Applying the Protective Mn-Co-La2O3 Coating on Crofer 22 APU Ferritic Stainless Steel Used as Solid Oxide Fuel Cell Interconnects

doi:10.1007/s40195-024-01660-w

Abstract

Abstract:

This research studies the effect of Mn-Co-La₂O₃ coating synthesized by the electrodeposition method on the oxidation resistance and electrical conductivity of the Crofer 22 APU stainless steel interconnect plates in solid oxide fuel cells. The test samples were characterized by a field emission scanning electron microscope (FESEM) equipped with energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The oxidation kinetics of the coated and uncoated samples were studied by tracking their weight changes over time at 800 °C, showing that the oxidation mechanism for all samples follows the parabolic law. Lower oxidation rate constant (k_p) values of the coated sample compared with that of the uncoated one indicated a reduction in the oxidation rate of the steel substrate in the presence of the Mn-Co-La₂O₃ coating. The examination of the cross-section of different samples after the isothermal oxidation for 500 h at 800 °C exhibited that applying the composite coating leads to a decrease in the thickness of the chromia layer formed on the steel surface. Furthermore, under these conditions, the area-specific resistance (ASR) of the coated sample (13.11 mΩ cm²) is significantly lower than that of the uncoated one (41.45 mΩ cm²).

Key words: Area specific resistance, Oxidation, Fuel cell, Composite coating

Farhad Mohsenifar, Hadi Ebrahimifar, Ahmad Irannejad. Applying the Protective Mn-Co-La₂O₃ Coating on Crofer 22 APU Ferritic Stainless Steel Used as Solid Oxide Fuel Cell Interconnects[J]. Acta Metallurgica Sinica (English Letters), 2024, 37(5): 872-888.

Figures/Tables 16

Table 1 Chemical composition of Crofer 22 APU steel

C	Cr	Mn	Si	Ni	Al	Ti	La	Fe
0.01	22.7	0.38	0.02	0.02	0.02	0.07	0.06	Bal

Table 2 Chemical compositions and operating conditions for Mn-Co-La2O3 electrodeposition

Manganese sulfate, monohydrate (MnSO₄∙H₂O)	84.5 g L⁻¹ (0.5 M)
Cobalt sulphate, heptahydrate (CoSO₄∙7H₂O)	28.11 g L⁻¹ (0.1 M)
Sodium gluconate (NaC₆H₁₁O₇)	152.7 g L⁻¹ (0.7 M)
Lanthanum oxide (La₂O₃)	20 g L⁻¹
Boric acid (H₃BO₃)	61.84 g L⁻¹ (1 M)
Ammonium sulfate (NH₄)₂SO₄	13.2 g L⁻¹ (0.1 M)
Current density	250 mA cm⁻²
Temperature	25 °C
pH	2
Time	45 min

Fig. 1 Experimental setup used for measuring the ASR

Fig. 2 a, b FESEM micrographs; c EDX analysis; d EDX mappings of the Mn-Co-La2O3 coating

Table 3 Quantitative results of EDX analysis of Mn-Co-La2O3 coating

Element	Line	Int	Error	K	Kr	W%	A%	ZAF^*	Peak/background
O	Ka	100.8	5.0219	0.0973	0.0900	13.58	37.23	0.6624	7.84
Mn	Ka	71.8	0.5800	0.0995	0.0920	8.22	6.56	1.1203	7.30
Co	Ka	366.4	0.5800	0.7597	0.7028	73.57	54.75	0.9553	35.25
La	La	18.9	0.5800	0.0435	0.0402	4.63	1.46	0.8689	3.10
				1.0000	0.9250	100.00	100.00

Fig. 3 X-ray diffraction patterns of Mn-Co-La2O3 coating

Fig. 4 High-resolution spectra and fitted curve of a Mn 2p; b Co 2p; c La 3d; d O 1s of Mn-Co-La2O3 coating

Fig. 5 a FESEM cross-section micrograph; b EDS line scan of the Mn-Co-La2O3-coated steel

Fig. 6 Oxidation kinetics of bare and Mn-Co-La2O3-coated steel in air for 500 h at 800 °C expressed as: a weight gain; b squared weight gain as a function of time during isothermal oxidation

Fig. 7 a, b FESEM surface morphology; c, d EDS analysis of uncoated Crofer 22 APU stainless steel at point 1 (c), point 2 (d) after 500 h of isothermal oxidation at 800 °C

Fig. 8 a, b FESEM surface morphology; c, d EDS analysis of Mn-Co-La2O3-coated Crofer 22 APU stainless steel at point 1 (c), point 2 (d) after 500 h of isothermal oxidation at 800 °C

Fig. 9 XRD pattern of: a uncoated; b Mn-Co-La2O3-coated specimens after 500 h of isothermal oxidation at 800 °C

Fig. 10 FESEM cross-section image and EDS line scan of: a, b uncoated; c, d Mn-Co-La2O3-coated specimens after 500 h of isothermal oxidation at 800 °C

Fig. 11 SEM images of: a, b uncoated; c, d Mn-Co-La2O3-coated samples after cyclic oxidation at 800 °C, and as well as e specific weight gain as a function of cycle number during cyclic oxidation

Table 4 Thermal expansion coefficients of the phases formed on samples specimens after 500 h of isothermal oxidation at 800 °C

Material	α (× 10⁻⁶ °C⁻¹)
Crofer 22 APU [53]	11.5
Cr₂O₃ [54]	9.6
MnCr₂O₄ [55]	7.2
FeCr₂O₄ [56]	8.5
Co₃O₄ [20]	9.3
MnCo₂O₄ [20]	9.7
La₂O₃ [57]	9.1

Fig. 12 ASR values of the uncoated and Mn-Co-La2O3-coated samples against the oxidation time: a at 800 °C; b against the temperature

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Applying the Protective Mn-Co-La₂O₃ Coating on Crofer 22 APU Ferritic Stainless Steel Used as Solid Oxide Fuel Cell Interconnects

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