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Double Perovskite Material as Anode for Solid Oxide Fuel Cells

Yang Zhang , Min Zhang , Hailei Zhao

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 272 -284.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (2) : 272-284 DOI: 10.7536/PC201205
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Double Perovskite Material as Anode for Solid Oxide Fuel Cells
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Abstract

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

Graphical abstract

Keywords

solid oxide fuel cells / anode / double perovskite / lattice structure / defect

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Yang Zhang, Min Zhang, Hailei Zhao. Double Perovskite Material as Anode for Solid Oxide Fuel Cells. Progress in Chemistry, 2022, 34(2): 272-284 DOI:10.7536/PC201205

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1 Introduction

With the continuous development of human society, the development of clean, efficient, safe and economical new energy has become an inevitable trend of energy development in the future. Solid oxide fuel cell (SOFC) has attracted much attention in many clean energy sources due to its high energy conversion efficiency, environmental friendliness, fuel adaptability, all-Solid-state, modular assembly flexibility and other advantages[1]. SOFC has broad application prospects in large-scale centralized power supply, medium-sized distributed generation, small combined heat and power and other fields. In recent years, SOFC is developing in the field of transportation power supply such as ships and vehicles[2][3].
The SOFC is mainly composed of a cathode, an anode and an electrolyte. For the solid electrolyte based SOFC with oxygen ion conduction, oxygen gets electrons at the cathode and becomes oxygen ions, which are then transmitted to the anode through the electrolyte. At the anode, oxygen reacts with fuel gas to generate oxidation products and release electrons. The electrons drive the load back to the cathode through an external circuit. The anode and the cathode are made of porous materials, which are convenient for gas transmission and provide more active sites for electrode reaction. The electrolyte is a dense material that provides ion transport and prevents gas leakage. The common cathode materials are La0.8Sr0.2MnO3-δ and La0.6Sr0.4Co0.2Fe0.8O3-δ, and the common electrolyte materials are Y0.16Zr0.84O2-δ(YSZ) and La0.8Sr0.2Ga0.8Mg0.2O3-δ(LSGM)[4][5]. The anode provides an electrochemical reaction site for fuel gas oxidation, and also provides a fast channel for fuel gas input, reaction products and electron output, so its structure and performance play a vital role in the performance of the cell[6]. Anode materials should not only have good chemical stability and thermal stability in reducing atmosphere, good chemical compatibility with materials in contact and matching thermal expansion coefficient, but also need high ionic and electronic conductivity, as well as good catalytic activity for fuel gas[7].
Initially, coke was used as the anode, but its poor catalytic activity limited the power characteristics of the cell. Later, Pt, a noble metal with strong catalytic activity, was used as anode material. However, the scarcity and high price of Pt limit its large-scale application[8]. Transition metal Ni has good catalytic activity for the hydrogen oxidation process, but it is not suitable for direct use as an anode because of its large thermal expansion coefficient and easy mismatch with the electrolyte[9].
The composite of electrolyte and nickel can effectively reduce the expansion coefficient of the anode and improve the thermal expansion matching between the anode and the electrolyte. At present, the most widely used anode material is the metal-ceramic composite Ni-YSZ[10]. Electrolyte provides ionic conductivity, while nickel provides high electronic conductivity and excellent catalytic activity, so Ni-YSZ shows better anode performance when hydrogen is used as fuel. However, Ni and YSZ only provide electronic and ionic conductivity, respectively, so the anodic reaction is confined to the three-phase interface of Ni-YSZ-fuel gas, which limits the anodic reaction kinetics. At the same time, after working at high temperature for a long time, the Ni particles are easy to agglomerate, the specific surface area decreases, and the electrocatalytic activity becomes worse[11]. In addition, when using hydrocarbon fuels (such as natural gas), Ni-YSZ anode will also suffer from carbon deposition (Ni will catalyze the decomposition of C — H bonds to form carbon deposition) and sulfur poisoning (S reacts with Ni to form NiS), which will lead to the deactivation of the anode[12,13]. Therefore, the development of SOFC with wide fuel adaptability and good structural stability requires the research and development of new anode materials.
Mixed ion electron conductor (MIEC) can extend the electrochemical reaction sites to the whole electrode surface, thus expanding the catalytic active area and improving the working activity of the electrode. At the same time, common ceramic mixed conductor materials have good resistance to carbon deposition and sulfur poisoning, which lays a foundation for the direct use of hydrocarbon fuels[14]. Among them, perovskite materials have simple structure and strong structural tolerance, and the electrochemical properties of materials can be effectively improved by adjusting the element composition[15]. Compared with the single perovskite, the double perovskite structure has two A or two B positions, so the structure and performance are more adjustable, which has attracted wide attention and become the key research direction of new anode materials[16]. However, compared with the traditional anode Ni-YSZ, the double perovskite anode material still has the problems of weak catalytic activity and low conductivity. The double perovskites have been modified from different scales such as microstructure, crystal structure and electronic structure, and the modification mechanism has been deeply studied, and some gratifying achievements have been made.
In this paper, the structural characteristics of A-site and B-site double perovskite materials are introduced firstly, and then the typical chemical compositions of the two double perovskite materials used for anodes and their modification progress are summarized, including doping modification and electrode surface modification. Finally, the future development of SOFC anode materials is briefly discussed. It is hoped that this paper can provide a reference for the development and application of the next generation of double perovskite anode materials.

2 Double perovskite type anode material

2.1 Double perovskite type oxide crystal structures

The general chemical formula of single perovskite-type oxides is ABO3, where A is usually an alkaline earth metal or a Lanthanide (Lanthanide, Ln), and B is a transition metal[17]. In the perovskite structure, the lattice framework is composed of BO6 octahedra, and the A-site elements are filled in the gaps of the octahedral framework, as shown in fig. 1. The structure has strong tolerance, 80% of elements in the periodic table can form the perovskite structure, and the electrochemical properties of the material can be effectively improved by doping other elements at the A and B sites[18]. Ideal perovskite materials are cubic structure, but in fact there are some distortions. The crystal structure of the perovskite oxide is closely related to the ionic radii of the A-site and B-site elements, and there is a structural criterion as shown in formula (1):[19,20]
t = ( r A + r O ) / 2 ( r B + r O )
Where rA, rB, rO are the average radius of A-site ions, B-site ions and the radius of oxygen ions, respectively, and t is the tolerance factor. It is generally believed that the perovskite structure can exist stably when 0.75 < t < 1[21]. When t increases from 0.75 to 1, the symmetry of perovskite changes from low symmetry (such as monoclinic, orthorhombic, etc.) To high symmetry (such as cubic). When 0.95 < t < 1.04, the perovskite is usually cubic. When t > 1, the perovskite structure tends to exist in the hexagonal form.
The double perovskite structure is derived from a single perovskite with the general chemical formula AA'BB'O6. According to the difference of A-site and B-site elements and structures, it can be divided into B-site double perovskite structure and A-site double perovskite structure. When A and A 'are the same element, i.e., A2BB'O6, it is called B-site double perovskite, and the structure is shown in Fig. 2. Among them, A-site is alkaline earth metal or rare earth element with larger radius, B-site is transition metal element with lower valence (such as Fe, Co, Ni, etc.), and B-site is transition metal element with higher valence (such as Mo, Nb, W, etc.). As that valence state and sizes of the element at the B site and the B 'site are greatly different, in order to balance the charge distribution in the lattice, the elements at the B site and the B' site are orderly arranged, oxygen octahedron formed by B and B 'are alternately arranged along three axial directions of a/B/C respectively, and B and B' atoms are connected into B-O-B 'through oxygen atoms[22]. B-site double perovskite materials usually have smaller thermal expansion coefficient and lower electrical conductivity because of the interaction of two B-site elements with different chemical and physical properties.
When B and B 'are the same element, that is, AA'B2O6, it is called A-site double perovskite, and the structure is shown in fig. 3A. Generally, A is a lanthanide element with a small radius (such as Pr, Nd, Sm, etc.), A 'is an alkaline earth metal Ba with a large radius, and B is a transition metal element with multiple valence States (such as Mn, Fe, Co, etc.). A and a 'are easy to form layere ordered arrangement, namely,- [AO]- [BO]- (A' O)- [BO]- [AO]-alternate arrangement along that c-axis due to the large difference of the radii of the elements at the a site and the a 'site[23]. In order to alleviate the lattice stress caused by the difference of element radius, a large number of oxygen vacancies will appear in the [AO] layer with smaller radius. Because of this, the general chemical formula of A-site double perovskite is usually written as AA'B2O5+δ. Depending on the oxygen partial pressure in preparation or use, the oxygen in the A-element layer can be fully occupied, half-occupied, or even completely removed (Fig. 3B). The highly ordered oxygen vacancies provide a fast ion migration channel for oxygen ion transport, so the A-site double perovskite behaves as a two-dimensional oxygen ion conductor, and the expansion coefficient of the material is also anisotropic[24,25].

