La/Ni共掺杂SrTi0.35Fe0.65O3-δ对称电极用于SOEC共电解H2O/CO2研究

doi:10.3969/j.issn.2097-0706.2022.08.004

综合智慧能源 ›› 2022, Vol. 44 ›› Issue (8): 43-49.doi: 10.3969/j.issn.2097-0706.2022.08.004

La/Ni共掺杂SrTi_0.35Fe_0.65O_3-_δ对称电极用于SOEC共电解H₂O/CO₂研究

韩倩雯¹(), 张琨¹(), 陈晓阳¹^,²(), 朱腾龙¹^,^*()

1.南京理工大学化学与化工学院,南京 210094
2.哈尔滨工业大学（深圳）材料科学与工程学院,广东深圳 518055

收稿日期:2022-07-17 修回日期:2022-08-09 出版日期:2022-08-25 发布日期:2022-09-15
通讯作者: 朱腾龙
作者简介:韩倩雯（1998）,女,在读硕士研究生,从事固体氧化物燃料电池方面的研究, hanqw1998@163.com;
张琨（1999）,男,在读硕士研究生,从事固体氧化物燃料电池方面的研究, 2498249631@qq.com;
陈晓阳（1998）,男,在读硕士研究生,从事电催化、锌离子电池的研究, 21S155060@stu.hit.edu.cn。
基金资助:
国家重点研发计划项目(2018YFB1502203);中央高校基本科研业务费专项资金资助项目(30920041108)

Study on La/Ni co-doped SrTi_0.35Fe_0.65O_3-_δ symmetric electrode for H₂O/CO₂ co-electrolysis in SOECs

HAN Qianwen¹(), ZHANG Kun¹(), CHEN Xiaoyang¹^,²(), ZHU Tenglong¹^,^*()

1. School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
2. School of Materials Science and Engineering, Harbin Institute of Technology（Shenzhen）, Shenzhen 518055, China

Received:2022-07-17 Revised:2022-08-09 Online:2022-08-25 Published:2022-09-15
Contact: ZHU Tenglong

摘要/Abstract

摘要：

通过固体氧化物电解池（SOEC）电解水蒸气制氢及共电解H₂O/CO₂生产合成气是拓展可再生能源应用、促进化学工业绿色低碳转型的重要技术路线。面向SOEC对高性能、稳定电极的需求,采用La/Ni共掺杂SrTi_0.35Fe_0.65O_3-_δ的电极策略,设计并制备了La_0.1Sr_0.85Ti_0.35Fe_0.6Ni_0.05O₃（LSTFN）,并将其同时作为SOEC的氢电极和氧电极。通过扫描电子显微镜（SEM）、能量分散光谱（EDS）和X射线衍射（XRD）等方法,对LSTFN电极结构组成及微观形貌演化进行研究,并考察了单电池共电解H₂O/CO₂性能和可逆运行稳定性。结果表明,在还原气氛中,LSTFN氢电极表面原位析出了纳米Ni-Fe合金颗粒,并在含水和含碳复杂气氛中稳定存在;在800 ℃,10% H₂保护气和1.8 V的条件下（H₂/H₂O/CO₂=10∶45∶45）,LSTFN的共电解电流达到了1.8 A/cm²,并在发电/电解可逆条件下稳定运行,表现出良好的应用前景。

关键词: 固体氧化物电解池, CO₂/H₂O共电解, 对称电极, SrTi_0.35Fe_0.65O_3-_δ, 绿色低碳转型, 制氢, 钙钛矿, 可再生能源

Abstract:

