Ni、Cu共浸渍的LSCM-GDC复合阴极性能研究

硅酸盐通报 ›› 2022, Vol. 41 ›› Issue (7): 2458-2466.

Ni、Cu共浸渍的LSCM-GDC复合阴极性能研究

刘欣楠, 肖彦之, 黄美琪, 蒋菡, 孔江榕, 周涛

中南大学化学化工学院,湖南省锰资源高效清洁利用重点实验室,长沙 410083

收稿日期:2022-03-17 修回日期:2022-05-07 出版日期:2022-07-15 发布日期:2022-08-01
通讯作者: 孔江榕,博士,副教授。E-mail:kongjr@csu.edu.cn
作者简介:刘欣楠(1997—),男,硕士研究生。主要从事固体氧化物电解池阴极材料研究。E-mail:876025070@qq.com
基金资助:
国家自然科学基金(21506259);湖南省科技计划项目(2016TP1007);湖南省教育厅优秀青年科研项目(19B038)

Properties of LSCM-GDC Composite Cathode Impregnatedwith Ni and Cu

LIU Xinnan, XIAO Yanzhi, HUANG Meiqi, JIANG Han, KONG Jiangrong, ZHOU Tao

Hunan Key Laboratory of Efficient and Clean Utilization of Manganese Resources, School of Chemistry and Chemical Engineering,Central South University, Changsha 410083, China

Received:2022-03-17 Revised:2022-05-07 Online:2022-07-15 Published:2022-08-01

摘要/Abstract

摘要： 固体氧化物电解池可以清洁、高效地将电能和热能转化为化学能,在新能源领域具有广阔的应用前景。La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ(LSCM)具有较好的高温稳定性,但离子电导率相对较低,在电解过程中电催化性能不足。本文将LSCM与具有较高离子导电性的Ce_0.8Gd_0.2O_2-δ(GDC)复配构造复合电极,并以共负载的形式在复合电极中浸渍纳米Ni、Cu金属催化剂提高电极的水蒸气吸附和转化能力,Ni、Cu共负载能够同时保留单一Ni或Cu负载对电极电解机制的改善。结果表明,Ni、Cu共负载相比于单一Ni或Cu负载电极在还原性气氛下具有更高的电化学性能,在还原性气氛和800 ℃工作温度下,镍铜质量比2∶8的负载电极在-0.1 V过电位下的电流密度可达到2.36 A·cm^-2,极化阻抗为0.92 Ω·cm²。

关键词: 固体氧化物电解池, 阴极材料, LSCM, LSCM-GDC复合电极, 离子电导率, 电化学性能, 高温水蒸气电解, 浸渍法

Abstract: Solid oxide electrolysis cell can cleanly and efficiently convert electric and thermal energy into chemical energy, which has broad application prospects in the new energy field. La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ (LSCM) has high temperature stability and is one of hotspots in the research of solid oxide electrolysis cell cathode materials. However, the relatively low ionic conductivity of LSCM results in insufficient electrocatalytic performance during electrolysis. In this paper, Ce_0.8Gd_0.2O_2-δ (GDC) with high ionic conductivity was composited on the basis of LSCM to construct a composite electrode, and Ni and Cu were impregnated into the composite electrode as metal catalysts to improve the water vapor adsorption and conversion capacity of the electrode. Ni, Cu co-loaded can keep single Ni or Cu loaded at the same time to improve the electrode electrolysis mechanism. The results show that compared with single Ni or Cu impregnation cathodes, the electrode with Ni and Cu co-impregnation has higher electrochemical performance under reducing atmosphere. The electrochemical performance of the electrode under reducing atmosphere at 800 ℃ is better than that under oxidizing atmosphere. The electrode with the nickel-copper mass ratio of 2∶8 has the best performance among the Ni, Cu-loaded cathodes, which current density reaches 2.36 A·cm^-2 at -0.1 V overpotential, and the polarization resistance is 0.92 Ω·cm².

Key words: solid oxide electrolysis cell, cathode material, LSCM, LSCM-GDC composite electrode, ionic conductivity, electrochemical performance, high temperature steam electrolysis, impregnation method

中图分类号:

TQ151

刘欣楠, 肖彦之, 黄美琪, 蒋菡, 孔江榕, 周涛. Ni、Cu共浸渍的LSCM-GDC复合阴极性能研究[J]. 硅酸盐通报, 2022, 41(7): 2458-2466.

LIU Xinnan, XIAO Yanzhi, HUANG Meiqi, JIANG Han, KONG Jiangrong, ZHOU Tao. Properties of LSCM-GDC Composite Cathode Impregnatedwith Ni and Cu[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(7): 2458-2466.