2.2 B-site double perovskite type anode material Sr2MmoO6-δ.

For the B-site double perovskite oxide, the electrochemical properties are closely related to the B/B 'site transition metal. When the variable valence 3D transition group elements (such as Mn, Co, Ni, Fe, etc.) Are selected at the B site and Mo is selected at the B' site, the material shows better conductivity and catalytic activity[26,27]. A site element is usually selected as Sr with moderate radius in alkaline earth metals, so a large number of studies use Sr2MMoO6(M as the low valence metal) as the matrix.

2.2.1 Sr2MgMoO6-δ

The thermal expansion coefficient of Sr2MgMoO6-δ(SMM) from RT (Room temperature) to 800 ℃ is between (11.7~12.7)×10-6K-1, which has a good thermal expansion matching with common electrolytes YSZ(10.6×10-6K-1[30]), LSGM(11.1×10-6K-1[31]) and Gd0.2Ce0.8O1.9(GDC,9.5×10-6K-1[32])[28,29]. SMM is an n-type semiconductor, and its conductivity is 8.6 S·cm-1 at 800 ℃ in pure hydrogen atmosphere, which is higher than that of traditional single perovskite chromate anode materials[28].
SMM was first reported by Huang et al for SOFC anodes, which exhibited good resistance to carbon deposition and sulfur poisoning[28,33]. However, the direct contact between SMM and LSGM electrolyte is prone to element diffusion, so it is necessary to add La0.4Ce0.6O2-δ(LDC) or GDC as a buffer layer in the preparation of the electrode[28][34]. An electrolyte (300 μm) -supported single cell was fabricated with SMM as the anode material in SMM/LDC/LSGM/SrFe0.2Co0.8O3-δ(SFC) configuration. The maximum power density of the cell was 438 and 838 mW·cm-2 at 800 ℃ with methane and pure hydrogen as the fuel, respectively. The maximum output power of 829 mW·cm-2 was still maintained when hydrogen containing 5 ppm H2S was used as the fuel, showing good resistance to sulfur poisoning. Considering that Mg ion is in a fixed valence state, it is difficult to gain or lose electrons in the electrode reaction, so the catalytic activity of SMM is weak. Researchers later found that the higher output power of the SMM battery was mainly due to the catalysis of the current collector Pt, not the SMM material itself[35].
For perovskite-type oxides, B-site doping with transition metals can effectively improve the catalytic activity of the materials. Because Mg is a divalent alkaline earth metal, and the average valence of transition metal Mn/Fe is higher than that of divalent in perovskite under reducing atmosphere, according to the principle of defect chemistry, high-valence doping is conducive to the reduction of Mo ion valence or the reduction of oxygen vacancy concentration. The results show that the introduction of Mn/Fe can effectively increase the concentration of Mo5+, thus improving the conductivity of SMM double perovskite materials[36,37]. The conductivity of Sr2Mg0.5Fe0.5MoO6-δ is more than three times higher than that of SMM in pure hydrogen atmosphere at 800 ℃, reaching 28 S·cm-1. The trivalent main group metal element Al has a similar effect, and the conductivity of the sample doped with 5% Al instead of Mg (Sr2Mg0.95Al0.05MoO6-δ) is more than three times higher than that of the undoped sample under the same conditions[38]. If part of Mg is substituted by transition metal Co/Ni with weak metal-oxygen bond, more lattice oxygen will be released in the reducing atmosphere at high temperature, and the oxygen vacancy concentration of the material will be increased[39]. Meanwhile, the average valence of Co/Ni is slightly higher than that of + 2 in the reducing atmosphere at the B-site of perovskite, and the substitution of Co/Ni for Mg is beneficial to increase the Mo5+ content. The conductivity of Sr2Mg0.25Ni0.75MoO6-δ reaches 33.22 S·cm-1,Sr2Mg0.3Co0.7MoO6-δ under the same conditions mentioned above, and it is about 7 S·cm-1[40,41] in the 5%H2/Ar atmosphere at the same temperature.
Compared with Mg site doping, Mo site doping is less studied. The substitution of W/Nb with strong metal-oxygen bond for Mo can effectively enhance the reduction resistance of the material and keep its structural stability in the reducing atmosphere above 1000 ℃[42]. Based on the principle of defect chemistry, equivalent or low-valence doping can not increase the free electron concentration of the material, so the doping of W/Nb reduces the electronic conductivity of the material, and the conductivity of Sr2MgMo0.8Nb0.2O6-δ at 800 ℃ in 10%H2/N2 atmosphere is only 0.2 S·cm-1[43].

2.2.2 Sr2Co(Ni)MoO6-δ

In order to solve the problems of low conductivity and poor catalytic activity of Sr2MgMoO6-δ, people use variable valence transition metals to replace Mg to effectively improve the catalytic activity of materials, such as Sr2CoMoO6(SCM) and Sr2NiMoO6(SNM). At the same time, the above two kinds of materials have good chemical compatibility with LSGM, so the anode buffer layer can be omitted in the preparation of LSGM electrolyte-based single cell, thus simplifying the battery preparation process. The thermal expansion coefficient of SCM is between (11.2~14.5)×10-6K-1 (RT ~ 850 ℃), and that of SNM is between (12.35~14.0)×10-6K-1 (RT ~ 1100 ℃)[44][45].
SNM was first reported by Wei et al. As an anode for SOFCs and exhibited high electrical conductivity and power output[46]. The conductivity of SNM in pure hydrogen atmosphere at 850 ℃ reaches 67 S·cm-1, which is much higher than that of SMM. The electrolyte (300 μm) supported single cell assembled with SNM as the anode, LSGM as the electrolyte, and Ba0.5Sr0.5Co0.8Fe0.2O3-δ(BSCF) as the cathode has a maximum power density of 819 mW·cm-2 and a total polarization impedance of only 0.26Ω·cm2 at 850 ℃ when hydrogen is used as the fuel. SCM not only has good catalytic activity for hydrogen, but also shows high output power for hydrocarbon fuels. Electrolyte (300 μm) -supported single cell prepared with SCM as anode, LSGM as electrolyte and SFC as cathode has a maximum power density of 735 and 527 mW·cm-2[47] at 800 ℃ with pure hydrogen and wet methane as fuel, respectively. However, when dry methane was used as fuel, carbon deposition appeared on the surface of SCM electrode, the active sites of electrode reaction decreased, and the output power decreased sharply[48].
The electrochemical properties of double perovskite oxides are also closely related to the content of Mo5+/Mo6+ redox pairs, and the electrochemical properties of SCM and SNM can be directly changed by adjusting the ratio of B-site elements to Mo. Because the Co/Ni — O bond is weaker than the Mo — O bond, the oxygen ion conductivity of the material can be significantly improved when the Co/Ni: Mo ratio is greater than 1[49]. However, according to the principle of defect chemistry, the substitution of low-valence elements Co/Ni for Mo will lead to the decrease of Mo5+ concentration, that is, with the increase of Co/Ni content, the electronic conductivity will decrease. The experimental results show that the coupling effect of the two will lead to the gradual weakening of the catalytic ability of the material for hydrogen oxidation with the excessive increase of Co/Ni content.The polarization resistance of Sr2Co1.2M o 0 . 8 O6 in hydrogen is even Sr2Co1.1M.The o 0 . 9 is more than twice the O6[50].

