原位双金属纳米颗粒YST复合阳极的构筑及其直接碳催化性能研究

doi:10.11949/0438-1157.20200497

摘要/Abstract

摘要：

研究了原位Cu析出和CuCo双金属析出的钇掺杂钛酸锶（YST）材料在作为直接碳燃料电池（DC-SOFCs）阳极时的结构及性能。首先采用燃烧法制备系列Co掺杂的Y_0.08Sr_0.92Ti_0.9-_xCu_0.1Co_xO_3-_δ（x = 0,0.1,0.2,0.3）阳极材料。通过XRD、SEM、TEM等表征材料微观结构，结果表明Co掺杂量达到0.2时，氢气还原后的阳极材料析出均匀分布的CuCo双金属纳米颗粒。电导率测试表明CuCo双金属纳米颗粒有效提高了材料的电导率。CO氛围下的阻抗测试表明，析出CuCo双金属纳米颗粒的Co0.2阳极材料具有最小的极化阻抗，催化活性优于其他阳极材料，以其作为阳极的电池在800℃和碳为燃料时，最大功率密度可达591 mW·cm^-2，且具有良好的稳定性，是一种优异的DC-SOFC阳极材料。

关键词: 原位析出, 纳米颗粒, 阳极, 燃料电池, 电化学

Abstract:

In this paper, the structure and performance of in-situ Cu precipitation and CuCo bimetallic precipitation of yttrium-doped strontium titanate (YST) materials as direct carbon fuel cell (DC-SOFCs) anodes were studied. A series of Co doped Y_0.08Sr_0.92Ti_0.9-_xCu_0.1Co_xO_3-_δ (x = 0, 0.1, 0.2, 0.3) anode materials are prepared by combustion method. XRD, SEM and TEM techniques are used to study the anode materials?? microstructure. When Co doping content reaches to 0.2, the CuCo bimetal nanoparticles are uniformly precipitated on anode after hydrogen reduction. The conductivity test shows that CuCo bimetallic nanoparticles can effectively improve the conductivity of the material. The impedance test in CO atmosphere showed that the smallest polarization impedance is obtained for Co0.2 anode material with precipitated CuCo bimetallic nanoparticles, and its catalytic activity is better than that of other samples. Then, the cell using Y_0.08Sr_0.92Ti_0.7Cu_0.1Co_0.2 material as the anode exhibits good stability and excellent electrochemical performance at 800℃, with a maximum power density of 591 mW·cm^-2. It is shown that the Y_0.08Sr_0.92Ti_0.7Cu_0.1Co_0.2is an excellent DC-SOFC anode material.

Key words: in-situ precipitation, nanoparticles, anode, fuel cells, electrochemistry

中图分类号:

TQ 152

陈海涛, 乔金硕, 王振华, 孙旺, 李海军, 孙克宁. 原位双金属纳米颗粒YST复合阳极的构筑及其直接碳催化性能研究[J]. 化工学报, 2020, 71(9): 4270-4281.

Haitao CHEN, Jinshuo QIAO, Zhenhuan WANG, Wang SUN, Haijun LI, Kening SUN. Investigation on preparation and carbon catalytic ability of in-situ bimetallic nanoparticle YST composite anode[J]. CIESC Journal, 2020, 71(9): 4270-4281.

图/表 11

图1 以Co0样品为阳极的电解质支撑型全电池截面SEM图像

Fig.1 The cross section SEM images of the electrolyte-supported fuel cell used Co0 sample as the anode

图2 YST0.9-xCCox阳极材料在950℃的空气中煅烧5 h后的XRD谱图：（a）2θ从20°~80°，（b）2θ从32°~33°；YST0.9-xCCox阳极材料的Rietveld精修XRD谱图：（c）Co0，（d）Co0.1，（e）Co0.2，（f）Co0.3；YST0.9-xCCox阳极材料在10％H2和90％Ar气氛中于800℃煅烧5 h后的XRD谱图：（g）2θ从20°~80°，（h）2θ从41°~50°；（i）YST0.9-xCCox阳极材料与碳燃料以质量比1∶1均匀混合后于Ar气中800℃煅烧5 h后的XRD谱图

Fig.2 XRD patterns for YST0.9-xCCox sample after calcination at 950℃ in air for 5 h: (a) 2θ from 20°to 80°, (b) 2θ from 32° to 33°. Rietveld-refined XRD pattern of the YST0.9-xCCox samples: (c) Co0 sample, (d) Co0.1 sample, (e) Co0.2sample, (f) Co0.3 sample. XRD patterns of YST0.9-xCCox sample calcined at 800℃ for 5 h in 10% H2 and 90% Ar atmosphere: (g) 2θ from 20° to 80°, (h) 2θ from 41° to 50°. (i) XRD patterns for YST0.9-xCCox sample mixed with carbon fuel at a mass ratio of 1∶1 and calcined at 800℃ for 5 h in Ar gas

表1 YST0.9-xCCox阳极材料XRD数据精修后得到的晶体结构数据汇总

Table 1 Summary of rietveld refinement results of XRD data for YST0.9-xCCox samples

阳极材料	空间群	晶胞参数
Co0	Pm $3 ˉ$ m	a=b=c=3.8990?,α=β=γ=90°，5.129 g·cm^-3
Co0.1	Pm $3 ˉ$ m	a=b=c=3.8988 ?，α=β=γ=90°，5.142 g·cm^-3
Co0.2	Pm $3 ˉ$ m	a=b=c=3.8887 ?，α=β=γ=90°，5.182 g·cm^-3
Co0.3	Pm $3 ˉ$ m	a=b=c=3.8820 ?，α=β=γ=90°，5.209 g·cm^-3

