Fluorination of BaZr0.1Ce0.7Y0.1Yb0.1O3 as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell

doi:10.15541/jim20240535

Abstract

Abstract:

Proton-conducting solid oxide fuel cells (H⁺-SOFC) have gained great attention due to weak temperature dependence and high energy conversion efficiency. However, how to improve their proton conductivity still remains an open problem. In this work, a fluorination strategy based on the BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ (BZCYYb) electrolyte was proposed to improve the proton conductivity. It is found that the conductivity (σ) of the fluorinated BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_2.9F_0.1 (BZCYYbF) is 4.59×10^-3-2.14×10^-2 S/cm at 450-800 ℃ in dry H₂, higher than that of the primitive BZCYYb electrolyte (σ=3.99×10^-3-1.86×10^-2 S/cm). The electrolyte fluorination significantly reduces anode polarization resistance for hydrogen oxidation reaction from 2.50 Ω·cm² to 1.94 Ω·cm², and total resistance of the single cell with 300-μm-thick electrolyte supporting from 1.54 Ω·cm² to 1.47 Ω·cm². Therefore, the BZCYYbF single cell shows much higher maximum power density (172 mW·cm^-2) than the BZCYYb single cell (144 mW·cm^-2) at 700 ℃. This result is attributed to the fact that the electrolyte fluorination not only improves the proton conduction capacity but also enhances the rates of H₂ diffusion and adsorption/dissociation on the anode sides. In conclusion, the fluorination of BZCYYb electrolyte can significantly improve its proton conductivity and thereby contribute to superior electrochemical performance of H⁺-SOFC.

Key words: proton-conducting solid oxide fuel cell, proton conducting electrolyte, fluorination, conductivity, electrochemical performance

CLC Number:

TQ15

JIANG Yuehong, SONG Yunfeng, ZHANG Leilei, MA Ji, SONG Zhaoyuan, LONG Wen. Fluorination of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell[J]. Journal of Inorganic Materials, 2025, 40(12): 1356-1364.

Figures/Tables 12

Fig. 1 XRD patterns and Rietveld refinements for BZCYYb and BZCYYbF samples (a) XRD patterns; Rietveld refinements for (b) BZCYYb and (c) BZCYYbF. Colorful figures are available on website

Fig. 2 (a) Thermal expansion and (b) first order differential curves of BZCYYb and BZCYYbF in air

Fig. 3 Ce3d XPS spectra for (a) BZCYYb and (b) BZCYYbF electrolytes

Fig. 4 (a) Electrical conductivities of BZCYYb and BZCYYbF in air; (b, c) Surface SEM images of (b) BZCYYb and (c) BZCYYbF; (d) Electrical conductivities of BZCYYb and BZCYYbF in dry H2

Fig. 5 (a, c, e, g) EIS spectra and (b, d, f, h) DRT curves for BZCYYb and BZCYYbF symmetric cells in (a-d) air and (e-h) wet H2 at (a, b, e, f) 600 and (c, d, g, h) 700 ℃

Fig. 6 (a) I-V/I-P curves and (b) EIS spectra for electrolyte-supported single cells at 700 ℃

Fig. 7 Time dependent current densities for single cells under a constant potential of 0.55 V

Fig. 8 (a) I-V/I-P curves for anode-supported single cell at 600 ℃ and (b) cross-sectional SEM image for anode-supported single cell with BZCYYbF electrolyte after cell stability test

Table S1 Rietveld refinement results for BZCYYb and BZCYYbF samples based on space group Pbnm

Sample	BZCYYb		BZCYYbF
Sample	Refined	Sigmas	Refined	Sigmas
a/Å	6.2146	0.000851	6.210605	0.000363
b/Å	6.2443	0.000511	6.197102	0.000486
c/Å	8.7578	0.00058	8.701261	0.00077
α/(°)	90	-	90	-
β/(°)	90	-	90	-
γ/(°)	90	-	90	-
V/Å³	339.858	0.054	334.892	0.04
χ²	1.711	-	2.346	-
R_wp/%	14.83	-	14.07	-
R_p/%	9.99	-	11.54	-

Fig. S1 F1s XPS spectra for BZCYYbF electrolyte

Fig. S2 (a, b) Electrical conductivity curves for (a) BZCYYb and (b) BZCYYbF in air measured by different models; (c) Schematic diagram for three different conductivity testing models; (d, e) Histograms of conductivities for (d) BZCYYb and (e) BZCYYbF measured by different models; (f) Comparison of conductivities for BZCYYb and BZCYYbF

Fig. S3 (a, b) Electrical conductivity curves for (a) BZCYYb and (b) BZCYYbF in H2 measured by different models; (c) Schematic diagram for two different conductivity testing models; (d) Histogram for BZCYYbF measured by different models; (e) Comparison of conductivities of BZCYYb and BZCYYbF

References 26

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Fluorination of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell

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