2.2.3 Sr2FeMoO6-δ

Because of the weak Co/Ni-O bond, it is easy to cause the precipitation of Co/Ni metal in the reducing atmosphere for a long time, which affects the long-term stability of the battery[51]. Therefore, people begin to pay attention to the transition metal Fe with strong metal-oxygen bond and mixed valence as a new anode material of B-site element[52]. Sr2FeMoO6-δ(SFM) has a coefficient of thermal expansion of about 13.4×10-6K-1[53] between 50 and 900 ° C.
He et al. First applied SFM to SOFC, and the results showed that SFM is a very potential anode material, which has good catalytic activity for the oxidation of hydrogen and hydrocarbon fuels[54,55]. It is difficult to obtain a single phase of SFM in air because it is difficult to keep all the divalent Fe when synthesized in air. In order to obtain a single double perovskite phase in air, it is a common means to change the Fe/Mo ratio. The results show that the single phase can be synthesized in a wide range of Fe/Mo ratio, but the double perovskite structure can not be maintained when the Fe/Mo ratio changes greatly[56,57]. The results show that the Mo content of SFM with double perovskite structure can not exceed 0.68 when it is synthesized in air[58]. At the same time, when Fe elements with different valence occupy B/B ′ sites respectively, the material will show excellent electrochemical performance. A single double perovskite phase can be directly synthesized in air by adopting 1/3 Fe to replace Mo(Sr2Fe4/3Mo2/3O6), the material has better catalytic activity and sulfur poisoning resistance, and the output power is quickly recovered after the fuel containing sulfur is switched back to pure hydrogen[59,60]. In our group, Du et al. Used Mg to replace part of Mo and synthesized Sr2FeMo2/3Mg1/3O6 in air. It is found that there are a large number of antisite defect structures in the material[61]. Since Mg has a low valence state and tends to occupy the B site, while Fe will occupy both the B and B ′ sites, the actual crystal structure of the material is Sr2(Fe2/3Mg1/3)(Mo2/3Fe1/3)O6 (Figure 4). The antisite defect provide an electron fast migration path for small polaron conduction, and simultaneously improves that catalytic activity of the material. Electrolyte (300 μm) -supported full cell was assembled in Sr2FeMo2/3Mg1/3O6/LDC/LSGM/LSCF configuration, and the maximum power density was 1316, 900, 1034 mW·cm-2 at 900 ℃ when H2, 40 vol%C3H8/N2, 100 ppm H2S/H2 were used as fuel, respectively. In addition, the material also has good adaptability to hydrocarbon fuel, and no obvious performance degradation is found after 210 hours of operation, and the output power of the cell can be quickly recovered after switching to hydrogen.

2.2.4 Sr2Fe1.5Mo0.5O6-δ

Sr2Fe1.5Mo0.5O6(SFM5) materials have become a research hotspot because of their simple preparation process and single phase in air. The thermal expansion coefficient of SFM5 is 14.9×10-6K-1(RT~800℃)[62].
Liu et al. First studied SFM5 as an anode and found that there were a large number of anti-site defects in SFM5 crystal, which showed high electronic conductivity and electrochemical performance. The conductivity of SFM5 in air and pure hydrogen at 780 ℃ was 550 and 310 S·cm-1, respectively, which was 1 to 2 orders of magnitude higher than that of SMM[63]. Electrolyte (265 μm) supported symmetric cells were assembled with LSGM as electrolyte and SFM5 as both cathode and anode, and the maximum power densities were 835 and 230 mW·cm-2 at 900 ℃ using wet hydrogen and methane as fuels, respectively. The anode showed excellent resistance to sulfur poisoning, and the power output did not decrease significantly after 25 H operation with 100 ppm H2S/H2 as fuel, and no sulfur fragments were found on the electrode even after treatment in 800 ppm H2S/H2[64,65].
In addition to hydrocarbon fuels, SFM5 also has good catalytic activity for alcohol fuels. Methanol is the simplest saturated monohydric alcohol, which is generally considered to be more active than general carbon-containing fuels[66]. Electrolyte (300 μm) -supported full cell was assembled with SFM5/LSGM/BSCF configuration, using pure hydrogen and methanol as fuel, the maximum power density was 520 and 391 mW·cm-2 at 800 ℃, respectively, and no carbon deposition was found after testing[67]. In addition to methanol, SFM5 also exhibits excellent resistance to carbon deposition on ethanol fuels[68].
Fe element still has the possibility of precipitation when the anode works in the reducing atmosphere for a long time, and the structural stability of the material in the reducing atmosphere can be improved by replacing Fe with Nb with strong metal-oxygen bond[69]. In addition, according to the principle of defect chemistry, the substitution of high valence Nb for part of Fe can increase the carrier Mo5+ concentration, thus improving the conductivity. In hydrogen atmosphere at 600 ℃, the conductivity of Sr2Fe1.4Nb0.1Mo0.5O6-δ reaches 15.86 S·cm-1, which is 1.5 times that of SFM5 under the same conditions.

