Investigation on preparation and carbon catalytic ability of in-situ bimetallic nanoparticle YST composite anode

doi:10.11949/0438-1157.20200497

Abstract

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

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

CLC Number:

TQ 152

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.

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.

Figures/Tables 11

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

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

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

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

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

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

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

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

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℃

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

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

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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