Hydrogen production from water steam electrolysis powered by solid oxide electrolysis cells （SOECs） and syngas production by co-electrolysis of H₂O/CO₂ are important routes to promote the application of renewable energy and development of green and low-carbon chemical industry. To meet the demands for high performance and stable operation of SOECs,La/Ni co-doped SrTi_0.35Fe_0.65O_3-_δ strategy was adopted,and La_0.1Sr_0.85Ti_0.35Fe_0.6Ni_0.05O₃ （LSTFN） was designed and prepared as both hydrogen and oxygen electrodes for SOECs. The structural composition and micromorphological evolution of LSTFN electrode were investigated by scanning electron microscopy（SEM）, energy dispersive spectroscopy （EDS） and X-ray diffraction （XRD）. The H₂O/CO₂ co-electrolysis performance and reversible operation stability were examined. The results show that, Ni-Fe alloy nanoparticles in-situ precipitated on LSTFN hydrogen electrode surface are stable in complex steam and carbon-containing atmospheres. The LSTFN co-electrolysis current reaches 1.8 A/cm² in 800 ℃,1.8 V and 10% H₂ protective atmosphere（H₂/H₂O/CO₂=10∶45∶45）. LSTFN symmetric cell performs stably in reversible operations between power generation and co-electrolysis, showing good application prospects.

Key words: solid oxide electrolysis cell, CO₂/H₂O co-electrolysis, symmetrical electrode, SrTi_0.35Fe_0.65O_3-_δ, green and low-carbon development, hydrogen production, perovskite, renewable energy

中图分类号:

TK91:TM911

韩倩雯, 张琨, 陈晓阳, 朱腾龙. La/Ni共掺杂SrTi_0.35Fe_0.65O_3-_δ对称电极用于SOEC共电解H₂O/CO₂研究[J]. 综合智慧能源, 2022, 44(8): 43-49.

HAN Qianwen, ZHANG Kun, CHEN Xiaoyang, ZHU Tenglong. Study on La/Ni co-doped SrTi_0.35Fe_0.65O_3-_δ symmetric electrode for H₂O/CO₂ co-electrolysis in SOECs[J]. Integrated Intelligent Energy, 2022, 44(8): 43-49.