表1 YST0.9-xCCox阳极材料XRD数据精修后得到的晶体结构数据汇总

Table 1 Summary of rietveld refinement results of XRD data for YST0.9-xCCox samples

阳极材料	空间群	晶胞参数
Co0	Pm $3 ˉ$ m	a=b=c=3.8990?,α=β=γ=90°，5.129 g·cm^-3
Co0.1	Pm $3 ˉ$ m	a=b=c=3.8988 ?，α=β=γ=90°，5.142 g·cm^-3
Co0.2	Pm $3 ˉ$ m	a=b=c=3.8887 ?，α=β=γ=90°，5.182 g·cm^-3
Co0.3	Pm $3 ˉ$ m	a=b=c=3.8820 ?，α=β=γ=90°，5.209 g·cm^-3

图3 （a）Co0阳极材料在10％H2和90％Ar气氛中800℃煅烧5 h后的SEM图像、TEM图像和HRTEM图像；（b）Co0.1阳极材料、（c）Co0.2阳极材料和（d）Co0.3阳极材料分别在10％H2和90％Ar气氛中于800℃ 煅烧5 h后的SEM图像；Co0.2阳极材料在10％H2和90％Ar气氛中800℃煅烧5 h后的谱图：（e）EDS图，（f）TEM图像，（g）和（h）HRTEM图像

Fig.3 (a) SEM image, TEM image and HRTEM image for Co0 sample calcined at 800℃ for 5 h in 10% H2 and 90% Ar atmosphere. SEM image for samples calcined at 800℃ for 5 h in 10% H2 and 90% Ar atmosphere: (b) Co0.1 sample, (c) Co0.2 sample, (d) Co0.3 sample. (e) EDS map, (f) TEM image, (g) and (h) HRTEM images for Co0.2 sample calcined at 800℃ for 5 h in 10% H2 and 90% Ar atmosphere

图4 YST0.9-xCCox阳极材料在10％H2气氛中电导率随温度的变化

Fig.4 The conductivity for YST0.9-xCCox samples in 10% H2 atmosphere from 500℃ to 800℃

图5 YST0.9-xCCox阳极材料于10％H2和90％Ar气氛中800℃ 煅烧5 h后在室温下测得的XPS谱图(a) Ti 2p; (b) O 1s

Fig.5 XPS spectra at room temperature for YST0.9-xCCox samples calcined at 800℃ for 5 h in 10% H2 and 90% Ar atmosphere

表2 通过XPS表征获得的Ti3+含量百分比和吸附氧含量百分比

Table 2 Ti3+ percentage and adsorbed oxygen percentage obtained by X-ray photoelectron spectra

阳极材料	Ti³⁺ 面积	Ti⁴⁺ 面积	Ti³⁺ 百分比/%	晶格氧面积	吸附氧面积	吸附氧百分比/%
Co0	5940.4	9627.1	38.16	155950	13737.4	46.83
Co0.1	6120.6	5145.8	54.33	11971.7	14410.1	54.62
Co0.2	5627.9	6005.1	48.38	10007.8	15004.0	59.99
Co0.3	6840.4	9327.0	42.31	10316.4	17691.3	63.17

图6 （a）YST0.9-xCCox阳极材料制备的对称电池在800℃下的EIS谱图；（b）800℃下YST0.9-xCCox阳极材料制备的对称电池的阻抗数据的DRT分析

Fig.6 (a) EIS spectra of the symmetrical cells fabricated with YST0.9-xCCox samples at 800℃. (b) DRT analysis of the symmetrical cells fabricated with YST0.9-xCCox samples at 800℃

表3 800℃下YST0.9-xCCox阳极材料制备的对称电池的阻抗数据经过拟合后的结果

Table 3 Results of resistances of the symmetrical cells fabricated with YST0.9-xCCox samples at 800℃

阳极材料	R_p/(Ω·cm²)	R_H/(Ω·cm²)	R_L/(Ω·cm²)
Co0	5.32	1.07	4.25
Co0.1	4.56	0.83	3.73
Co0.2	1.63	0.67	0.96
Co0.3	3.19	0.31	2.68

图7 基于LSCF阴极的全电池的电化学性能（a）800℃下以Co0和Co0.2阳极材料为阳极的全电池的I–V和I–P曲线；（b）和（c）在开路条件下以Co0和Co0.2阳极材料为阳极的全电池在800℃的EIS光谱和相应的DRT分析；（d）以Co0和Co0.2阳极材料为阳极的全电池在800℃下以200 mA·cm-2的恒定电流密度工作时电压随时间变化的曲线

Fig.7 Electrochemical performance of the single cells based on the LSCF cathode(a) I–V and I–P curves of the single cell with the Co0 and Co0.2 samples as anode at 800℃; (b) and (c) EIS spectra and the corresponding DRT analysis of single cell with the Co0 and Co0.2 samples as anode at 800℃ under open-circuit conditions; (d) Terminal voltages measured at 800℃ as a function of time for the cells with Co0 and Co0.2 samples as anode operated at a constant current density of 200 mA·cm-2

表4 以Co0和Co0.2阳极材料为阳极制备的全电池在800℃时的阻抗结果

Table 4 Results of resistances of the single cells fabricated with Co0 and Co0.2 samples as anodes at 800℃

阳极材料	R_Ω/(Ω·cm²)	R_p/(Ω·cm²)	R_H/(Ω·cm²)	R_L/(Ω·cm²)
Co0	0.16	0.89	0.07	0.82
Co0.2	0.13	0.34	0.05	0.29

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