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La3+-substituted Sr2Fe1.5Ni0.1Mo0.4O6-δ as Anodes for Solid Oxide Fuel Cells

2020-06-07 07:25:58XIATianMENGXieLUOTingZHANZhongliang
無機材料學報 2020年5期

XIA Tian, MENG Xie, LUO Ting, ZHAN Zhongliang

La3+-substituted Sr2Fe1.5Ni0.1Mo0.4O6-δas Anodes for Solid Oxide Fuel Cells

XIA Tian1,2, MENG Xie1, LUO Ting1, ZHAN Zhongliang1

(1. CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China)

Lanthanum-substituted LaSr2–3x/2Fe1.5Ni0.1Mo0.4O6-δ(LaSFNM,=0, 0.1, 0.2, 0.3, 0.4) oxides were synthesized by the solid-state reaction method, and investigated as potential anodes for Solid Oxide Fuel Cells(SOFC). X-ray diffraction patterns of as-synthesized powders confirm the formation of the cubic perovskite structure. Reduction in H2promotes the segregation of nano-scale metallic Fe-Ni alloy particles on the grain surfaces. Scanning electron microscopy observations indicate that increasing La3+dopants results in a decrease in the density of the exsolved nanoparticulates. Based upon impedance measurements on symmetrical fuel cells, the anode polarization resistance decreases with the La3+dopant increasing, and attains a minimal value of 0.16W?cm2for La0.3SFNM at 750 ℃, followed by a slight increase to 0.17W?cm2for La0.4SFNM. The highest catalytic activity of La0.3SFNM toward electro- oxidation of hydrogen fuels could be ascribed to the synergy between the exsolved Fe-Ni alloy nanoparticulates and the supporting LaSFNM oxides. Thin La0.9Sr0.1Ga0.8Mg0.2O3(LSGM) electrolyte fuel cells with La0.3SFNM anodes and SmBa0.5Sr0.5Co2O6cathodes exhibit the highest power densities,, 1.26, 0.90 and 0.52 W?cm-2at 750, 650 and 550 ℃, respectively. These results demonstrate La0.3SFNM oxide as a promising high performance SOFC anode.

Solid Oxide Fuel Cells; anode materials;exsolution

With increasing concerns on energy shortage and environment pollution over the last few decades, Solid Oxide Fuel Cells (SOFCs) have gained worldwide attention as a new means of power generation due to their coherent characteristics of high electrical efficiencies and low emissions. As the state-of-the-art anode materials, Ni/YSZ cermets exhibit excellent catalytic activity toward hydrogen oxidation reactions, but very poor redox stability with high susceptibility toward Ni coarsening during the long-term operation[1]. In order to overcome these issues, a series of conductive oxides were investigated as alternative anodes. Some perovskite oxides such as La1–3x/2SrTiO3-δ[2], La0.75Sr0.25Cr0.5Mn0.5O3-δ[3]and Sr2Fe1.5Mo0.5O6-δ[4]showed promising anode performance owing to their high thermal and chemical stability as well as high mixed ionic and electronic conductivities. Optimization of the chemical composition and the structural defects may allow for some improvements in the anode performance[5–7], nevertheless, their catalytic activity was still much lower than the typical Ni-cermet anodes. Adding a secondary catalyst to the perovskite oxide by infiltration[8-9]or vapor deposition[10]was effective in improving the overall anode performance. It remains a challenge to precisely control their surface morphology with enhanced long-term stability at elevated temperatures.

exsolution was demonstrated as an elegant and effective approach to obtain nano-scale metal catalysts on the surface of perovskite oxides[11–14].Specifically, transitional metals such as Ni, Co and Pt were selectedto partiallysubstitute the B-sites of the perovskite oxides during the powder synthesis in air, which were thensegregated from the lattice and precipitated as metal nanoparticulates in the reducing environments at high temperatures. With an ideal catalyst morphology, these exsolved metal nanoparticulates evenly distributed on the surface of the perovskite oxides. Note that the amounts and sizes of these metal nanoparticulates may significantly affect the anode performance[15]. Moreover, their physical distribution may also change due to the continuous precipitation in the reducing environments at high temperatures[16].Therefore, it becomes crucial to control the ion segregation kinetics so as to optimize the dimension and density of the exsolved nanoparticulates, thereby enhancing their performance as the anode catalysts[17].