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参考文献 30

[1]	SONG Y, ZHANG X, XIE K, et al. High-temperature CO₂ electrolysis in solid oxide electrolysis cells: Developments, challenges, and prospects[J]. Advanced Materials, 2019, 31(50): 1902033. doi: 10.1002/adma.201902033
[2]	MILLER H A, LAVACCHI A, VIZZA F. Storage of renewable energy in fuels and chemicals through electrochemical reforming of bioalcohols[J]. Current Opinion in Electrochemistry, 2020, 21: 140-145. doi: 10.1016/j.coelec.2020.02.001
[3]	张一民, 康建立, 赵乃勤. 过渡金属基电解水催化剂的发展现状及展望[J]. 综合智慧能源, 2022, 44(5): 15-29. doi: 10.3969/j.issn.2097-0706.2022.05.002
	ZHANG Yimin, KANG Jianli, ZHAO Naiqin. Development and perspectives of the transition metal-based catalysts for water splitting[J]. Integrated Intelligent Energy, 2022, 44(5):15-29. doi: 10.3969/j.issn.2097-0706.2022.05.002
[4]	吴林芮, 刘璐, 孟瑜, 等. 锌-空气电池阴极碳基催化剂材料研究进展[J]. 综合智慧能源, 2022, 44(4): 65-70. doi: 10.3969/j.issn.2097-0706.2022.04.008
	WU Linrui, LIU Lu, MENG Yu, et al. Research progress of carbon-based catalyst materials for cathodes of Zn-air batteries[J]. Integrated Intelligent Energy, 2022, 44(4): 65-70. doi: 10.3969/j.issn.2097-0706.2022.04.008
[5]	GOEPPERT A, CZAUN M, JONES J-P, et al. Recycling of carbon dioxide to methanol and derived products—Closing the loop[J]. Chemical Society Reviews, 2014, 43(23): 7995-8048. doi: 10.1039/C4CS00122B
[6]	HARTVIGSEN J, ELANGOVAN S, FROST L, et al. Carbon dioxide recycling by high temperature co-electrolysis and hydrocarbon synthesis[J]. Ecs Transactions, 2008, 12(1):625. doi: 10.1149/1.2921588
[7]	STOOTS C, O'BRIEN J, HARTVIGSEN J. Results of recent high temperature coelectrolysis studies at the Idaho National Laboratory[J]. International Journal of Hydrogen Energy, 2009, 34(9): 4208-4215. doi: 10.1016/j.ijhydene.2008.08.029
[8]	范慧. 可逆燃料电池——电解池氧电极复合改性研究[D]. 北京: 中国矿业大学, 2014.
[9]	BIAN L, DUAN C, WANG L, et al. An all-oxide electrolysis cells for syngas production with tunable H₂/CO yield via co-electrolysis of H₂O and CO₂[J]. Journal of Power Sources, 2021, 482: 228887. doi: 10.1016/j.jpowsour.2020.228887
[10]	KAMKENG A D, WANG M. Long-term performance prediction of solid oxide electrolysis cell (SOEC) for CO₂/H₂O co-electrolysis considering structural degradation through modelling and simulation[J]. Chemical Engineering Journal, 2022, 429: 132158. doi: 10.1016/j.cej.2021.132158
[11]	KAZEMPOOR P, ASADI J, BRAUN R. Validation challenges in solid oxide electrolysis cell modeling fueled by low steam/CO₂ ratio[J]. International Journal of Hydrogen Energy, 2022, 47(36): 15952-15959. doi: 10.1016/j.ijhydene.2022.03.115
[12]	MENON V, FU Q, JANARDHANAN V M, et al. A model-based understanding of solid-oxide electrolysis cells (SOECs) for syngas production by H₂O/CO₂ co-electrolysis[J]. Journal of Power Sources, 2015, 274: 768-781. doi: 10.1016/j.jpowsour.2014.09.158
[13]	NI M. An electrochemical model for syngas production by co-electrolysis of H₂O and CO₂[J]. Journal of Power Sources, 2012, 202: 209-216. doi: 10.1016/j.jpowsour.2011.11.080
[14]	LI S, LI Y, GAN Y, et al. Electrolysis of H₂O and CO₂ in an oxygen-ion conducting solid oxide electrolyzer with a La_{0. 2}Sr_{0. 8}TiO₃₊_δ composite cathode[J]. Journal of Power Sources, 2012, 218: 244-249. doi: 10.1016/j.jpowsour.2012.06.046
[15]	ZHAN Z, KOBSIRIPHAT W, WILSON J R, et al. Syngas production by coelectrolysis of CO₂/H₂O:The basis for a renewable energy cycle[J]. Energy & Fuels, 2009, 23(6): 3089-3096. doi: 10.1021/ef900111f
[16]	ZHANG L, ZHU X, CAO Z, et al. Pr and Ti co-doped strontium ferrite as a novel hydrogen electrode for solid oxide electrolysis cell[J]. Electrochimica Acta, 2017, 232: 542-549. doi: 10.1016/j.electacta.2017.02.168
