Effect of MgO and Fe2O3 Incorporation on the Microstructure and Electrochemical Performance of GDCSi System

doi:10.19894/j.issn.1000-0518.210150

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (5): 809-818.DOI: 10.19894/j.issn.1000-0518.210150

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Effect of MgO and Fe₂O₃ Incorporation on the Microstructure and Electrochemical Performance of GDCSi System

Jing ZHOU, Yu-Xuan CHEN, Jun-Ming MA, Xiao-Fei ZHU(), De-Feng ZHOU()

School of Chemistry and Life Science，Changchun University of Technology，Changchun 130012，China

Received:2021-03-29 Accepted:2021-07-29 Published:2022-05-01 Online:2022-05-24
Contact: Xiao-Fei ZHU,De-Feng ZHOU
About author:defengzhou65@126.com
zhuxiaofei@ccut.edu.cn
Supported by:
the National Natural Science Foundation of China(21471022);the Jilin Provincial Science Research Foundation of China(20190201230JC);the 13th Five?Year Plan for Science & Technology Research Sponsored by Department of Education of Jilin Province(JJKH20200647KJ)

Abstract

Abstract:

The incorporation of Fe₂O₃ and MgO in the Gd_0.2Ce_0.8O_3-_δ +0.05% （mass fraction） SiO₂ （GDCSi） can reduce the sintering temperature and improve the conductivity of the grain boundary. Single doping of MgO or Fe₂O₃ and simultaneous addition of MgO and Fe₂O₃ are performed to study the effects of the doping method on the microstructure and electrochemical performance of the GDCSi electrolyte. The results indicate that no matter whether MgO and Fe₂O₃ are single-doped or co-doped into the GDCSi system， no second phase is produced， and all the samples form the cubic fluorite phase. The addition of 4% molar fraction MgO， 4% molar fraction Fe₂O₃ and 2% molar fraction MgO-2% molar fraction Fe₂O₃ can promote the grain growth of the GDCSi system and reduce the inter-grain porosity， in addition， reduce the grain interior resistance （R_gi）， grain boundary resistance （R_gb） and total resistance （R_t）. It is of interest that MgO-Fe₂O₃ co-doped GDCSi-MF results in the highest grain boundary conductivity （σ_gb） and total conductivity （σ_t）. At 400 °C， the σ_gb and σ_t of the GDCSi-MF are 10.41 and 1.82 times higher than those of GDCSi， respectively.

Key words: Sintering aids, Grain boundary improvers, Conductivity, Doping, Electrolyte

CLC Number:

O646

Jing ZHOU, Yu-Xuan CHEN, Jun-Ming MA, Xiao-Fei ZHU, De-Feng ZHOU. Effect of MgO and Fe₂O₃ Incorporation on the Microstructure and Electrochemical Performance of GDCSi System[J]. Chinese Journal of Applied Chemistry, 2022, 39(5): 809-818.

Figures/Tables 8

Fig.1 （A） XRD spectra of synthesized GDCSi-based samples；（B） XRD spectra in the 2θ range from 27.0（°） to 30.0（°）

Table 1 Related parameters of GDCSi?based electrolyte sintered at 1200 ℃ for 10 h

样品 Samples	晶胞参数 a/nm	晶胞体积 V/nm³	理论密度 ρ_T/ （g·cm^-3）	实际密度 ρ_a/（g·cm^-3）	相对密度 ρ_Rel/%	微晶尺寸 d/nm
GDCSi	0.541 30	15.860	7.247	6.203	85.6	14.85
GDCSi?M	0.541 31	15.861	7.238	6.608	91.3	15.40
GDCSi?F	0.541 04	15.837	7.249	6.879	94.9	18.51
GDCSi?MF	0.541 29	15.862	7.251	6.939	95.7	25.20

Fig.2 Raman spectra of GDCSi-based electrolyte samples

Fig.3 Cross-sectional FE-SEM images of GDCSi-based electrolyte sintered at 1200 ℃ for 10 h

Fig.4 Electrochemical impedances of GDCSi-based electrolyte measured at （A） 350 ℃，（B） 800 ℃ in air. The illustration shows equivalent circuit diagrams for EIS analysis

Table 2 The resistance values of GDCSi?based electrolytes measured at 350 and 800 ℃

样品 Samples	350 ℃				800 ℃
样品 Samples	晶粒电阻 R_gi/Ω	晶界电阻 R_gb/Ω	总电阻 R_t/Ω	晶界电阻/总电阻 R_gb/R_t	总电阻=晶粒电阻 R_t =R_gi/Ω
GDCSi	1218.9	1269.6	2488.5	0.51	3.71
GDCSi?M	470.61	138.05	575.22	0.24	3.42
GDCSi?F	425.78	119.48	545.26	0.22	3.14
GDCSi?MF	348.89	98.35	447.24	0.21	3.10

Fig.5 Arrhenius curves of （A） the grain boundary conductivity，（B） grain conductivity and （C） total conductivity of GDCSi-based electrolytes

Fig.6 Peak power density （PPD） of （A） NiO-GDCSi/ GDCSi/LSCF （Cell-Ⅰ） and （B） NiO-GDCSi-MF/GDCSi-MF/LSCF （Cell-Ⅱ） at 600~700 °C. （C） Impedance spectra of single cells （Cell-Ⅰ， Cell-Ⅱ） measured at 700 °C under open circuit voltage （OCV）. （D） Long-term stability test of Cell-Ⅱ is conducted for 60 h at 600 °C and at a constant current of 0.3 A/cm2

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Effect of MgO and Fe₂O₃ Incorporation on the Microstructure and Electrochemical Performance of GDCSi System

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