Recently, non-stoichiometry[12]and additional electric field[18]were used to tailor the metal segregation process. Furthermore, the segregation driving force was analyzed by the distribution of relaxation time(DRT) calculations[11,19-20], indicating that ion size mismatch and electrostatic interaction played important roles in the segregation process. Altering the dopant valence and the ion size may change the exsolution behaviour.In this work, lanthanum was introduced into the A-site to partially replace Sr2+in Sr2Fe1.5Ni0.1Mo0.4O6-δ. A series of samples, LaSr2–3x/2Fe1.5Ni0.1Mo0.4O6-δ(=0–0.4), were synthesized in air. The chemical compositions were examined before and after reduction in H2by X-ray diffraction(XRD), with the surface morphology observed using scanning electron microscope (SEM). It was found that La doping could inhibitexsolution of Fe-Ni alloys and improve the stability of ceramic substrates. Symmetrical anode fuel cells and functioning fuel cells were fabricated by the impregnation method and tested to verify optimization of the anode performance for LaSr2–3x/2Fe1.5Ni0.1Mo0.4O6-δat= 0.3.

1 Experimental

LaSFNM (LaSr2–3x/2Fe1.5Mo0.4Ni0.1O6-δ,=0, 0.1, 0.2, 0.3, 0.4) powders used in this study were synthesized by the standard solid-state reaction method. The starting materials were La2O3(>99%), SrCO3(>98%), Fe2O3(>98%), MoO3(>99%) and NiO (>99%). La2O3was fired at 800 ℃ for 12 h before being weighed, and SrCO3was dried at 150 ℃ to remove the adsorbed water in air. Similar to the synthesis of Sr2Fe1.5Mo0.5O6(SFM) powders[21], the first step was to prepare Fe2Mo3O12. Fe2O3and MoO3oxides were mixed and thoroughly ground by ball milling in anhydrous ethanol at a stoichiometric ratio of 1:3 with 6wt% triethanolamine as the dispersant. The mixture was heat-treated at 750 ℃ for 12 h with the resulting phase pure Fe2Mo3O12oxide confirmed by XRD. Next, a sto-ichiometric ratio of La2O3, SrCO3, Fe2O3, Fe2Mo3O12and NiO were similarly mixed and ball milled for 12 h in an-hydrous ethanol. In order to ensure full decomposition of SrCO3to SrO and CO2, the mixture was heated at 3 ℃/min up to 1000 ℃ and held at this temperature for 12 h. After cooling to room temperature, the powders were reground in the mortar, followed by the second heattreatment at 1200 ℃ for 12 h.

The crystalline structure of as-synthesized LaSFNM powders was examined by XRD using Rigaku Ultima IV with monochromatic Cu Kα radiation. In order to analyze the ceramic surface morphology afterdissolution of metal particles in the reducing environments, ceramic pellets were prepared by uniaxially dry-pressing LaSFNM powders under 15 MPa, followed by sintering at 1400 ℃ for 5 h in air and reducing at 750 ℃ for 4 h in wet 10vol% H2/N2(3vol% H2O). SFNM and La0.3SFNM samples were further reduced at 800 ℃ in pure hydrogen for 24 h. The surface topography was observed by SEM (Hitachi SU8220 and FEI Inspect F50), and the chemical compositio-ns of the precipitated particles were analyzed by EDS.

Symmetrical anode fuel cells were prepared by the impregnation method, and La0.9Sr0.1Ga0.8Mg0.2O3(LSGM) was selected as the electrolyte due to its high oxide ionic conductivity. “Porous|dense|porous” LSGM scaffolds were obtained by laminating the tape-casted ceramic green tapes with rice starch as the fugitive material for the porous layers, as reported in our previous publication[22]. The LaSFNM anode catalysts were added by infiltrating an aqueous solution, containing La(NO3)3, Sr(NO3)2, Fe(NO3)3·9H2O, Ni(NO3)2, (NH4)6Mo7O24·4H2O and citric acid at an appropriate ratio, followed by calcinations at 850 ℃ for 30 min. Such a process was repeated until a catalyst loading of 30wt% was achieved after calcination at 1000 ℃ for 4 h to produce the perovskite oxides. The impedance data were measured on the symmetrical anode fuel cells in 97vol% H2-3vol% H2O at 100 sccm using the Electrochemical Workstation (ZAHNER IM6e, Germany) over the frequency range of 0.05 Hz to 100 kHz.