[17]	SHU L, SUNARSO J, HASHIM S S, et al. Advanced perovskite anodes for solid oxide fuel cells: A review[J]. International Journal of Hydrogen Energy, 2019, 44(59): 31275-31304. doi: 10.1016/j.ijhydene.2019.09.220
[18]	IRVINE J T, NEAGU D, VERBRAEKEN M C, et al. Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers[J]. Nature Energy, 2016, 1(1): 1-13.
[19]	SUN Y, LI J, ZENG Y, et al. A-site deficient perovskite: The parent for in situ exsolution of highly active, regenerable nano-particles as SOFC anodes[J]. Journal of Materials Chemistry A, 2015, 3(20): 11048-11056. doi: 10.1039/C5TA01733E
[20]	ZHU T, TROIANI H E, MOGNI L V, et al. Ni-substituted Sr(Ti, Fe)O₃ SOFC anodes: Achieving high performance via metal alloy nanoparticle exsolution[J]. Joule, 2018, 2(3): 478-496. doi: 10.1016/j.joule.2018.02.006
[21]	倪维婕, 朱腾龙, 陈晓阳, 等. Co/Ni掺杂SrTi_0.3Fe_0.7O_3-_δ钙钛矿电极材料制备及性能[J]. 硅酸盐学报, 2019, 47(3): 313-319.
	NI Weijie, ZHU Tenglong, CHEN Xiaoyang, et al. Fabrication and characterization of Co/Ni substituted SrTi_0.3Fe_0.7O_3-_δ perovskite electrode[J]. Journal of the Chinese Ceramic Society, 2019, 47(3): 313-319.
[22]	ZHANG L, LI Y, ZHANG B, et al. (La, Sr)(Ti, Fe)O_3-_δ perovskite with in-situ constructed FeNi₃ nanoparticles as fuel electrode for reversible solid oxide cell[J]. International Journal of Energy Research, 2021, 45(15): 21264-21273. doi: 10.1002/er.7177
[23]	LI Y, XIE K, CHEN S, et al. Efficient carbon dioxide electrolysis based on perovskite cathode enhanced with nickel nanocatalyst[J]. Electrochimica Acta, 2015, 153: 325-333. doi: 10.1016/j.electacta.2014.11.151
[24]	LV H, LIN L, ZHANG X, et al. In situ investigation of reversible exsolution/dissolution of CoFe alloy nanoparticles in a co-doped Sr₂Fe_{1. 5}Mo_{0. 5}O_6-_δ cathode for CO₂ electrolysis[J]. Advanced Materials, 2020, 32(6): 1906193. doi: 10.1002/adma.201906193
[25]	PARK S, KIM Y, HAN H, et al. In situ exsolved Co nanoparticles on Ruddlesden-Popper material as highly active catalyst for CO₂ electrolysis to CO[J]. Applied Catalysis B: Environmental, 2019, 248: 147-156. doi: 10.1016/j.apcatb.2019.02.013
[26]	LIANG J, HAN M. Different performance and mechanisms of CO₂ electrolysis with CO and H₂ as protective gases in solid oxide electrolysis cell[J]. International Journal of Hydrogen Energy, 2022.
[27]	TORRELL M, GARCÍA-RODRÍGUEZ S, MORATA A, et al. Co-electrolysis of steam and CO₂ in full-ceramic symmetrical SOECs: A strategy for avoiding the use of hydrogen as a safe gas[J]. Faraday Discussions, 2015, 182: 241-255. doi: 10.1039/C5FD00018A
[28]	WANG Y, LIU T, FANG S, et al. Syngas production on a symmetrical solid oxide H₂O/CO₂ co-electrolysis cell with Sr₂Fe_1.5Mo_0.5O₆-Sm_0.2Ce_0.8O_1.9 electrodes[J]. Journal of Power Sources, 2016, 305: 240-248. doi: 10.1016/j.jpowsour.2015.11.097
[29]	LI Q, ZHENG Y, SUN Y, et al. Understanding the occurrence of the individual CO₂ electrolysis during H₂O-CO₂ co-electrolysis in classic planar Ni-YSZ/YSZ/LSM-YSZ solid oxide cells[J]. Electrochimica Acta, 2019, 318: 440-448. doi: 10.1016/j.electacta.2019.06.108
[30]	ZHENG H, TIAN Y, ZHANG L, et al. La_0.8Sr_0.2Co_0.8Ni_0.2O_3-_δ impregnated oxygen electrode for H₂O/CO₂ co-electrolysis in solid oxide electrolysis cells[J]. Journal of Power Sources, 2018, 383: 93-101. doi: 10.1016/j.jpowsour.2018.02.041

La/Ni共掺杂SrTi_0.35Fe_0.65O_3-_δ对称电极用于SOEC共电解H₂O/CO₂研究

Study on La/Ni co-doped SrTi_0.35Fe_0.65O_3-_δ symmetric electrode for H₂O/CO₂ co-electrolysis in SOECs

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