Preparation and electrochemical properties of La0.5Sr0.5Co0.2Fe0.8O3 oxides as bifunctional catalysts for reversible single-component cells
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摘要: 利用SBA-15硬模板合成La0.5Sr0.5Co0.2Fe0.8O3 (LSCF)钙钛矿材料，通过研究LSCF的电化学性能，探究制备溶剂（甲醇/乙醇）对LSCF结构、表面性质及电化学性能的影响。结果表明，乙醇溶剂制备的LSCF具有更大的比表面积和更多的氧空位浓度，从而表现出更高的电导率以及对氧还原反应(ORR)和氢氧化反应(HOR)更好的催化活性。这是因为乙醇溶剂制备的LSCF具有更多的Co2 + /Co3 + 和Fe2 + /Fe3 + 电子对，促进了材料的电子传导。此外，对于HOR，电极反应的速率控制步骤(RDS)是吸附的氢原子转移到反应位点；吸附的氧原子在LSCF上的还原是ORR反应的RDS。此外，由乙醇溶剂制备的LSCF组成的可逆单部件电池(RSCC)具有更好的放电和电解水性能。700 ℃，H2-30%H2O燃料下，RSCC的最大功率密度为232.9 mW/cm2，并且在1.3 V的电解电流密度为−398.3 mA/cm2。Abstract: La0.5Sr0.5Co0.2Fe0.8O3 (LSCF) perovskite materials were prepared by hard template method with SBA-15 as the template in methanol and ethanol solvents and the electrochemical properties of LSCF were investigated. It is found that LSCF prepared with ethanol solvent has larger specific surface area and more oxygen vacancy concentration, which in turn exhibits higher electrical conductivity and better catalytic activity towards oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR). This is because the LSCF prepared by the ethanol solvent has more Co2 + /Co3 + and Fe2 + /Fe3 + electron pairs, which promotes the electronic conduction of the material. In addition, for HOR, the rate determining step (RDS) is the transfer of adsorbed H to the reaction site, and for ORR, the RDS is the reduction of the adsorbed oxygen atom on LSCF. In addition, the reversible single-component cell (RSCC) composed of LSCF prepared by ethanol solvent shows better performance for discharge and water electrolysis. The maximum power density (Pmax) of the RSCC is 232.9 mW/m2, and the current density at 1.3 V is −398.3 mA/cm2 at 700 ℃.
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图 1 (a) HOR和ORR的电化学性能测试系统示意图；(b) SCFC和RSCC的测试系统示意图
Figure 1 Schematic diagram of the test system for (a) electrochemical performance of HOR and ORR, (b) SCFC and RSCC
图 2 还原前后LSCF-SBA-1和LSCF-SBA-2 的(a) XRD谱图；(b)局部放大谱图；(c)晶格膨胀率；(d) LSCF-SBA-1和LSCF-SBA-2的N2吸附-脱附曲线；(e) LSCF-SBA-1的SEM照片；(f) LSCF-SBA-2的SEM照片
Figure 2 (a) XRD patterns, (b) partially magnified patterns, (c) the corresponding lattice parameters of non-reduced and reduced samples of LSCF-SBA-1 and LSCF-SBA-2, (d) N2 adsorption-desorption isotherms of LSCF-SBA-1 and LSCF-SBA-2, (e) SEM image of LSCF-SBA-1 and (f) SEM image of LSCF-SBA-2
图 3 LSCF-SBA-1和LSCF-SBA-2的XPS谱图：(a) Co 2p, (b) Fe 2p, (c) O 1s
Figure 3 XPS spectra of (a) Co 2p, (b) Fe 2p, (c) O 1s of LSCF-SBA-1 and LSCF-SBA-2