2.2.5 A-site doping modification

Different alkaline earth metal elements as A-site elements can affect the stability of double perovskite materials, for example, Ca2FeMoO6-δ can not exist stably at low oxygen partial pressure, while Sr2FeMoO6-δ and Ba2FeMoO6-δ can exist stably[70,71]. In the perovskite structure, the A-site element generally does not directly affect the catalytic activity of the material, but can affect the catalytic activity of the material by changing the lattice structure and the type and concentration of defects in the lattice. According to the principle of defect chemistry, the concentration of oxygen vacancies and/or the valence state of B-site elements can be changed by aliovalent A-site element doping, and the crystal structure can be adjusted by equivalent A-site element doping, thus indirectly changing the catalytic activity. Small radius Ca doping is beneficial to reduce the amount of coordination oxygen, thereby increasing the carrier Mo5+ content, improving the conductivity of the material, and then affecting the catalytic activity of the material. The conductivity of Sr1.5Ca0.5MgMoO6 reaches 25 S·cm-1 at 800 ℃ in hydrogen atmosphere, which is 16 times higher than that of SMM under the same conditions[72]. The polarization impedance of Sr1.85Ca0.15Fe1.5Mo0.5O6 at 800 ℃ in hydrogen atmosphere reaches the 0.12Ω·cm2, which is only 40% of that of SFM5 under the same conditions[73]. A small amount of Ca doping does not affect the structural stability of the material.When Sr1.75Ca0.25Fe1.5Mo0.5O6 is used as both the cathode and anode, LSGM as the electrolyte, and hydrogen as the fuel, there is no significant performance degradation after long-term operation at 750 ℃ for about 280 H[74].
Lanthanides are another common A-site doping element. The small-radius Ln substitution can effectively reduce the thermal expansion coefficient of the material, and the thermal expansion coefficient of LaSrFe1.5Mo0.5O6 is only 13.3×10-6K-1(RT~800℃), which is more compatible with common electrolyte materials[75]. According to the principle of defect chemistry, the replacement of some Sr2+ by Ln3+ will convert some Mo6+ into Mo5+, thus improving the electronic conductivity of materials[76]. The conductivity of Sr1.4La0.6MgMoO6 reached 40 S·cm-1 at 800 ℃ in 5%H2/Ar atmosphere, which was 10 times higher than that of the same batch of SMM[77]. However, the decrease of Mo valence makes it closer to the valence of B-site elements, which weakens the formation of B-site double perovskite structure. In other words, with the increase of Ln doping, the concentration of anti-site defects increases and gradually transforms to single perovskite structure. The results of first-principles calculations show that the anti-site defect structure is helpful to enhance the oxidation process of the fuel gas[78]. Electrolyte (300 μm) -supported full cells were assembled in Sr1.2La0.8MgMoO6/LDC/LSGM/SFC configuration with wet methane as fuel, and the maximum power density reached 492 mW·cm-2[79] at 800 ℃. It is worth mentioning that when the La content of the material is more than 0.5, it can not exist stably in the air atmosphere above 700 ℃, which greatly affects the preparation and application of the material[80]. Similar to the mechanism of La doping, Sm doping also significantly improves the conductivity of the material in reducing atmosphere[81]. The conductivity of Sr1.4Sm0.6MgMoO6 reaches 16 S·cm-1 in pure hydrogen atmosphere at 800 ℃, which is 14 times higher than that of the same batch of SMM[82].
The tolerance factor of SFM is about 0.99, which is slightly less than 1. Therefore, doping large radius ions at the A-site is beneficial to increase the tolerance factor and transform the material into a cubic structure. Alkali metals are rarely used as doping elements. Most people believe that alkali metals will volatilize during sintering. Hou et al. Used large-radius alkali metal K to replace part of Sr to stabilize the crystal structure[83]. In addition, the large radius element is beneficial to the expansion of the unit cell parameters and the increase of the electronic transition step, thus improving the conductivity of the material, and the conductivity of Sr1.6K0.4FeMoO6 at 900 ℃ is about 2. 5 times that of SFM[84]. When hydrogen was used as the fuel, the output voltage of the cell was switched between 1. 28 V and 0. 2 V (similar to the redox cycle of the anode), and the output power of the cell was significantly decreased.When Fe: Mo was increased to 4, the redox stability could be effectively improved[85].
In addition to A-site doping modification, A-site vacancy is also a common means. The partial Sr vacancy causes the local distortion of the crystal lattice and shortens the Mo-O bond, which is beneficial to the hybridization between the Mo 4D orbital and the O 2p orbital and increases the conductivity[86]. In hydrogen atmosphere at 800 ℃, the conductivity of Sr1.9MgMoO6 reached 15.7 S·cm-1, which was 6 times higher than that of the same batch of SMM. An electrolyte (280 μm) -supported single cell was constructed by using it as the anode, LSGM as the electrolyte, SDC as the buffer layer between the anode and the electrolyte, and BSCF as the cathode. The maximum power density of the cell using pure hydrogen as fuel reached 659 mW·cm-2 at 800 ℃, which was 1. 25 times that of the same batch of SMM[87].

2.2.6 Electrode surface modification

Perovskite anode materials have good structural stability and anti-carbon deposition ability, but its catalytic activity needs to be further improved. Therefore, researchers often modify the surface of double perovskite materials to enhance their electrochemical performance. The common surface modification methods include direct mixing, impregnation and in-situ precipitation.
(1) Direct mixing method
The direct mixing method has a simple preparation process, and the double perovskite electrode material is mixed with a material (such as an electrolyte material, SDC and GDC) with high ionic conductivity, so that the length of a three-phase interface can be prolonged, reaction active sites are increased, and the catalytic activity of the double perovskite electrode material is improved[88⇓⇓~91][92⇓~94]. The polarization impedance of SFM5 mixed with 30 wt% SDC as a symmetrical electrode at 700 ℃ in hydrogen atmosphere is 0.45Ω·cm2, which is only 1/2 of that of the pure SFM5 electrode[88]. SMM combined with GDC also showed good resistance to carbon deposition and sulfur poisoning, and remained stable even in the presence of 10 ppm PH3[92].
(2) Immersion method
B-site transition metals play an important role in the catalytic activity of perovskite structure materials, but A-site alkaline earth metals are easy to segregate in the surface layer under working conditions, resulting in less surface transition metal content and affecting the catalytic activity of materials[95]. A small amount of transition metals, such as Fe, Co, Ni, Mo, etc., are modified on the surface of the electrode by impregnation, which can increase the reactive sites on the surface of the electrode and improve the catalytic activity[96,97]. Electrolyte (300 μm) supported single cell was assembled with SFM5 impregnated with Ni as anode, LSGM as electrolyte and LSCF as cathode. The maximum power density of the cell using hydrogen and methane as fuel at 800 ℃ was 1134 and 663 mW·cm-2, respectively, which was 4 and 20 times higher than that of the single cell without catalyst, respectively[98]. At the same time, the battery still shows good resistance to carbon deposition and sulfur poisoning[99]. In addition to metal elements, impregnation of metal alloys can also greatly enhance the catalytic activity of materials. Electrolyte (300 μm) -supported single cell was assembled by impregnating Co-Ni-Mo alloy in SFM and using it as both cathode and anode, and LSGM as electrolyte. The maximum power density of the cell with hydrogen as fuel at 800 ℃ was 1066 mW·cm-2, while the maximum power density of the cell without alloy catalyst was only 1/4 of that under the same conditions[100]. Due to the good catalytic activity of double perovskite materials, they can also be used as catalysts impregnated in the porous framework of electrolyte, which can also make the electrode show higher catalytic activity[101,102].
(3) In-situ precipitation method
The impregnation method can significantly improve the catalytic activity of the electrode, but the impregnation process is complex and the efficiency is low. By adjust and controlling that component of the material, the B-site element can be precipitated in situ in the anode working atmosphere. Compared with the impregnation method, the in-situ precipitated nano metal or alloy particles are more firmly combined with the matrix and more uniformly distributed. Therefore, in situ precipitation is one of the hot methods of anode surface modification in recent years[103,104]. For example, when Sr2FeMo0.65Ni0.35O6-δ is used as the anode material, FeNi3 nano-alloy particles are precipitated on the surface of the material under the working state of the battery (fig. 5A). Since the existence of FeNi3 nano-alloy particles can promote the process of hydrogen adsorption and dissociation, the anode material shows better electrode catalytic properties[105]. Co particles can be precipitated in situ from the Sr2Fe1.3Co0.2Mo0.5O6-δ in a reducing atmosphere.The material has high catalytic activity and good resistance to carbon deposition, and no significant performance degradation is found after working for nearly 300 H with methane as the fuel[106].

2.2.7 Performance Summary

In order to facilitate comparative analysis, the conductivity, polarization impedance and maximum power density of the B-site double perovskite anode materials summarized above are listed in Table 1, Table 2 and Table 3, respectively.

2.3 A site double perovskite type anode material LnBaM2O5+δ

The structural stability of A-site double perovskites in reducing atmosphere is closely related to the B-site elements. When the B-site elements are Mn and Fe, they can remain stable under the working conditions of the anode. Therefore, LnBaMn2O5+δ and LnBaFe2O5+δ are the two most studied A-site double perovskite anode materials.

