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Progress in Chemistry 2022, Vol. 34 Issue (2): 272-284 DOI: 10.7536/PC201205 Previous Articles   Next Articles

• Review •

Double Perovskite Material as Anode for Solid Oxide Fuel Cells

Yang Zhang1, Min Zhang1, Hailei Zhao1,2()   

  1. 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
  • Received: Revised: Online: Published:
  • Contact: Hailei Zhao
  • Supported by:
    National Key R&D Program of China(2018YFB1502202); Global Energy Interconnection Research Institute Co. Ltd(SGGR0000WLJS1900863)
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Solid oxide fuel cell (SOFC) is an energy conversion device with advantages of high conversion efficiency, eco-friendliness, fuel flexibility, etc. The anode is one of the key components of SOFC, where the fuel oxidation reaction takes place. Compared to the traditional anode Ni-YSZ, perovskite oxides show strong resistance to carbon deposition and sulfur poisoning. Due to the diversity of ion occupancy site in the lattice, double perovskite oxides exhibit a more tailorable feature in terms of lattice structure and electrochemical properties and therefore have attracted extensive attention as SOFC anode material. However, their poor catalytic activity and low electrical conductivity, compared with the traditional Ni-YSZ anode, limit the practical application. This work summaries the recent research work and advancement of double perovskite oxides as SOFC anode in the past decade. With a brief introduction of the structure characteristics and formation origins of A-site and B-site perovskite, the properties and modification strategies of the two kinds of double perovskite anode materials are reviewed, including Sr2MgMoO6, Sr2CoMoO6, Sr2NiMoO6, Sr2FeMoO6, PrBaMn2O5+δ, etc. In the end, we propose the main future research directions.

