硅酸盐学报

对称型固体氧化物燃料电池ReBaMn₂O₅₊_δ基电极材料结构与性能的理论预测与实验验证

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张敏 ¹ , 张旸 ¹ , 杜志鸿 ¹^,² , 赵海雷 ¹^,²

硅酸盐学报 | 氢能储能专题—研究论文 2024,52(6): 1799-1809

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硅酸盐学报 |氢能储能专题—研究论文 2024 , 52 (6) : 1799 -1809

对称型固体氧化物燃料电池ReBaMn₂O₅₊_δ基电极材料结构与性能的理论预测与实验验证

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张敏¹, 张旸¹, 杜志鸿¹^,², 赵海雷¹^,²

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．新能源材料与技术北京市重点实验室，北京 100083

通讯作者:

赵海雷（1966—），女，博士，教授。

作者简介:

张敏（1998—），女，博士研究生。

Structure and Performance of ReBaMn₂O₅₊_δ based Electrodes for Symmetric Solid Oxide Fuel Cells

Min ZHANG¹, Yang ZHANG¹, Zhihong DU¹^,², Hailei ZHAO¹^,²

Affiliations

^1.School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

^2.Beijing Municipal Key Lab for Advanced Energy Materials and Technologies, Beijing 100083, China

Corresponding Author:

ZHAO Hailei (1966-), female, Ph.D., Professor. E-mail: hlzhao@ustb.edu.cn

ZHANG Min (1998-), female, Doctoral candidate. E-mail: mzhang_ustb@163.com

出版时间: 2024-06-20 doi: 10.14062/j.issn.0454-5648.20230639

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摘要

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为获得高性能ReBaMn₂O₅₊_δ对称电极材料，本工作通过第一性原理计算分析了不同稀土元素（La, Pr, Nd, Sm, Gd, Y）对材料结构和性能的影响。计算结果表明LaBaMn₂O₅₊_δ不易形成层状钙钛矿结构，GdBaMn₂O₅₊_δ的结合能最高，对应结构稳定性最好，而NdBaMn₂O₅₊_δ则具有较小的Mn 3d和O 2p轨道之间的能量差、以及较低的O 2p轨道中心与Fermi面的能量差，对应材料较高的电导率和优异的催化活性。选用La，Nd和Gd作为A位元素进行实验研究。结果表明，LaBaMn₂O₅₊_δ难以形成单相钙钛矿，但成功合成了具有层状结构的NdBaMn₂O₅₊_δ和GdBaMn₂O₅₊_δ，其在氧化和还原气氛下均保持良好的结构稳定性。相比于GdBaMn₂O₅₊_δ，NdBaMn₂O₅₊_δ在空气和5%（体积分数）H₂/Ar中均具有较高的电导率。且NdBaMn₂O₅₊_δ电极在空气和氢气气氛下的极化阻抗均小于GdBaMn₂O₅₊_δ，表现出更强的催化活性。以NdBaMn₂O₅₊_δ为对称电极，300 μm的La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-_δ为电解质制备的对称全电池，在850 ℃下最大功率密度达到335 mW·cm^-2。

关键词

对称性固体氧化物燃料电池 / 第一性原理计算 / A位双钙钛矿 / 稀土元素

Abstract

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Introduction

Compared with conventional solid oxide fuel cell, using one material as both the cathode and anode to construct a symmetrical solid oxide fuel cell (SSOFC) configuration can simplify the fabrication processes and reduce the cost, while mitigating the chemical incompatibility and thermal mismatching issues. A-site double perovskite PrBaMn₂O_5+δ, with a matched thermal expansion coefficient with electrolytes, good structural stability in both oxidizing and reducing atmospheres as well as a modest catalytic activity is a promising symmetrical electrode. However, PrBaMn₂O_5+δ has a low electrical conductivity in reducing atmosphere and an inferior catalytic activity towards fuel oxidation. To address these issues, a lattice doping strategy was employed to regulate the charge carrier and oxygen vacancy concentrations, as well as the energy band structure. In addition, theoretical calculation could predict the properties of the material, and screen doping elements for high-performance material. The A site elements have a great impact on the properties of material in terms of structure, conductivity, and catalytic activity. In this paper, first-principles calculation was employed to investigate the effect of A-site Re (rare-earth) element species (i.e., La, Pr, Nd, Sm, Gd, and Y) on the structure and properties of ReBaMn₂O₅₊_δ materials, and the calculated results were verified by experimental data.

Methods

The Cambridge sequential total energy package (CASTEP) module in Material Studio software was utilized to calculate the binding energy, formation energy from oxides, and density of states (DOS) of LaBaMn₂O₅₊_δ (LBM), PrBaMn₂O₅₊_δ (PBM), NdBaMn₂O₅₊_δ (NBM), SmBaMn₂O₅₊_δ (SBM), GdBaMn₂O₅₊_δ (GBM), and YBaMn₂O₅₊_δ (YBM) materials, respectively. The selected materials were prepared by a sol-gel method. The phase structure of the synthesized powder was examined by X-ray diffraction (XRD). The electrical conductivities of the samples were measured by the DC four-terminal method in air and 5% H₂/Ar atmosphere, respectively. The electrochemical impedance spectroscopy (EIS) and current-voltage curves of the La_0.8Sr_0.2Ga_0.8Mg_0.2O_3-_δ (LSGM, 300 μm) electrolyte supported symmetrical cell were obtained using Solartron 1260 with 1287.

