LaxSr2-xFe1.5Ni0.1Mo0.4O6-δ对称电池电解CO2研究

doi:10.15541/jim20210206

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1323-1329.DOI: 10.15541/jim20210206

所属专题：【虚拟专辑】碳中和(2020~2021)；【虚拟专辑】钙钛矿材料(2020~2021)；【能源环境】钙钛矿；【能源环境】CO2绿色转换

La_xSr_2-_xFe_1.5Ni_0.1Mo_0.4O_6-_δ对称电池电解CO₂研究

王玥¹^,²(), 崔常松¹^,², 王士维¹^,², 占忠亮¹^,²^,³()

1.中国科学院上海硅酸盐研究所, 上海 200050
2.中国科学院大学, 北京 100049
3.中国科学技术大学化学与材料科学学院, 合肥 230026

收稿日期:2021-03-26 修回日期:2021-04-27 出版日期:2021-12-20 网络出版日期:2021-05-25
通讯作者: 占忠亮, 教授. E-mail: zzhan@ustc.edu.cn
作者简介:王玥(1994-), 女, 博士研究生. E-mail: wangyue@mail.sic.ac.cn

Symmetrical La³⁺-doped Sr₂Fe_1.5Ni_0.1Mo_0.4O_6-_δ Electrode Solid Oxide Fuel Cells for Pure CO₂ Electrolysis

WANG Yue¹^,²(), CUI Changsong¹^,², WANG Shiwei¹^,², ZHAN Zhongliang¹^,²^,³()

1. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. School of Chemistry and Materials Science, University of Science & Technology of China, Hefei 230026, China

Received:2021-03-26 Revised:2021-04-27 Published:2021-12-20 Online:2021-05-25
Contact: ZHAN Zhongliang, professor. E-mail: zzhan@ustc.edu.cn
About author:WANG Yue (1994-), female, PhD candidate. E-mail: wangyue@mail.sic.ac.cn
Supported by:
National Natural Science Foundation of China(51672298);State Grid Corporation of China(521205200011)

摘要/Abstract

摘要：

固态氧化物电解池(SOECs)因较高的能量转化效率在电化学还原CO₂, 实现“碳中和”社会方面备受关注。与非对称电池结构相比, 对称SOECs的空气极和燃料极是相同或相近的材料, 可以减少界面种类, 改善电极与电解质的热膨胀匹配性, 简化电池的制备工艺。本研究合成了钙钛矿氧化物La_xSr_2-_xFe_1.5Ni_0.1Mo_0.4O_6-_δ (L_xSFNM, x=0.1、0.2、0.3、0.4), 作为固体氧化物电解池的对称电极用于评估纯CO₂的电化学还原性能。掺入La³⁺可以有效提高反应催化活性, 其中L_0.3SFNM为电极的电解池表现出最高的电化学性能, 800 ℃下, 在空气中的极化电阻为0.07 Ω∙cm², 在50% CO-50% CO₂中的极化电阻为0.62 Ω∙cm²。单电池L_0.3SFNM@LSGM|LSGM|L_0.3SFNM@LSGM在800 ℃和1.5 V电压下的电解电流密度为1.17 A∙cm^-2, 在初始的50 h CO₂短期电解测试中表现出优异的稳定性, 是一种理想的对称电极材料。

关键词: 对称固体氧化物电解池, 钙钛矿结构, 电极材料

Abstract:

Electrochemical reduction of the greenhouse gas CO₂ in solid oxide electrolysis cells (SOECs) has attracted much attention due to their high energy conversion efficiency and great potential for carbon cycling. Compared with the asymmetrical configuration, symmetrical SOECs with the same material as anode and cathode, can greatly simplify the fabrication process and reduce the complication associated with varied interfaces. Perovskite oxides La_xSr_2-_xFe_1.5Ni_0.1Mo_0.4O_6-_δ (L_xSFNM, x=0.1, 0.2, 0.3 and 0.4) are prepared and evaluated as symmetrical electrodes in solid oxide electrolysis cells for electrochemical reduction of pure CO₂. The polarization resistances are 0.07 Ω∙cm² in air and 0.62 Ω∙cm² in 50% CO-50% CO₂ for L_0.3SFNM electrode at 800 ℃. An electrolysis current density of 1.17 A∙cm^-2 under 800 ℃ at 1.5 V is achieved for the symmetrical SOECs in pure CO₂. Furthermore, the symmetrical cell demonstrates excellent stability during the preliminary 50 h CO₂ electrolysis measurements.