2.3.1 LnBaMn2O5+δ

LnBaMn2O5+δ is an A-site ordered layered double perovskite structure material. Because of the strong Mn — O bond, the oxygen vacancies of this kind of material can not be spontaneously ordered at high temperature and in air. Therefore, the A-site ordered LnBaMn2O5+δ can not be directly synthesized in air, and generally need to be further treated in reducing atmosphere[107⇓~109].
Sengodan et al. First proposed the A-site layered ordered double perovskite material PrBaMn2O5+δ(PBM) for SOFC anode[110]. The conductivity of PBM was 8.16 S·cm-1 at 800 ° C in 5%H2/Ar atmosphere, which exhibited high catalytic activity for fuel gas and excellent carbon deposition resistance, and no significant performance degradation was observed after 500 H operation in propane (Fig. 6). According to the structural characteristics of A-site layered perovskite, the concentration of oxygen vacancies can be increased by using lanthanide elements with smaller radius (such as Gd, Nd, etc.), which is beneficial to the improvement of catalytic activity of the material[111,112]. Zhang et al. of our group selected Sm with moderate radius as the A-site element, and assembled an electrolyte (300 μm) supported single cell with SmBaMn2O5+δ(SBM) as both the cathode and anode and LSGM as the electrolyte. When pure hydrogen was used as the fuel, the maximum power density at 850 ℃ was 421 mW·cm-2, and good long-term stability was demonstrated[113].
Sun et al. Used a small amount of Mo to replace the Mn(PrBaMn1.8Mo0.2O5+δ) in order to improve the catalytic oxidation ability of the material for fuel gas[114]. The maximum power density at 850 ℃ of an electrolyte-supported single cell with the PBM anode was about 33% higher than that of the cell with the PBM anode. According to the structural characteristics of A-site double perovskite, the concentration of oxygen vacancies is usually high in reducing atmosphere, and long-term work may lead to structural collapse. In order to enhance the structural stability of the material in reducing atmosphere, Zhang et al. Used Mg with strong metal-oxygen bond to replace part of Mn[115]. The size change of the material was measured by thermal dilatometer when the atmosphere was switched between oxidation and reduction, and the results showed that the chemical expansion of the material caused by the change of working atmosphere was significantly reduced by Mg doping. It is worth mentioning that the introduction of Mg with low catalytic activity does not significantly increase the polarization impedance of the electrode, but slightly decreases due to the better matching between the anode and the electrolyte after doping Mg.

2.3.2 PrBaFe2O5+δ

LnBaFe2O5+δ was initially used as cathode materials, such as PrBaFe2O5+δ, SmBaFe2O5+δ and GdBaFe2O5+δ, because of its good structural stability in air and excellent catalytic activity for oxygen reduction[116][117][118]. Chen et al. First used PrBaFe2O5+δ(PBF) as the anode material of SOFC, and doped Ni at the Fe site[119]. The polarization impedance of PrBaFe1.6Ni0.4O5+δ at 650 ℃ in hydrogen atmosphere is 0.034Ω·cm2, which is only 1/2 of that of PBF. Similar to Ni, the doping of low-valence element Sn is also beneficial to increasing the concentration of oxygen vacancies in the material, thereby improving the catalytic activity of the material. The oxygen content of PBF is 5.58, while the oxygen content of 0.3 Sn doping is only 5.35[120]. With LSGM as the electrolyte, the polarization impedance of PrBaFe1.7Sn0.3O5+δ at 850 ℃ in hydrogen atmosphere is 0.095Ω·cm2.
The conductivity of PBF in hydrogen at 800 ℃ is only 0.5 S·cm-1, which is much lower than that of common anode materials[119]. Considering that PBF is an n-type semiconductor in reducing atmosphere, doping high-valence elements at Fe site is beneficial to reduce the average valence of Fe, thus improving the conductivity of the material in reducing atmosphere. PrBa0.5Sr0.5Fe2-xGexO5+δ(PBSFG) has a conductivity of about 1.1 S·cm-1 in 800 ℃, 20%H2/Ar, while the conductivity of PBF is only 0.018 S·cm-1[121] under the same conditions. The doping of high-valence Mo with variable valence characteristics has a better effect, and the conductivity of the (PrBa)0.95(Fe0.9Mo0.1)2O5+δ reaches the 59.2 S·cm-1 at 800 ℃ and 5%H2/Ar, while the material also shows good resistance to carbon deposition and sulfur poisoning, and no significant performance degradation is found after operating in methane and 30 ppm H2S/H2 for about 500 H[122].

2.3.3 Electrode surface modification

Generally speaking, A-site double perovskite materials have low conductivity in reducing atmosphere and weak catalytic activity for fuel gas, which affects the power characteristics of the cell. Conventional doping is difficult to significantly improve the catalytic activity of the material, at this time, nano-modification of the electrode surface can greatly improve the output power of the battery. Similar to B-site double perovskite materials, impregnation and in-situ precipitation methods are usually used for surface modification.
(1) Immersion method
Compared with the single metal catalyst, the alloy can effectively reduce the carbon deposition phenomenon of the anode and inhibit the abnormal growth of grains[123,124]. Kim et al. studied the change rule of cell performance after impregnating Ni-M (M = Ni, Co, Cu, Fe) alloy catalyst in PBM electrode skeleton, and the results showed that Ni-Fe alloy had the most obvious effect on improving the catalytic activity of the material[125]. Electrolyte (250 μm) -supported single cell was assembled in PBM/YSZ/GdBa0.5Sr0.5CoFeO5+δ configuration, and the maximum power density was 0. 81 and 0.3 W·cm-2 at 700 ℃ when the anode was impregnated with Ni-Fe alloy and H2 and C3H8 were used as fuels, which were 1. 5 times and 3. 3 times higher than that of the non-impregnated sample, respectively. In addition, the alloy catalyst has excellent tolerance to hydrocarbon fuels, and the anode impregnated with Co-Fe alloy has no obvious performance degradation after long-term operation in propane and octane for 250 H[126].
Because PBM has good electrical conductivity and catalytic activity, it can also be impregnated in other electrode materials as a catalyst. The Ni-YSZ/YSZ/GDC/LSCF-GDC configuration was used to assemble an anode-supported single cell. After a small amount of PBM was impregnated on the anode side of the Ni-YSZ, the maximum power density was 1.91 and 1.12 W·cm-2 at 800 ℃ when hydrogen and CH4/CO2 mixture were used as fuel, which was about 30% higher than that of the unimpregnated catalyst sample, and the anode material showed good resistance to carbon deposition and sulfur poisoning[127].
(2) In-situ precipitation method
In-situ precipitation method with simple preparation process is also an important research direction of surface modification. When Mn was partially substituted by a single transition metal, Co and Ni were more likely to precipitate metal nanoparticles on the surface of PBM, and showed better catalytic activity, while the undoped substrate tended to precipitate a small amount of MnO[128⇓~130]. An electrolyte-supported single cell was constructed with doped PBM as the anode, LSGM as the electrolyte, LDC as the buffer layer between the anode and the electrolyte, and NdBa0.5Sr0.5Co1.5Fe0.5O5+δ-GDC(NBSCF-GDC) as the cathode.The maximum power density was 0. 661,0.690,1.15 and 1.12 W·cm-2(800℃) when hydrogen was used as fuel, and the undoped and B-site doped elements were Fe, Co and Ni, respectively. When the PBF is used as the substrate material, the B-site doped Co/Ni is easier to precipitate the iron-containing alloy phase rather than the simple substance, for example, the (PrBa)0.95Fe1.9-xNixMo0.1O5+δ is easy to uniformly precipitate FeNi3 nano-alloy particles on the surface in a reducing atmosphere, and the anode also shows good resistance to carbon deposition and sulfur poisoning, and no obvious performance degradation is found after using sulfur-containing syngas (H2/CO)[131]. According to the principle of defect chemistry, doping with transition metals that do not form an alloy phase with Fe, such as high-valence Nb elements, will lead to the reduction of the valence state of Fe, and even the precipitation of Fe in the form of simple substances in a reducing atmosphere, accompanied by the decomposition of materials to form a small amount of Pr2O3[132].

