sn)O₃陶瓷的结构与压电性能[J]. 无机材料学报, 2024, 39(10): 1100-1106.
[14]	柯鑫, 谢炳卿, 王忠, 张敬国, 王建伟, 李占荣, 贺会军, 汪礼敏. 第三代半导体互连材料与低温烧结纳米铜材的研究进展[J]. 无机材料学报, 2024, 39(1): 17-31.
[15]	罗淑文, 马名生, 刘峰, 刘志甫. Ca-B-Si体系LTCC材料腐蚀行为及腐蚀机理[J]. 无机材料学报, 2023, 38(5): 553-560.