To fabricate the functioning fuel cells, SmBa0.5Sr0.5Co2O5+δ(SBSCO) was infiltrated as the cathode catalyst into the porous LSGM of the tri-layered scaffolds on one side, with the LaSFNM anode catalysts infiltrated on the other side. SBSCO was selected as the cathode catalyst owing to its high electrical conductivity and excellent catalytic activity toward oxygen reduction reactions. The effective area of as-prepared fuel cells was 1.05 cm2. Silver paste (DAD-87, Shanghai Research Institute of Synthetic Resins) was printed on the electrode surface to collect the electrical current. Single cells were sealed on the alumina tubes using the ceramic glue. The anode was reduced in humidified H2for 5 h before any electrochemical measurement.

2 Results and discussion

The crystalline structure of as-synthesized powders was determined by room temperature XRD. Fig. 1(a) summarizes the XRD patterns of a series of LaSFNM (=0, 0.1, 0.2 0.3 and 0.4) oxides, which can be well indexed in single perovskite structure with cubic symmetry. Fig. 1(b) shows the XRD patterns of the thermally treated oxides in wet H2(3vol% H2O) at 750 ℃, showing the formation of minor amounts of secondary FeNi3(#88-1715) phases at 2=44° and 51° for=0–0.2. Fig. 1(b) also shows that diffraction peaks from FeNi3decreased with the La3+dopant increasing, which became difficult to be detected at=0.3 and 0.4. These results suggest that doping La3+in the A-site seemingly inhibit theexsolution behavior of Sr2Fe1.5Ni0.1Mo0.4O6-δoxides and thereby enhance the structural stability of LaSFNM oxides in the reducing environments.

Fig. 1 Room temperature XRD patterns of LaxSFNM (x=0, 0.1, 0.2, 0.3, 0.4)

(a) After calcination at 1200 ℃ for 12 h; (b) Reduced in wet H2(3vol% H2O) at 750 ℃ for 12 h

To better understand the influence of lanthanum dopants on the exsolution behavior and the resulting morphology of nanoparticulates, a series of LaSFNM (=0, 0.1, 0.2, 0.3, 0.4) pellets were prepared at 1400 ℃in air and then reduced in 10vol% H2/N2at 750 ℃ for 4 h. Fig. 2 shows the surface morphologies of as-prepared and reduced perovskite oxides. The as-prepared SFNM sample shows clean and smooth grains without any visible secondary phases (Fig. 2(a)). Upon reduction, many nano-scale particles exsolved and homogeneously distributed on the oxide surface (Fig. 2(b-f)). EDS analysis confirms that these precipitated nanoparticulates exist largely as Fe-Ni alloys (Fig. 3), consistent with the XRD peaks of FeNi3in Fig.1(b). The diameter of Fe-Ni alloy nanoparticles is 40–60 nm. Fig. 2 also shows that the density of exsolved nanoparticulates on the oxide surface decreases significantly with the La3+dopant increasing, supporting the conclusion from the XRD analysis that doping La3+in the A-site helps to inhibit the exsolution of metal nanoparticulates and thus improve the structural stability of the pristine perovskite oxides.

Fig. 2 Surface morphologies of (a) SFNM ceramic pellets before reduction and (b-f) LaxSFNM ceramic pellets after reduction in humidified 10vol% H2/N2 (3vol% H2O) at 750 ℃ for 4 h

(b) SFNM; (c) La0.1SFNM; (d) La0.2SFNM; (e) La0.3SFNM; (f) La0.4SFNM

Fig. 3 (a) SEM image of reduced La0.3SFNM ceramic surface and (b-g) elemental mapping of La (b, blue), Sr (c, magenta), Fe (d, red), Ni (e, yellow), Mo (f, brown) and O (g, green)