参考文献

[1] ZHENG Y F, ZHOU J, ZHANG L, et al. High-temperature electrolysis of simulated flue gas in solid oxide electrolysis cells[J]. Electrochimica Acta, 2018, 280: 206-215.
[2] MOÇOTEGUY P, BRISSE A. A review and comprehensive analysis of degradation mechanisms of solid oxide electrolysis cells[J]. International Journal of Hydrogen Energy, 2013, 38(36): 15887-15902.
[3] HANSEN J B. Solid oxide electrolysis: a key enabling technology for sustainable energy scenarios[J]. Faraday Discussions, 2015, 182: 9-48.
[4] RAZMJOO A, KAIGUTHA L G, VAZIRI RAD M A, et al. A Technical analysis investigating energy sustainability utilizing reliable renewable energy sources to reduce CO₂ emissions in a high potential area[J]. Renewable Energy, 2021, 164: 46-57.
[5] KODIROV D, MURATOV K, TURSUNOV O, et al. The use of renewable energy sources in integrated energy supply systems for agriculture[J]. IOP Conference Series: Earth and Environmental Science, 2020, 614(1): 012007.
[6] YANG X D, IRVINE J T S. (La_0.75Sr_0.25)_0.95Mn_0.5Cr_0.5O₃ as the cathode of solid oxide electrolysis cells for high temperature hydrogen production from steam[J]. Journal of Materials Chemistry, 2008, 18(20): 2349.
[7] XING R M, WANG Y R, LIU S H, et al. Preparation and characterization of La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ-yttria stabilized zirconia cathode supported solid oxide electrolysis cells for hydrogen generation[J]. Journal of Power Sources, 2012, 208: 276-281.
[8] BUTTLER A, SPLIETHOFF H. Current status of water electrolysis for energy storage, grid balancing and sector coupling via power-to-gas and power-to-liquids: a review[J]. Renewable and Sustainable Energy Reviews, 2018, 82: 2440-2454.
[9] UDAGAWA J, AGUIAR P, BRANDON N P. Hydrogen production through steam electrolysis: model-based steady state performance of a cathode-supported intermediate temperature solid oxide electrolysis cell[J]. Journal of Power Sources, 2007, 166(1): 127-136.
[10] XU S S, CHEN S G, LI M, et al. Composite cathode based on Fe-loaded LSCM for steam electrolysis in an oxide-ion-conducting solid oxide electrolyser[J]. Journal of Power Sources, 2013, 239: 332-340.
[11] STOOTS C M, O’BRIEN J E, CONDIE K G, et al. High-temperature electrolysis for large-scale hydrogen production from nuclear energy: experimental investigations[J]. International Journal of Hydrogen Energy, 2010, 35(10): 4861-4870.
[12] 张文强,于波.高温固体氧化物电解制氢技术发展现状与展望[J].电化学,2020,26(2):212-229.
ZHANG W Q, YU B. Development status and prospects of hydrogen production by high temperature solid oxide electrolysis[J]. Journal of Electrochemistry, 2020, 26(2): 212-229 (in Chinese).
[13] WANG Y F, LEUNG D Y C, XUAN J, et al. A review on unitized regenerative fuel cell technologies, part B: unitized regenerative alkaline fuel cell, solid oxide fuel cell, and microfluidic fuel cell[J]. Renewable and Sustainable Energy Reviews, 2017, 75: 775-795.
[14] PENNER S, GÖTSCH T, KLÖTZER B. Increasing complexity approach to the fundamental surface and interface chemistry on SOFC anode materials[J]. Accounts of Chemical Research, 2020, 53(9): 1811-1821.
[15] WOO S H, BAEK S W, PARK D S, et al. Microstructural and electrochemical properties of impregnated La_0.4Sr_0.6Ti_0.8Mn_0.2O_3±d into a partially removed Ni SOFC anode substrate[J]. Journal of Alloys and Compounds, 2021, 854: 157250.
[16] SREEDHAR I, AGARWAL B, GOYAL P, et al. Recent advances in material and performance aspects of solid oxide fuel cells[J]. Journal of Electroanalytical Chemistry, 2019, 848: 113315.
[17] GÓMEZ S Y, HOTZA D. Current developments in reversible solid oxide fuel cells[J]. Renewable and Sustainable Energy Reviews, 2016, 61: 155-174.
[18] LI Y X, GAN Y, WANG Y, et al. Composite cathode based on Ni-loaded La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ for direct steam electrolysis in an oxide-ion-conducting solid oxide electrolyzer[J]. International Journal of Hydrogen Energy, 2013, 38(25): 10196-10207.
[19] JIN C, YANG C H, ZHAO F, et al. La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ as hydrogen electrode for solid oxide electrolysis cells[J]. International Journal of Hydrogen Energy, 2011, 36(5): 3340-3346.
[20] DELEEBEECK L, FOURNIER J L, BIRSS V. Comparison of Sr-doped and Sr-free La_1-xSr_xMn_0.5Cr_0.5O_3±δ SOFC anodes[J]. Solid State Ionics, 2010, 181(25/26): 1229-1237.
[21] 谢益林,孔江榕,潘迪,等.固体氧化物电解池La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ-Ce_0.8Gd_0.2O_2-δ梯度型复合阴极制备及性能研究[J].稀有金属,2021,45(11):1343-1351.
XIE Y L, KONG J R, PAN D, et al. Preparation and performance study of La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ-Ce_0.8Gd_0.2O_2-δ gradient composite cathode for solid oxide electrolysis cell[J]. Chinese Journal of Rare Metals, 2021, 45(11): 1343-1351 (in Chinese).
[22] ZHANG X M, SONG Y F, GUAN F, et al. Enhancing electrocatalytic CO₂ reduction in solid oxide electrolysis cell with Ce_0.9Mn_0.1O_2-δ nanoparticles-modified LSCM-GDC cathode[J]. Journal of Catalysis, 2018, 359: 8-16.
[23] XING R M, WANG Y R, ZHU Y Q, et al. Co-electrolysis of steam and CO₂ in a solid oxide electrolysis cell with La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ-Cu ceramic composite electrode[J]. Journal of Power Sources, 2015, 274: 260-264.