Results and discussion

The theoretical lattice parameters of ReBaMn₂O₆ and ReBaMn₂O₅ were obtained through geometric optimization in DFT calculation. The ReBaMnO₅ shows an enlarged lattice volume rather than that of ReBaMnO₆. Also, the lattice volume of RBM shrinks with decreasing Re³⁺ ion radius. The binding energy results show that GBM has the maximum absolute value of binding energy, indicating an intense structural stability, which is related to the half-filled electronic configuration (4f⁷) of Gd³⁺. YBM has the minimum binding energy, indicating a poor structural stability. For the formation energy, SBM and GBM show a negative formation energy from corresponding oxides, inferring an intense synthesis preference. LBM and YBM exhibit a positive formation energy, and they prefer to maintain two phases, i.e., La(Y)MnO₃ and BaMnO₃. The energy difference between the O 2p orbital center and the Fermi surface of perovskite materials is related to the catalytic activity. Based on the conduction mechanism of B—O—B small polaron of electrons in perovskite structure, the energy difference between O 2p and Mn 3d orbital center can be related to the conductivity of the material. In this regard, the DOS of ReBaMn₂O₆ and ReBaMn₂O₅ is calculated to predict the corresponding properties. The results show that ReBaMn₂O₅₊_δ exhibits a better catalytic activity towards oxygen reduction than fuel oxidation because of the lower energy difference between the O 2p orbital center and Fermi surface of ReBaMn₂O₆ than that of ReBaMn₂O₅. In addition, PBM shows the minimum O 2p-Fermi energy difference, indicating a superior catalytic activity. While YBM and LBM possess high these values, indicating a poor catalytic activity. For the energy difference between O 2p and Mn 3d orbital center of the material, ReBaMn₂O₆ shows a smaller value than that of ReBaMn₂O₅, inferring that a higher electrical conductivity can be obtained in oxidizing atmosphere than in reducing atmosphere. PBM and NBM exhibit lower O 2p-Mn 3d energy difference values, indicating that they can realize a high conductivity. While YBM and LBM show the opposite results, indicating a low conductivity of the material. To verify these calculation results, ReBaMn₂O₅₊_δ with La, Nd, and Gd A-site elements are synthesized for properties characterization.

The XRD patterns demonstrate that NBM and GBM show a tetragonal structure with P4/mmm space group in both air and 5% H₂/Ar atmosphere, while LBM sample consists of BaMnO₃, La_1-_xM_1-_zO₃, and MnO phases. This result is consistent with the calculation results that LBM possesses a positive formation energy, showing a thermodynamic instability. NBM and GBM exhibit a higher conductivity in air rather than in 5% H₂/Ar, and NBM displays higher conductivities than GBM. At 900 ℃, the conductivities of NBM are 48.8 S·cm^-1 and 10.0 S·cm^-1 in air and 5% H₂/Ar, respectively, which are higher than those of GBM (i.e., 38.9 and 8.8 S·cm^-1). For the EIS results, NBM and GBM-based symmetrical cells exhibit lower polarization resistance in air than that in 3%H₂O/H₂. In addition, NBM shows superior catalytic activity than GBM, as confirmed by a lower polarization resistance of NBM than GBM (i.e., 1.78 vs. 3.4 Ω·cm² in air, 2.60 vs. 3.7 Ω·cm² in 3% H₂O/H₂). The conductivity and EIS results both are in accordance with the theoretical calculation results.

Conclusions

The computation results indicated that LBM is not stable at single phase layered perovskite structure. GBM showed the maximum binding energy, indicating the optimum structural stability, while NBM exhibited a smaller energy difference between Mn 3d and O 2p orbital center, and a lower energy difference between the O 2p orbital center and Fermi surface, implying the good conductivity and excellent catalytic activity among the investigated materials. Based on the calculation results, La, Nd and Gd were selected as A-site elements for verification. The results manifested that LBM was difficult to form single-phase perovskite, but it was easy to synthesize the single phases NBM and GBM. They showed a good structural stability in both reducing and oxidizing atmospheres. NBM exhibited higher conductivities in both air and 5% H₂/Ar, compared to GBM. In addition, NBM electrode displayed much lower polarization resistance than GBM, demonstrating a superior catalytic activity. The LSGM electrolyte (300 μm) supported symmetrical cell with NBM electrode delivered a maximum power density of 335 mW·cm^-2 at 850 ℃.

Key words

symmetrical solid oxide fuel cell / first principles calculation / layered double perovskite / rare-earth element.

引用本文

张敏, 张旸, 杜志鸿, 赵海雷. 对称型固体氧化物燃料电池ReBaMn₂O₅₊_δ基电极材料结构与性能的理论预测与实验验证. 硅酸盐学报, 2024 , 52 (6) : 1799 -1809 . DOI: 10.14062/j.issn.0454-5648.20230639

Min ZHANG, Yang ZHANG, Zhihong DU, Hailei ZHAO. Structure and Performance of ReBaMn₂O₅₊_δ based Electrodes for Symmetric Solid Oxide Fuel Cells[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (6) : 1799 -1809 . DOI: 10.14062/j.issn.0454-5648.20230639

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国家重点研发计划(2018YFB1502202)

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2024年第52卷第6期

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doi: 10.14062/j.issn.0454-5648.20230639

接收时间：2023-08-27
首发时间：2026-10-22
出版时间：2024-06-20

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收稿日期：2023-08-27
修回日期：2023-10-07

基金

国家重点研发计划(2018YFB1502202)

作者信息

^1．北京科技大学材料科学与工程学院，北京 100083

^2．新能源材料与技术北京市重点实验室，北京 100083

通讯作者:

赵海雷（1966—），女，博士，教授。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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