Key words: symmetrical solid oxide electrolysis cells, perovskite, electrode materials

中图分类号:

TQ174

王玥, 崔常松, 王士维, 占忠亮. La_xSr_2-_xFe_1.5Ni_0.1Mo_0.4O_6-_δ对称电池电解CO₂研究[J]. 无机材料学报, 2021, 36(12): 1323-1329.

WANG Yue, CUI Changsong, WANG Shiwei, ZHAN Zhongliang. Symmetrical La³⁺-doped Sr₂Fe_1.5Ni_0.1Mo_0.4O_6-_δ Electrode Solid Oxide Fuel Cells for Pure CO₂ Electrolysis[J]. Journal of Inorganic Materials, 2021, 36(12): 1323-1329.

图/表 8

Fig. 1 (a) XRD patterns of LxSFNM (x=0-0.4) powder calcined at 1000 ℃ in air for 5 h and (b) corresponding magnified patterns within 2θ=31°-35°

Fig. 2 TGA analysis of LxSFNM in air

Fig. 3 Electricity conductivities of LxSFNM at 650-800 ℃ in (a) air and (b) 50% CO-50% CO2

Fig. 4 (a) Cross-sectional SEM image of the tri-layer symmetrical structure of “porous|dense|porous” LSGM and (b) high magnification view of symmetrical cell, and (c) high-magnification view of impregnated L0.3SFNM catalyst

Fig. 5 Nyquist plots of impedance data measured with LxSFNM at 800 ℃ in (a) air and (c) 50% CO-50% CO2; (b, d) DRT curves of impedance data shown in (a, c)

Fig. 6 Measured polarization resistances versus the temperature reciprocal in (a) air and (b) 50% CO-50% CO2

Fig. 7 (a) I-V curves and (b) impedance spectra measured at the 1.5 V of a single electrolyte-supported electrolysis cell with L0.3SFNM at different temperatures with inset in (b) showing corresponding enlarged spectrum of the cell with L0.3SFNM at 800 ℃, (c) current densities with varied LaxSFNM anodes at 1.5 V under different temperatures, and (d) short-term stability test of the symmetrical SOECs with L0.3SFNM electrode, operating under 800 ℃ at an applied voltage of 1.3 V

Table 1 Comparison of literature values of current densities achieved for pure CO2 electrolysis in electrolyte-supported cells at 1.5 V under 800 ℃

Electrode	Electrolyte	Performance/(A∙cm^-2)	Ref.
La_0.3Sr_0.7Fe_0.7Ti_0.3O₃	YSZ	0.52 (2V)	[27]
La_0.6Sr_0.4Fe_0.9Mn_0.1O_3-_δ-GDC	YSZ	1.107 (2V)	[25]
La_0.6Sr_0.4Fe_0.8Ni_0.2O_3-_δ-GDC	YSZ	1.03	[28]
La_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3-_δ	YSZ	0.442	[29]
La_0.6Ca_0.4Fe_0.8Ni_0.2O_3-_δ-GDC	YSZ	0.78	[13]
La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-_δ	YSZ	0.09	[30]
La_0.3Sr_0.7Cr_0.3Fe_0.7O_3-_δ	YSZ	0.32	[31]
(PrBa)_0.95(Fe_0.9Mo_0.1)₂O₅₊_δ	LSGM	0.51 (1.3V)	[32]
La_0.3Sr_1.7Fe_1.5Ni_0.1Mo_0.4O_6-_δ	LSGM	1.17	This work

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La_xSr_2-_xFe_1.5Ni_0.1Mo_0.4O_6-_δ对称电池电解CO₂研究

Symmetrical La³⁺-doped Sr₂Fe_1.5Ni_0.1Mo_0.4O_6-_δ Electrode Solid Oxide Fuel Cells for Pure CO₂ Electrolysis

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