2.3.4 Performance Summary

The conductivity, power density and polarization impedance of typical A-site double perovskite anode materials are summarized, and the electrochemical performance results at 800 ℃ are shown in Table 4 ~ 6.

3 Conclusions and outlook

In the past decade, the double perovskite structure anode materials have been studied in depth, and great progress has been made in the structure analysis and performance improvement. Double perovskite oxides usually show good resistance to carbon deposition and sulfur poisoning, and have good thermal expansion matching with common electrolyte materials, which make them promising anode materials for SOFC. However, compared with the traditional Ni-YSZ anode, the catalytic activity of the double perovskite anode is still poor, and there are few reports on the preparation of the stack. At the same time, the understanding of the dependence of doping elements on the crystal structure, electronic structure and catalytic properties of materials is not deep enough, which affects the targeted improvement of material properties.
For the B-site double perovskite material, due to the different catalytic properties of the two B-site elements, the crystal orientation of the particles can be controlled, and the types of the B-site elements on the bare crystal face can be controlled, so that the surface catalytic activity of the material can be regulated and controlled. At the same time, the doping of B-site elements can build anti-site defects in the lattice, thus improving the transport capacity of oxygen ions and improving the working characteristics of the electrode. Due to the high anisotropy of A-site double perovskites, the preparation of particles oriented along the c-axis will be conducive to obtaining more surface oxygen active sites and improving the catalytic activity of the material. At the same time, the ordered arrangement of B-site elements with different valence States in A-site double perovskite materials will also affect the electronic structure and catalytic activity of the materials, and further research in this area is needed. In the aspect of electrode surface modification, the precipitation of in-situ nanoparticles is still an efficient and time-saving technical approach with obvious enhancement effect, which shows broad application prospects.
The development of high performance double perovskite anode materials will promote the industrialization of SOFC technology and provide technical support for other high temperature solid-state ion technology.

References

Publishing order | Descend order by publishing year | Descend order by cited within
[1]

Joon K. J. Power Sources, 1998, 71(1/2): 12.
[2]

Choudhury A, Chandra H, Arora A. Renew. Sustain. Energy Rev., 2013, 20: 430.
[3]

van Biert L, Godjevac M, Visser K, Aravind P V. J. Power Sources, 2016, 327: 345.
[4]

Sun C W, Hui R, Roller J. J. Solid State Electrochem., 2010, 14(7): 1125.
[5]

Fergus J W. J. Power Sources, 2006, 162(1): 30.
[6]

Mogensen M, Jensen K V, Jørgensen M J, Primdahl S. Solid State Ionics, 2002, 150(1/2): 123.
[7]

Atkinson A, Barnett S, Gorte R J, Irvine J T S, McEvoy A J, Mogensen M, Singhal S C, Vohs J. Nat. Mater., 2004, 3(1): 17.
[8]

Service R F. Science, 2007, 315(5809): 172.
[9]

Setoguchi T, Okamoto K, Eguchi K, Arai H. J. Electrochem. Soc., 1992, 139(10): 2875.
[10]

Spacil H S. US3503809A, 1970.
[11]

Simwonis D, Tietz F, Stöver D. Solid State Ionics, 2000, 132(3/4): 241.
[12]

Edwards J H, Maitra A M. Fuel Process. Technol., 1995, 42(2/3): 269.
[13]

Zhan Z, Barnett S A. Science, 2005, 308(5723): 844.
[14]

Sun C W, Sun J, Yang W, Ma C H, Li S, Xian C N, Wang S F, Xiao R J, Shi S Q, Li H, Chen L Q. Strategic Study of CAE, 2013, 15(2): 77.
[15]

( 孙春文, 孙杰, 杨伟, 马朝晖, 李帅, 仙存妮, 王少飞, 施思齐, 李泓, 陈立泉. 中国工程科学, 2013, 15(2): 77.)
[16]

Zheng Y, Zhou W, Ran R, Shao Z P. Prog. Chem., 2008, 20(2): 413.
[17]

( 郑尧, 周嵬, 冉然, 邵宗平. 化学进展, 2008, 20(2): 413.)
[18]

Shu L N, Sunarso J, Hashim S S, Mao J K, Zhou W, Liang F L. Int. J. Hydrog. Energy, 2019, 44(59): 31275.
[19]

Ishihara T.. Perovskite Oxide for Solid Oxide Fuel Cells. Boston, MA: Springer US, 2009: 1/16.
[20]

Jonker G H, van Santen J H. Physica, 1950, 16(3): 337.
[21]

Shannon R D. Acta Crystallogr. Sect. A, 1976, 32(5): 751.
[22]

Ullmann H, Trofimenko N. J. Alloys Compd., 2001, 316(1/2): 153.
[23]

Cook R L, Sammells A F. Solid State Ion., 1991, 45(3/4): 311.
[24]

Anderson M T, Greenwood K B, Taylor G A, Poeppelmeier K R. Prog. Solid State Chem., 1993, 22(3): 197.
[25]

King G, Woodward P M. J. Mater. Chem., 2010, 20(28): 5785.
[26]

Taskin A A, Lavrov A N, Ando Y. Appl. Phys. Lett., 2005, 86(9): 091910.
[27]

Taskin A A, Lavrov A N, Ando Y. Prog. Solid State Chem., 2007, 35(2/4): 481.
[28]

Yamazoe N, Teraoka Y. Catal. Today, 1990, 8(2): 175.
[29]

Danilovic N, Vincent A, Luo J L, Chuang K T, Hui R, Sanger A R. Chem. Mater., 2010, 22(3): 957.
[30]

Huang Y H, Dass R I, Denyszyn J C, Goodenough J B. J. Electrochem. Soc., 2006, 153(7): A1266.
[31]

Marrero-LÓpez D, Peña-Martínez J, Ruiz-Morales J C, Martín-Sedeño M C, Núñez P. J. Solid State Chem., 2009, 182(5): 1027.
[32]

Nielsen T H, Leipold M H. J. Am. Ceram. Soc., 1964, 47(3): 155.
[33]

Vasylechko L, Vashook V, Savytskii D, Senyshyn A, Niewa R, Knapp M, Ullmann H, Berkowski M, Matkovskii A, Bismayer U. J. Solid State Chem., 2003, 172(2): 396.
[34]

Hayashi H, Kanoh M, Quan C J, Inaba H, Wang S R, Dokiya M, Tagawa H. Solid State Ionics, 2000, 132(3/4): 227.
[35]

Huang Y H, Dass R I, Xing Z L, Goodenough J B. Science, 2006, 312(5771): 254.
[36]

Marrero-LÓpez D, Peña-Martínez J, Ruiz-Morales J C, Gabás M, Núñez P, Aranda M A G, Ramos-Barrado J R. Solid State Ion., 2010, 180(40): 1672.
[37]

Bi Z H, Zhu J H. J. Electrochem. Soc., 2011, 158(6): B605.
[38]

Li C, Wang W D, Zhao N, Liu Y X, He B, Hu F C, Chen C S. Appl. Catal. B: Environ., 2011, 102(1/2): 78.
[39]

Dorai A K, Masuda Y, Joo J H, Woo S K, Kim S D. Mater. Chem. Phys., 2013, 139(2/3): 360.
[40]

