燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极

doi:10.15541/jim20240025

无机材料学报 ›› 2024, Vol. 39 ›› Issue (8): 911-919.DOI: 10.15541/jim20240025

燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极

潘建隆(), 马官军, 宋乐美, 郇宇(), 魏涛()

济南大学材料科学与工程学院, 济南 250022

收稿日期:2024-01-11 修回日期:2024-03-08 出版日期:2024-08-20 网络出版日期:2024-03-30
通讯作者: 郇宇, 副教授. E-mail: mse_huany@ujn.edu.cn;
魏涛, 教授. E-mail: mse_weit@ujn.edu.cn
作者简介:潘建隆(1998-), 男, 硕士研究生. E-mail: pjl2812054@163.com
基金资助:
国家自然科学基金(51972146);国家自然科学基金(52072150);国家自然科学基金(52372194);山东省重点基础研究项目(ZR2022ZD39)

High Stability/Catalytic Activity Co-based Perovskite as SOFC Anode: In-situ Preparation by Fuel Reducing Method

PAN Jianlong(), MA Guanjun, SONG Lemei, HUAN Yu(), WEI Tao()

School of Materials Science and Engineering, University of Jinan, Jinan 250022, China

Received:2024-01-11 Revised:2024-03-08 Published:2024-08-20 Online:2024-03-30
Contact: HUAN Yu, associate professor. E-mail: mse_huany@ujn.edu.cn;
WEI Tao, professor. E-mail: mse_weit@ujn.edu.cn
About author:PAN Jianlong (1998-), male, Master candidate. E-mail: pjl2812054@163.com
Supported by:
National Natural Science Foundation of China(51972146);National Natural Science Foundation of China(52072150);National Natural Science Foundation of China(52372194);Shandong Province Key Fundamental Research Program(ZR2022ZD39)

摘要/Abstract

摘要：

受固体氧化物燃料电池(SOFCs)原位还原脱溶纳米金属阳极技术的启发, 本工作采用煅烧后的Sr₂V_0.1Co_0.9MoO₆前驱体(包含其他相的钙钛矿)在空气气氛下与电解质共烧制备出单电池, 避免了为防止阳极氧化而需在还原/惰性气氛下制备电池的苛刻条件。制备电解质片上的阳极前驱体仅需在燃料侧原位还原4 h, 便可形成纯相Sr₂V_0.1Co_0.9MoO₆ (R-SVCMO)阳极。结果表明, R-SVCMO在活化能显著降低的同时电导率由2.7 S•cm^-1提高至21.6 S•cm^-1。当R-SVCMO为阳极的单电池分别以H₂和湿CH₄为燃料气时, 在850 ℃的最大功率密度(P_max)分别达到862和514 mW•cm^-2, 显示出优秀的催化性能。还原前后阳极在100~850 ℃的平均热膨胀系数(TEC)分别为1.15×10^-5和1.23×10^-5 K^-1, 均与传统SOFC电解质相近。因此, 还原过程不会导致阳极层体积产生变化, 可以显著提高电池结构稳定性(退化率仅为0.13%)。加之R-SVCMO是在燃料气氛下合成的, 其作为阳极表现出极高的长期稳定性和催化活性。R-SVCMO对湿CH₄的催化效率达到60%, 并能够稳定运行1450 h, 相应的单电池可在0.7 V稳定运行450 h。综上所述, 本研究采用燃料原位还原法制备了具有优异电化学性能和结构稳定性的单电池。

关键词: 固体氧化物燃料电池, 燃料还原制备技术, 高稳定性阳极, 甲烷燃料

Abstract:

Taking inspiration from the in-situ reduction technique employed for exsolved nano-metal as anodes in solid oxide fuel cells (SOFCs), this study utilized Sr₂V_0.1Co_0.9MoO₆, which was synthesized in an ambient air environment, with perovskites of other phases to co-fire with the electrolyte under atmospheric conditions for direct fabrication of a single cell. By this way, the procedure of subjecting the cell to harsh preparative conditions in a reducing/inert atmosphere to prevent its anodic oxidation can be circumvented. After preparation of the anode precursor on the electrolyte sheet, we adopted a simple process of in-situ reduction at 750 ℃ for 4 h on the fuel side to achieve formation of a pure phase Sr₂V_0.1Co_0.9MoO₆ (R-SVCMO) as anode. The results demonstrate a significant reduction in the activation energy of R-SVCMO, accompanied by an increase in conductivity from 2.7 to 21.6 S•cm^-1. Moreover, when employing R-SVCMO as anode in a single cell with H₂ and wet CH₄ as fuel gases, the maximum power density (P_max) at 850 ℃ can reach up to 862 and 514 mW·cm^-2, respectively, showcasing exceptional catalytic performance. The anodes before and after reduction exhibit average thermal expansion coefficient (TEC) of 1.15×10^-5 and 1.23×10^-5 K^-1, respectively, within the temperature range of 100-850 ℃, comparable to those observed in conventional SOFC electrolytes. Therefore, the reduction process does not induce any volumetric changes in the anode layer, significantly enhancing its structural stability. Meanwhile, degradation rate of only 0.13% is occurred. It is worth noting that this R-SVCMO synthesis method can result in remarkable long-term stability and high catalytic activity as an anode material. The obtained R-SVCMO can achieve a 60% catalytic efficiency for wet CH₄ and last for 1450 h. Based on this R-SVCMO, the single cell can maintain stability for 450 h at 0.7 V. In conclusion, this study demonstrates an effective way of employing an in-situ fuel reduction method to prepare a single cell with exceptional electrochemical performance and structural stability.

Key words: solid oxide fuel cell, fuel reducing method, high stable anode, methane fuel

中图分类号:

TM911

潘建隆, 马官军, 宋乐美, 郇宇, 魏涛. 燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极[J]. 无机材料学报, 2024, 39(8): 911-919.

PAN Jianlong, MA Guanjun, SONG Lemei, HUAN Yu, WEI Tao. High Stability/Catalytic Activity Co-based Perovskite as SOFC Anode: In-situ Preparation by Fuel Reducing Method[J]. Journal of Inorganic Materials, 2024, 39(8): 911-919.

图/表 18

图1 SCMO和SVCMO在不同条件下煅烧前后的XRD谱图

Fig. 1 XRD patterns of SCMO and SVCMO before and after calcination under different conditions (a) SCMO powders before and after H2 reduction at 750 ℃ for 4 h; (b) SVCMO powders before and after H2 reduction at different temperatures for 4 and 72 h; (c) Enlarged patterns of 2θ=26°-30° in (b)

表1 SCMO以及R-SVCMO粉体XRD精修后的晶格参数

Table 1 Lattice parameters of SCMO and R-SVCMO obtained by XRD Rietveld refinement

Parameter	SCMO	R-SVCMO
Space group	I4/m	I4/m
a=b/Å	5.6374	5.6218
c/Å	7.9128	7.8823
α/(º)	90	90
β/(º)	90	90
γ/(º)	90	90
Sr-O/Å	2.8130	2.8071
Co-O/Å	2.0765	2.0532
V-O/Å	—	1.7758
Mo-O/Å	1.8945	1.9191

图2 R-SVCMO样品的微观结构

Fig. 2 Microstructure of R-SVCMO sample (a) TEM image; (b) HRTEM image and (c) corresponding SAED pattern; (d) STEM image and corresponding EDX elemental mappings

图3 不同材料的热膨胀现象

Fig. 3 Thermal expansion of different materials (a) Thermal expansion (ΔL/L0) curves of electrolyte LSGM, anodes SCMO and R-SVCMO from room temperature to 850 ℃; (b) TEC curves of SCMO, SVCMO and R-SVCMO in the range of 100−850 ℃; (c) Comparison of TEC of SCMO, SVCMO and R-SVCMO with conventional electrolytes and other perovskite anode materials[7⇓-9,11,14 -15,17,26]

图4 SCMO和R-SVCMO材料的XPS谱图

Fig. 4 XPS spectra for SCMO and R-SVCMO (a) Co2p, (b) Mo3d, (d) O1s XPS spectra for SCMO and R-SVCMO; (c) V2p XPS spectrum for R-SVCMO