Contents

1 Introduction

2 Double perovskite anode materials

2.1 Crystal structure of double perovskite oxides

2.2 B-site double perovskite anode materials Sr2MMoO6-δ

2.3 A-site double perovskite anode materials LnBaM2O5+δ

3 Conclusion and outlook

Key words: solid oxide fuel cells, anode, double perovskite, lattice structure, defect
Fig. 1 Schematic diagram of simple perovskite structure.
Fig. 2 Schematic diagram of B-site double perovskite A2BB'O6
Fig. 3 Schematic diagrams of A-site double perovskite: (a) AA'B2O6, (b) AA'B2O5
Fig. 4 I-V curves of single cell (a), schematic diagram of crystal structure (b), HRTEM images of Sr2FeMo2/3Mg1/3O6 (c, d), anti-site defect in the lattice (d)[61]
Fig. 5 SEM images and I-V curves of Sr2FeMo0.65Ni0.35O6 (a, c) and Sr2Fe1.3Co0.2Mo0.5O6 (b, d) electrode with in-situ exsolved metal nanoparticles[105,106]
Table 1 Comparison of electrical conductivity of B-site double perovskite anode materials
Material σ/S·c m - 1 * Atmosphere ref
SMM 8.6 H2 28
4.26 5% H2/Ar 28
Sr2Mg0.5Fe0.5MoO6-δ 28 H2 37
Sr2Mg0.95Al0.05MoO6-δ 5.4 5% H2/Ar 38
Sr2Mg0.25Ni0.75Mo O 6 - δ 33.217 H2 40
Sr2MgMo0.8Nb0.2O6-δ 0.2 10% H2 43
SNM 67 (850 ℃) H2 46
Sr2Fe4/3Mo2/3O6 16 H2 59
SFM5 310 (780 ℃) H2 63
Sr2Fe1.4Nb0.1Mo0.5O6-δ 15.86 (600 ℃) H2 69
SFM5 11.11 (600 ℃) H2 69
Sr1.5Ca0.5MgMoO6 25 H2 72
Sr1.85Ca0.15Fe1.5Mo0.5O6 33.1 H2 73
Sr1.4La0.6MgMoO6 40 5% H2/Ar 77
Sr1.4Sm0.6MgMoO6 16 H2 82
Sr1.9MgMoO6 15.7 H2 87
Table 2 Comparison of polarization resistance of B-site double perovskite anode materials
Material Rp/Ω·c m 2 * Atmosphere ref
Sr2Mg0.3Co0.7MoO6-δ 0.49 5% H2/Ar 41
Sr2MgMo0.8Nb0.2O6-δ 0.16** CH4 71
Sr2Co1.2Mo0.8O6 0.66** H2 50
Sr2Co1.1Mo0.9O6 0.35** H2 50
Sr2Fe1.2Mo0.8O6-δ 0.176 H2 60
SFM5 0.235 H2 60
SFM5 0.24 H2 63
Sr2Fe1.4Nb0.1Mo0.5O6-δ 0.22 Ar 69
Sr1.85Ca0.15Fe1.5Mo0.5O6 0.12 H2 73
Sr1.75Ca0.25Fe1.5Mo0.5O6 0.2** H2 74
Sr1.5Ca0.5Fe1.5Mo0.5O6 0.32** H2 74
Pt@SFM 0.085 H2 100
(Co-Ni-Mo)@SFM 0.062 H2 100
Sr2Fe1.3Co0.2Mo0.5O6-δ 0.29 H2 106
Table 3 Comparison of maximum power density (MPD) of single-cell with B-site double perovskite as SOFC anodes
Anode materials Electrolyte thickness*/μm MPD/
W·c m - 2 * *		 Fuel ref
SMM 300 0.838 H2 33
300 0.438 CH4 33
300 0.829 5 ppm H2S/H2 33
Sr2Mg0.3Co0.7Mo O 6 - δ 400 0.12 H2 41
SMM 400 0.038 H2 41
SNM 300 0.595 H2 46
SCM 300 0.735 H2 47
300 0.527 CH4 47
SFM 300 0.584 H2 54
SFM 300 0.603 H2 55
300 0.429 CH4 55
Sr2Fe4/3Mo2/3O6 300 0.547 H2 59
300 0.472 100 ppm
H2S/H2		 59
Sr2FeMo2/3Mg1/3O6 300 0.4*** 40%
C3H8/N2		 61
300 1.034
(900 ℃)		 100 ppm
H2S/H2		 61
300 0.803 H2 61
SFM5 265 0.5*** H2 63
265 0.23
(900 ℃)		 CH4 63
SFM5 300 0.52 H2 67
300 0.391 CH3OH 67
Sr2Fe1.4Nb0.1Mo0.5O6-δ 243 0.531 H2 69
Sr1.75Ca0.25Fe1.5Mo0.5O6 430 0.709 H2 74
Sr1.2La0.8MgMoO6 300 0.492 CH4 79
Sr1.6Sm0.4MgMoO6 300 0.5*** H2 82
300 0.45*** natural gas 82
Sr1.9MgMoO6 280 0.659 H2 87
(Ni)@SFM5 300 1.134 H2 98
300 0.663 CH4 98
(Co-Fe-Mo)@SFM 300 1.066 H2 100
Sr2FeMo0.65Ni0.35O6-δ 300 0.792 H2 105
Sr2Fe1.3Co0.2Mo0.5O6-δ 170 0.808 H2 106
Fig. 6 (a) TGA curves of transition from Pr0.5Ba0.5MnO3 to layered PrBaMn2O5+δ, (b) Long-term stability of PBM anode with Co-Fe catalyst using C3H8 as fuel[110]
Table 4 Comparison of electrical conductivity of A-site double perovskite anode materials
Material σ/S·c m - 1 * Atmosphere ref
PBM 8.16 5% H2/Ar 110
SBM 4.06 5% H2/Ar 113
SmBaMn1.9Mg0.1O5+δ 5.5 5% H2/Ar 115
PBF 0.5 H2 119
PBF 0.018 20% H2/Ar 121
PBSFG 1.1 20% H2/Ar 121
(PrBa)0.95(Fe0.9Mo0.1)2O5+δ 59.2 5% H2/Ar 122
PrBa0.8Ca0.2Mn2O5+δ 5.6** 5% H2 126
PrBaFe1.75Nb0.25O5+δ 4.43 10% H2/N2 132
Table 5 Comparison of polarization resistance of A-site double perovskite anode materials
Material Rp/Ω·c m 2 * Atmosphere ref
SBM 1.226 H2 113
PrBaMn1.8Mo0.2O5+δ 0.2 H2 114
PBM 0.3 H2 114
SmBaMn1.9Mg0.1O5+δ 0.670 H2 115
PrBaFe1.6Ni0.4O5+δ 0.034
(650 ℃)		 H2 119
PrBaFe1.7Sn0.3O5+δ 0.141 H2 120
PrBaFe1.75Nb0.25O5+δ 0.76 H2 132
Table 6 Comparison of MPD of single-cell with A-site double perovskite as SOFC anodes
Anode
materials		 Electrolyte thickness*/
μm		 MPD/
W·c m - 2 * *		 Fuel ref
PBM 300 0.42*** H2 110
(Co-Fe)@PBM 300 1.42 H2 110
300 1.3 5 ppm H2S/H2 110
300 0.7** C3H8 110
SBM 300 0.326 H2 113
(Co-Fe)@SBM 300 0.481 H2 113
PrBaMn1.8Mo0.2O5+δ 100 (YSZ) 0.56 H2 114
SmBaMn1.9Mg0.1O5+δ 300 0.317 H2 115
PBF SDC/ 0.07 (650 ℃) H2 119
PrBaFe1.6Ni0.4O5+δ SDC / 0.049 (650 ℃) H2 119
PrBaFe1.9Sn0.1O5+δ 300 0.710 H2 120
PBF 100 (SSZ) 0.4976 H2 121
PBSFG 100 (SSZ) 0.8384 H2 121
(Ni-Fe)@PBM 55~57
(YSZ)		 0.81
(700 ℃)		 H2 125
0.3
(700 ℃)		 C3H8 125
(Co-Fe)@
PrBa0.8Ca0.2Mn2O5+δ		 250 0.74 C3H8 126
250 0.47 C8H18 126
250 1.101 H2 126
(PBM)@Ni-YSZ 10 (YSZ) 1.91 H2 127
10 (YSZ) 1.12 CH4/CO2 127
(PrBa ) 0 . 95
Fe1.6Ni0.3Mo0.1O5+δ		 200 (SDC) 0.588(700 ℃) H2 131
PrBaFe1.75Nb0.25 O 5 + δ 300 0.7 H2 132
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