Xie Z X, Zhao H L, Chen T, Zhou X, Du Z H. Int. J. Hydrog. Energy, 2011, 36(12): 7257.
[41]

Dager P K, Mogni L V, Zampieri G, Caneiro A. ECS Trans., 2017, 78(1): 1367.
[42]

Xie Z X, Zhao H L, Du Z H, Chen T, Chen N. J. Phys. Chem. C, 2014, 118(33): 18853.
[43]

Xie Z X, Zhao H L, Du Z H, Chen T, Chen N, Liu X T, Skinner S J. J. Phys. Chem. C, 2012, 116(17): 9734.
[44]

Vasala S, Lehtimäki M, Haw S C, Chen J M, Liu R S, Yamauchi H, Karppinen M. Solid State Ion., 2010, 181(15/16): 754.
[45]

Escudero M J, GÓmez de Parada I, Fuerte A, Daza L. J. Power Sources, 2013, 243: 654.
[46]

Aguadero A, Alonso J A, Martínez-Coronado R, Martínez-Lope M J, Fernández-Díaz M T. J. Appl. Phys., 2011, 109(3): 034907.
[47]

Filonova E A, Dmitriev A S. Eurasian Chem. Technol. J., 2012, 14(2): 139.
[48]

Wei T, Ji Y, Meng X W, Zhang Y L. Electrochem. Commun., 2008, 10(9): 1369.
[49]

Huang Y H, Liang G, Croft M, Lehtimäki M, Karppinen M, Goodenough J B. Chem. Mater., 2009, 21(11): 2319.
[50]

Zhang P, Huang Y H, Cheng J G, Mao Z Q, Goodenough J B. J. Power Sources, 2011, 196(4): 1738.
[51]

Kumar P, Singh N K, Singh R K, Singh P. Appl. Phys. A, 2015, 121(2): 635.
[52]

Wei T, Zhang Q, Huang Y H, Goodenough J B. J. Mater. Chem., 2012, 22(1): 225.
[53]

Zheng K, Świerczek K, Zajᶏc W, Klimkowicz A. Solid State Ion., 2014, 257: 9.
[54]

Zheng K, Świerczek K. J. Eur. Ceram. Soc., 2014, 34(16): 4273.
[55]

Wei T, Zhang Q, Huang Y H. J. Electrochem. Soc., 2012 (6): 332.
[56]

Zhang L L, Zhou Q J, He Q, He T M. J. Power Sources, 2010, 195(19): 6356.
[57]

Wang Z M, Tian Y, Li Y D. J. Power Sources, 2011, 196(15): 6104.
[58]

Liu G Y, Rao G H, Feng X M, Yang H F, Ouyang Z W, Liu W F, Liang J K. J. Alloys Compd., 2003, 353(1/2): 42.
[59]

Li H J, Zhao Y C, Wang Y C, Li Y D. Catal. Today, 2016, 259: 417.
[60]

Rager J, Zipperle M, Sharma A, Macmanus-Driscoll J L. J. Am. Ceram. Soc., 2004, 87(7): 1330.
[61]

Xiao G L, Liu Q, Dong X H, Huang K, Chen F L. J. Power Sources, 2010, 195(24): 8071.
[62]

Xiao G, Liu Q, Nuansaeng S, Chen F. ECS Trans., 2012, 45(1): 355.
[63]

Du Z H, Zhao H L, Li S M, Zhang Y, Chang X W, Xia Q, Chen N, Gu L, Świerczek K, Li Y, Yang T R, An K. Adv. Energy Mater., 2018, 8(18): 1800062.
[64]

Dai N N, Feng J, Wang Z H, Jiang T Z, Sun W, Qiao J S, Sun K N. J. Mater. Chem. A, 2013, 1(45): 14147.
[65]

Liu Q, Dong X H, Xiao G L, Zhao F, Chen F L. Adv. Mater., 2010, 22(48): 5478.
[66]

Liu Q, Bugaris D E, Xiao G L, Chmara M, Ma S G, zur Loye H C, Amiridis M D, Chen F L. J. Power Sources, 2011, 196(22): 9148.
[67]

Zheng K, Świerczek K, Polfus J M, Sunding M F, Pishahang M, Norby T. J. Electrochem. Soc., 2015, 162(9): F1078.
[68]

Himmel M E, Ding S Y, Johnson D K, Adney W S, Nimlos M R, Brady J W, Foust T D. Science, 2007, 315(5813): 804.
[69]

Li H J, Tian Y, Wang Z M, Qie F C, Li Y D. RSC Adv., 2012, 2(9): 3857.
[70]

Bode G L, McIntyre M D, Neuberger D M, Walker R A, Thorstensen B P, Eigenbrodt B C. ChemElectroChem, 2018, 5(21): 3162.
[71]

Gou M L, Ren R Z, Sun W, Xu C M, Meng X G, Wang Z H, Qiao J S, Sun K N. Ceram. Int., 2019, 45(12): 15696.
[72]

Zhang L L, Zhou Q J, He Q, He T M. J. Power Sources, 2010, 195(19): 6356.
[73]

Cowin P I, Lan R, Petit C T G, Tao S W. Mater. Chem. Phys., 2015, 168: 50.
[74]

Osinkin D A, Zabolotskaya E V, Kellerman D G, Suntsov A Y. J. Solid State Electrochem., 2018, 22(4): 1209.
[75]

Osinkin D A, Beresnev S M, Khodimchuk A V, Korzun I V, Lobachevskaya N I, Suntsov A Y. J. Solid State Electrochem., 2019, 23(2): 627.
[76]

Xu Z Q, Hu X Y, Wan Y H, Xue S S, Zhang S W, Zhang L J, Zhang B Z, Xia C R. Electrochimica Acta, 2020, 341: 136067.
[77]

Qi H, Thomas T, Li W Y, Li W, Liu X B. ACS Appl. Energy Mater., 2019, 2(6): 4244.
[78]

Kumar P, Jena P, Patro P K, Lenka R K, Sinha A S K, Singh P, Singh R K. ACS Appl. Mater. Interfaces, 2019, 11(27): 24659.
[79]

Xie Z X, Chen T, Zhao H L, Du Z H, Li Y M. J. Chin. Ceram. Soc., 2016, 44(6): 817.
[80]

( 谢志翔, 陈婷, 赵海雷, 杜志鸿, 李月明. 硅酸盐学报, 2016, 44(6): 817.)
[81]

Yang X, Chen J, Panthi D, Niu B B, Lei L B, Yuan Z H, Du Y H, Li Y F, Chen F L, He T M. J. Mater. Chem. A, 2019, 7(2): 733.
[82]

Ji Y, Huang Y H, Ying J R, Goodenough J B. Electrochem. Commun., 2007, 9(8): 1881.
[83]

Howell T G, Kuhnell C P, Reitz T L, Eigenbrodt B C, Singh R N. J. Am. Ceram. Soc., 2014, 97(11): 3636.
[84]

Wang Y, Li P, Li H, Zhao Y, Li Y. Fuel Cells, 2014, 14(6): 973.
[85]

Zhang L L, He T M. J. Power Sources, 2011, 196(20): 8352.
[86]

Hou S E, Aguadero A, Alonso J A, Goodenough J B. J. Power Sources, 2011, 196(13): 5478.
[87]

Sugahara T, Araki T, Ohtaki M, Suganuma K. J. Ceram. Soc. Japan, 2012, 120(1402): 211.
[88]

Cowin P I, Lan R, Petit C T G, Wang H T, Tao S W. J. Mater. Sci., 2016, 51(8): 4115.
[89]