The polarization resistance provides a quantitative measurement of the catalytic activity of LaSFNM oxides toward electro-oxidation of hydrogen, which can be readily obtained from impedance measurements on symmetrical anode fuel cells,, Nano-LaSFNM@LSGM|LSGM|Nano-LaSFNM@ LSGM. Fig. 4(a) summarizes Nyquist plots of impedance spectra measured at 750 ℃in a homogeneous- environment of 97vol% H2–3vol% H2O for symmetrical anode fuel cells with varied La3+dopants, where the ohmic resistances due to the electrolytes and the collecting wires were removed and the polarization resistances were divided by two to account for contributions of two symmetrical anodes. The anode specific polarization resistances (P, A) are taken as the overall widths of depressed arcs in Fig. 4(a). The anode polarization resistance isP,A=0.21W?cm2for SFNM, decreases gradually with the La3+dopant increasing, and attains a minimal value of 0.16W?cm2at=0.3. Further increasing the La3+dopant yields a slightly increasedP,Avalue (0.17 Ω?cm2) for La0.4SFNM cell. The Bode plots of impedance data in Fig. 4(b) show that the response difference mainly occurs over the frequency range of 10–1000 Hz. Analysis of Distribution of Relaxation Time (DRT) was performed to effectively separate the multiple time constants[23-24], with the results summarized in Fig. 4(c). Notably, the impedance spetra consist of three different processes (denoted asH,M,L) in the frequency range of 100–1000, 10–100 and 0.1–10 Hz, respectively. Similar to the SFNM anode, the high-frequency resistanceHrelates to charge transfer across the electrolyte/electode interface, whereas the medium- and low-frequency resistances (MandL) are associated with the surface reactions[13,25]. Increasing the La3+dopant yields a pronounced decrease inMwithHandLalmost unchanged, indicating that doping La3+in the A-site effectively promotes the surface reaction on the perovskite oxides. Since the SEM observations show inhibited exsolution of FeNi3nanoparticulates and increased stability of the perovskite oxides with more La3+dopants, the optimal catalytic activity at=0.3 may be associated with the synergy between the exsolved catalysts and the supporting perovskite oxides.

The anode behavior was further examined on the functioning fuel cells as fabricated from tri-layer structures of “porous|dense|porous” LSGM. The dense LSGM electrolytes are typically ~22mm thick (Fig. 5(a)). SBSCO and La0.3SFNM were impregnated into the two porous LSGM scaffolds, respectively. High magnification view of the anode after the fuel cell measurements show the formation ofexsolved nanoparticulates on the surface of La0.3SFNM oxides (Fig. 5(b)). Fig. 6(a) shows the representative polarization curves of the cell voltages () and power densities () as functions of current densities ()for the single cells with La0.3Sr1.55Fe1.5Ni0.1Mo0.4O6-δas anode catalyst. The maximum power densities are 1.26, 1.13, 0.90, 0.74 and 0.52 W?cm–2at 750, 700, 650, 600 and 550 ℃, respectively. Cells with varied La3+doped anodes were also prepared and measured under similar conditions, with the results compared in Fig. 6(b). The cells (=0.3) exhibit the highest power densities at all temperatures. The present values are also much higher than previously reported power densities,, 0.59 W?cm–2for SFNiM[13]and 0.85 W?cm–2for SFM[26]at 750 ℃.

Long-term stability of nano-scale FeNi3catalysts as shown in Fig. 2 is very questionable due to their high susceptibility to continuous agglomeration and coarsening at elevated temperatures. Although extended measurements are required for better evaluation of the long- term stability of these nano-scale catalysts, some of the cells were operated for a few hundred hours. Fig. 7 shows a representative plot of the cell voltage as a function of time. The single cell was run at 0.5 A?cm–2under 550 ℃ for 120 h, followed by another 80 h operation at 1.0 A?cm–2, 650 ℃, showing negligible decay in the power output at both temperatures. These results demonstrate great promise of La0.3Sr1.55Fe1.5Mo0.4Ni0.1O6-δas efficient catalyst for electro-oxidation of hydrogen fuels.