表2 XPS计算的SCMO与R-SVCMO材料中不同价态Mo和Co元素以及不同形式O的面积含量百分比

Table 2 Area content percentages of Mo and Co elements in different valences, and different O types for SCMO and R-SVCMO samples based on XPS data

Sample	Valence ratio/%
	Mo		O			Co
	Mo⁵⁺	Mo⁶⁺	O_latt.	O_ad.	H₂O	Co²⁺	Co³⁺
SCMO	34.1	65.9	31.4	60.5	8.2	74.0	26.0
R-SVCMO	58.5	41.5	31.1	65.5	3.4	62.9	37.1

图5 SCMO和R-SVCMO在H2气氛下测试的电导率和H2-TPR曲线

Fig. 5 Conductivity and H2-TPR curves for SCMO and R-SVCMO in testing H2 (a) Temperature dependence of conductivity curves; (b) Arrhenius curves; (c) H2-TPR curves; Colorful figures are available on website

图6 以SCMO和R-SVCMO为阳极的单电池电化学性能

Fig. 6 Electrochemical performance of single cells with SCMO and R-SVCMO as anode materials (a, b) I-V-P curves for single cells with (a) SCMO and (b) R-SVCMO as anodes obtained under H2 at different temperatures; (c, d) Electrochemical Impedance spectra for (c) SCMO and (d) R-SVCMO single cells under H2 at different temperatures; (e) Durability of single cells with SCMO and R-SVCMO as anodes under 0.7 V at 750 ℃; Colorful figures are available on website

图7 以SCMO、R-SVCMO为阳极或对称电极的单电池或对称电池的电化学性能

Fig. 7 Electrochemical performance of single cells or symmetric cells with SCMO and R-SVCMO as anodes or symmetric electrodes (a) EIS and (b) DRT spectra of SCMO and R-SVCMO symmetric cells under H2 at different temperatures; (c) I-V-P curves and (d) DRT spectra of R-SVCMO single cell under different H2 partial pressures at 750 ℃; Colorful figures are available on website

图8 以SCMO和R-SVCMO为阳极的单电池在CH4气氛下的电化学性能

Fig. 8 Electrochemical performance of single cells with SCMO and R-SVCMO as anodes in CH4 atmosphere (a, b) I-V-P curves of (a) SCMO and (b) R-SVCMO based SOFC with humidified CH4 as fuel gas at different temperatures; (c, d) EIS spectra of (c) SCMO and (d) R-SVCMO based SOFC in humidified CH4 at different temperatures; (e) CH4 conversion rate of R-SVCMO catalyst for CH4 reforming and R-SVCMO based single cell working at 0.7 V under humidified CH4 at 750 ℃ as a function of testing time; Colorful figures are available on website

图S1 (a) SCMO和(b) R-SVCMO的XRD精修图

Fig. S1 ietveld refined XRD patterns of (a) SCMO and (b) R-SVCMO

图S2 复合阳极SVCMO 和 D-SVCMO的XRD图谱

Fig. S2 XRD patterns of SVCMO and D-SVCMO composite anodes

图S3 SVCMO和SCMO的O1s XPS谱图

Fig. S3 O1s XPS spectra for SVCMO and SCMO samples

图S4 SVCMO与LSGM 在空气下共烧5 h后的XRD图谱

Fig. S4 XRD patterns of SVCMO and LSGM after co-firing in air for 5 h

图S5 SVCMO与SDC 在空气下共烧5 h后的XRD图谱

Fig. S5 XRD patterns of SVCMO and SDC after co-firing in air for 5 h

图S6 LSCF的XRD图谱

Fig. S6 XRD pattern of LSCF

图S7 R-SVCMO单电池的SEM照片

Fig. S7 SEM image of the single cell with R-SVCMO anode

图S8 电池EIS的等效电路图

Fig. S8 Equivalent circuit for the fitting EIS of different cells

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燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极

High Stability/Catalytic Activity Co-based Perovskite as SOFC Anode: In-situ Preparation by Fuel Reducing Method

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