Yao G B, Cai H D, Zhang L L, Xu J S, Song Z Y. J. Liaoning Shihua Univ., 2019, 39(4): 28.
[90]

( 姚桂彬, 蔡洪东, 张磊磊, 徐璟升, 宋昭远. 辽宁石油化工大学期刊社, 2019, 39(4): 28.)
[91]

Jiang L, Liang G, Han J T, Huang Y H. J. Power Sources, 2014, 270: 441.
[92]

He B B, Zhao L, Song S X, Liu T, Chen F L, Xia C R. J. Electrochem. Soc., 2012, 159(5): B619.
[93]

Osinkin D A, Lobachevskaya N I, Kuz’min A V. Russ. J. Appl. Chem., 2017, 90(1): 41.
[94]

Osinkin D A, Beresnev S M, Lobachevskaya N I. Russ. J. Electrochem., 2017, 53(6): 665.
[95]

Osinkin D A, Lobachevskaya N I, Suntsov A Y. J. Alloys Compd., 2017, 708: 451.
[96]

Gansor P, Xu C C, Sabolsky K, Zondlo J W, Sabolsky E M. J. Power Sources, 2012, 198: 7.
[97]

Guo Y Y, Guo T M, Zhou S J, Wu Y J, Chen H, Ou X M, Ling Y H. Ceram. Int., 2019, 45(8): 10969.
[98]

Xie Z X, Zhao H L, Lei Y M, Chen T. J. Ceram., 2016, 37(1): 53.
[99]

( 谢志翔, 赵海雷, 李月明, 陈婷. 陶瓷学报, 2016, 37(1): 53.)
[100]

Suthirakun S, Ammal S C, Muñoz-García A B, Xiao G L, Chen F L, zur Loye H C, Carter E A, Heyden A. J. Am. Chem. Soc., 2014, 136(23): 8374.
[101]

Jiang S P. Mater. Sci. Eng.: A, 2006, 418(1/2): 199.
[102]

Jiang S P. Int. J. Hydrog. Energy, 2012, 37(1): 449.
[103]

Xiao G L, Chen F L. Electrochem. Commun., 2011, 13(1): 57.
[104]

Xiao G L, Jin C, Liu Q, Heyden A, Chen F L. J. Power Sources, 2012, 201: 43.
[105]

Rath M K, Lee K T. Electrochimica Acta, 2016, 212: 678.
[106]

Han Z Y, Wang Y H, Yang Y R, Li L L, Yang Z B, Han M F. J. Alloys Compd., 2017, 703: 258.
[107]

Liu J, Lei Y, Li Y M, Gao J, Han D, Zhan W T, Huang F Q, Wang S R. Electrochem. Commun., 2017, 78: 6.
[108]

Neagu D, Tsekouras G, Miller D N, MÉnard H, Irvine J T S. Nat. Chem., 2013, 5(11): 916.
[109]

Sun Y F, Li J H, Cui L, Hua B, Cui S H, Li J, Luo J L. Nanoscale, 2015, 7(25): 11173.
[110]

Du Z H, Zhao H L, Yi S, Xia Q, Swierczek K. ACS Nano, 2016, 10(9): 8660.
[111]

Yang Y R, Wang Y R, Yang Z B, Lei Z, Jin C, Liu Y D, Wang Y H, Peng S P. J. Power Sources, 2019, 438: 226989.
[112]

Trukhanov S V, Trukhanov A V, Szymczak H, Szymczak R, Baran M. J. Phys. Chem. Solids, 2006, 67(4): 675.
[113]

Nakajima T, Yoshizawa H, Ueda Y. J. Phys. Soc. Jpn., 2004, 73(8): 2283.
[114]

Rykov A I, Ueda Y, Nomura K. J. Solid State Chem., 2009, 182(8): 2157.
[115]

Sengodan S, Choi S, Jun A, Shin T H, Ju Y W, Jeong H Y, Shin J, Irvine J T S, Kim G. Nat. Mater., 2015, 14(2): 205.
[116]

Jeamjumnunja K, Gong W Q, Makarenko T, Jacobson A J. J. Solid State Chem., 2016, 239: 36.
[117]

Pineda O L, Moreno Z L, Roussel P, Świerczek K, Gauthier G H. Solid State Ion., 2016, 288: 61.
[118]

Zhang Y, Zhao H L, Du Z H, Świerczek K, Li Y Y. Chem. Mater., 2019, 31(10): 3784.
[119]

Sun Y F, Zhang Y Q, Hua B, Behnamian Y, Li J, Cui S H, Li J H, Luo J L. J. Power Sources, 2016, 301: 237.
[120]

Zhang Y, Zhang B, Zhao H, Świerczek K, Li H. Catal. Today, 2020.
[121]

Ding H P, Xue X J. J. Power Sources, 2010, 195(20): 7038.
[122]

He Z P, Xia L N, Chen Y H, Yu J C, Huang X W, Yu Y. RSC Adv., 2015, 5(71): 57592.
[123]

Ding H P, Xue X J. J. Power Sources, 2010, 195(15): 4718.
[124]

Chen Y H, Cheng Z X, Yang Y, Gu Q W, Tian D, Lu X Y, Yu W L, Lin B. J. Power Sources, 2016, 310: 109.
[125]

Dong G H, Yang C Y, He F, Jiang Y M, Ren C L, Gan Y, Lee M, Xue X J. RSC Adv., 2017, 7(37): 22649.
[126]

Lee D, Kim D, Son S J, Kwon Y I, Lee Y, Ahn J H, Joo J H. J. Power Sources, 2019, 434: 226743.
[127]

Ding H P, Tao Z T, Liu S, Zhang J J. Sci. Rep., 2015, 5(1): 1.
[128]

Miyake M, Iwami M, Takeuchi M, Nishimoto S, Kameshima Y. J. Power Sources, 2018, 390: 181.
[129]

Ding G C, Gan T, Yu J, Li P, Yao X L, Hou N J, Fan L J, Zhao Y C, Li Y D. Catal. Today, 2017, 298: 250.
[130]

Kim S, Kim C, Lee J H, Shin J, Lim T H, Kim G. Electrochimica Acta, 2017, 225: 399.
[131]

Choi S, Sengodan S, Park S, Ju Y W, Kim J, Hyodo J, Jeong H Y, Ishihara T, Shin J, Kim G. J. Mater. Chem. A, 2016, 4(5): 1747.
[132]

Hua B, Li M, Sun Y F, Zhang Y Q, Yan N, Li J, Etsell T, Sarkar P, Luo J L. Appl. Catal. B: Environ., 2017, 200: 174.
[133]

Kwon O, Sengodan S, Kim K, Kim G, Jeong H Y, Shin J, Ju Y W, Han J W, Kim G. Nat. Commun., 2017, 8(1): 1.
[134]

Sengodan S, Ju Y W, Kwon O, Jun A, Jeong H Y, Ishihara T, Shin J, Kim G. ACS Sustainable Chem. Eng., 2017, 5(10): 9207.
[135]

Bahout M, Managutti P B, Dorcet V, Le Gal la Salle A, Paofai S, Hansen T C. J. Mater. Chem. A, 2020, 8(7): 3590.
[136]

Xue S S, Shi N, Wan Y H, Xu Z Q, Huan D M, Zhang S W, Xia C R, Peng R R, Lu Y L. J. Mater. Chem. A, 2019, 7(38): 21783.
[137]

Li J W, Wei B, Yue X, Li H, Lü Z. Electrochimica Acta, 2019, 304: 30.

Funding

National Key R&D Program of China(2018YFB1502202)

Global Energy Interconnection Research Institute Co. Ltd(SGGR0000WLJS1900863)

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