图 4 LSCF-SBA-1和LSCF-SBA-2 组成的SCFCs在700 ℃时的((a)、(b)) I-V-P曲线和Pmax值; ((c)、(d))交流阻抗谱图和对应的ASR值(氢电极侧：H2；氧电极侧：O2)；((e)、(f)) LSCF-SBA-2 组成的SCFCs在700−550 ℃时的I-V-P曲线和Pmax值
Figure 4 ((a), (b)) Current density-voltage-power density curves and Pmax values; ((c), (d)) Impedance spectra and the corresponding ASR values of the SCFCs composed of LSCF-SBA-1 and LSCF-SBA-2 oxides at 700 ℃ (hydrogen side: H2; oxygen side: O2); ((e), (f)) I-V-P curves and Pmax values of SCFCs composed of LSCF-SBA-2 at 700−550 ℃
图 5 SDC-LN-30%LSCF-SBA-1和SDC-LN-30%LSCF-SBA-2在550−700 ℃下的电导率：(a) O2气氛，(b) H2气氛
Figure 5 Electrical conductivities of SDC-LN-30%LSCF-SBA-1 and SDC-LN-30%LSCF-SBA-2 in (a) O2 atmosphere, and (b) H2 atmosphere at 550−700 ℃
图 6 H2气氛中不同温度下由LSCF-SBA-1和LSCF-SBA-2组成的SCFCs的(a)交流阻抗谱图；((b)、(c))相应的ASR值；(d) Rp与温度的阿伦尼乌斯曲线
Figure 6 (a) Impedance spectra; ((b), (c)) the corresponding ASR values, (d) Arrhenius plots of Rp for SCFCs with LSCF-SBA-1 and LSCF-SBA-2 at various temperatures in H2 atmosphere
图 7 不同PH2下LSCF-SBA-1和LSCF-SBA-2的(a)交流阻抗谱；((b)、(c))相应的ASR值；(d) Rp与PH2的关系图
Figure 7 (a) Impedance spectra; ((b), (c)) the corresponding ASR values under various PH2 and (d) PH2 dependence of Rp for SCFC composed of LSCF-SBA-1 and LSCF-SBA-2
图 8 ((a)、(b)) 700 ℃氧气气氛下SCFC的阻抗谱和对应的Rp值；(c) 不同pO2下由LSCF-SBA-2组成的SCFC的交流阻抗谱图；(d) Rp与pO2的关系
Figure 8 ((a), (b)) Impedance spectra and the corresponding Rp values of the SCFCs at 700 ℃ in O2 atmosphere (c) Impedance spectra under various pO2 at 700 ℃ for SCFC composed of LSCF-SBA-2 and (d) pO2 dependence of Rp
图 9 ((a)、(b)) RSCCs在700 ℃下的I-V和I-P曲线以及对应的Pmax值和1.3 V下的电流密度；((c)、(d)) 由LSCF-SBA-2组成的RSCCs在700、650、600和550 ℃的I-V和I-P曲线以及对应的Pmax值和1.3 V下的电流密度
Figure 9 I-V, I-P curves, the corresponding Pmax values and current densities (at 1.3 V) of the RSCCs composed of ((a), (b)) LSCF-SBA-1 and LSCF-SBA-2 oxides at 700 ℃ and ((c), (d)) LSCF-SBA-2 at 700, 650, 600 and 550 ℃ (oxygen side: O2; hydrogen side: 70%H2-30%H2O)
表 1 还原前后LSCF-SBA钙钛矿氧化物的晶格参数
Table 1 Lattice parameters of the LSCF-SBA perovskite oxides before and after reduction
Sample Space group a=b /Å c /Å LSCF-SBA-1 R-3c 5.511 13.416 LSCF-SBA-2 R-3c 5.527 13.421 Reduced LSCF-SBA-1 R-3c 5.530 13.436 Reduced LSCF-SBA-2 R-3c 5.544 13.445 
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表 2 LSCF系列样品的Fe 2p、Co 2p和O 1s光谱曲线拟合后各峰的相对面积
Table 2 Relative areas derived from curve deconvolutions of Fe 2p, Co 2p and O 1s spectra for LSCF series samples
Sample Content /% Fe2 + Fe3 + Co2 + Co3 + surface O adsorbed O lattice O LSCF-SBA-1 37.4 62.6 28.8 71.2 49.4 31.0 19.6 LSCF-SBA-2 54.3 45.7 43.5 56.5 39.8 35.0 25.2
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