Fig. 4 (a) Nyquist and (b) Bode plots of impedance data for symmetrical anode fuel cells, i.e., Nano-LaxSFNM@LSGM | LSGM | Nano-LaxSFNM@ LSGM, operating in humidified H2 (3vol% H2O, 100 mL·min–1) at 750 ℃, (c) distributions of relation time (DRT) plots of the data shown in (a) and (b)

Fig. 5 (a) Cross-sectional micrograph of measured fuel cell (Nano-La0.3SFNM@LSGM|LSGM|Nano-SBSCO@LSGM), and (b) high magnification view of the impregnated catalyst

Fig. 6 (a) Voltage and power density versus current density for the functioning fuel cell (Nano-La0.3SFNM@LSGM|LSGM| Nano-SBSCO@LSGM), measured in 97vol% H2-3vol% H2O at 100 sccm; (b) Peak power densities at different temperatures for single cells with varied LaxSFNM anodes

3 Conclusion

In summary, a series of LaSr2-3x/2Fe1.5Ni0.1Mo0.4O6-δ(=0–0.4) oxides were synthesized, and their structural stability in reducing environments was examined. Both XRD patterns and SEM observations confirm the exsolution of nano-scale FeNi3particles on the oxide surface after the thermal treatment in H2. Increasing the La3+dopant enhances the structural stability of these oxides with inhibited exsolution of FeNi3nanoparticulates. Synergy between the exsolved FeNi3nanoparticulates and the supporting oxides yields the highest catalytic activities toward hydrogen oxidation reactions with the lowest polarization resistances at=0.3,, 0.16W?cm2at 750 ℃. Thin LSGM electrolyte SOFCs with nano- La0.3Sr1.55Fe1.5Mo0.4Ni0.1O6-δ@LSGM anodes and nano- SBSCO@LSGM cathodes produces peak power densities of 1.26, 0.90 and 0.52 W?cm–2at 750, 650 and 550 ℃, respectively.

Fig. 7 Cell voltage as a function of operation time for the singlefuel cell (Nano-La0.3SFNM@LSGM|LSGM|Nano-SBSCO@ LSGM), operated under constant current density at 550 and 650 ℃

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固體氧化物燃料電池LaSr2-3x/2Fe1.5Ni0.1Mo0.4O6-δ陽極性能研究

夏天1,2, 孟燮1, 駱婷1, 占忠亮1

(1. 中國科學院 上海硅酸鹽研究所, 能量轉換材料重點實驗室, 上海 200050;2. 中國科學院大學, 北京 100049)

本研究利用固相反應法合成了一系列鑭取代LaSr2-3x/2Fe1.5Ni0.1Mo0.4O6-δ(LaSFNM,=0, 0.1, 0.2, 0.3, 0.4)鈣鈦礦陶瓷材料, 并研究其作為固體氧化物燃料電池陽極的電化學性能。X射線衍射(XRD)測試表明合成的粉末具有立方鈣鈦礦結構。在高溫下利用氫氣還原LaSFNM樣品, 發現其晶粒表面析出納米尺度的Fe-Ni合金顆粒, 并且偏析納米顆粒的密度隨著La3+摻雜量的增加而顯著降低。在對稱電池阻抗測試中, 隨著La3+摻雜量的增加, 陽極極化阻抗逐漸降低, 摻入量為0.3時阻抗達到最小值。La0.3SFNM對稱電池在750 ℃下極化阻抗僅為0.16W?cm2, 進一步增加摻雜量時, La0.4SFNM對稱電池極化阻抗增加至0.17W?cm2。La0.3SFNM材料良好的電極反應催化活性源于適當分布的Fe-Ni合金納米偏析顆粒與LaSFNM陶瓷基體的共同作用。利用流延法制備一系列以LaSFNM為陽極、SmBa0.5Sr0.5Co2O6為陰極、LSGM為電解質的單電池, 使用氫氣作為燃料時, La3+摻雜量=0.3的單電池表現出最高的功率密度, 在750、650和550 ℃時峰值功率密度可達1.26、0.90和0.52 W·cm–2。上述結果表明, La0.3Sr1.55Fe1.5Ni0.1Mo0.4O6-δ可以用作高性能SOFC陽極催化劑。

固體氧化物燃料電池; 陽極材料; 高溫原位脫溶

TM911

A

2019-05-15;

2019-05-29

National Natural Science Foundation of China (51672298, 51702344, 51737011); The State of Grid (SGSDJN00FZQT1700446)

XIA Tian (1993–), male, Master candidate. E-mail: xiatian@student.mail.sic.ac.cn

夏天(1993–), 男, 碩士研究生. E-mail: xiatian@student.mail.sic.ac.cn

ZHAN Zhongliang, professor. E-mail: zzhan@mail.sic.ac.cn

占忠亮, 研究員. E-mail: zzhan@mail.sic.ac.cn

1000-324X(2020)05-0617-06

10.15541/jim20190225

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