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Li y Zhang 2022 Preparation MnCoO Spinel
Li y Zhang 2022 Preparation MnCoO Spinel
Li y Zhang 2022 Preparation MnCoO Spinel
ScienceDirect
Fangxin Li, Pengchao Zhang*, Yang Zhao, Deming Yang, Juncai Sun
Department of Materials Science and Engineering, Dalian Maritime University, Dalian 116026, PR China
Article history: To meet the performance requirements of solid oxide fuel cell (SOFC) metallic intercon-
Received 26 November 2022 nect, the MneCoeO spinel coating is prepared on the surface of AISI430 by pack cemen-
Received in revised form tation method to reduce the growth kinetics of oxides and inhibit the outward diffusion of
3 January 2023 Cr. The microstructural characterization shows that a dense, uniform, defect-free spinel
Accepted 5 January 2023 coating is successfully fabricated on the surface of AISI430. Under the simulated SOFC
Available online 27 January 2023 cathode environment, the weight gain of coated steel (0.608 mg cm2) after oxidation at
800 C for 800 h is significantly lower than that of uncoated (1.586 mg cm2). In addition, the
Keywords: area specific resistance (ASR) of the coated steel oxidized for 500 h is 17.69 mU cm2, much
SOFC smaller than that of the bare steel, indicating that the oxidation resistance and electrical
Metallic interconnect conductivity of AISI430 are significantly improved by MneCoeO spinel coating. Cross-
MneCoeO spinel Coating sectional observations of the MneCoeO spinel coating are conducted to assess the
Oxidation compatibility of substrate with the adjacent coating and its effectiveness in reducing the
Area specific resistance growth of the Cr2O3 layer.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author.
E-mail address: zpc@dlmu.edu.cn (P. Zhang).
https://doi.org/10.1016/j.ijhydene.2023.01.065
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 0 4 8 e1 6 0 5 6 16049
Fig. 2 e Schematic diagram of the setup for the ASR test of samples.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 0 4 8 e1 6 0 5 6 16051
Fig. 3 e SEM image of MneCo alloy coating prepared on AISI430 surface (a) surface morphology (b) cross-section morphology
and corresponding EDS analysis.
derived from substrate because the coating was not thick Mn þ 2Co þ 2O2 ¼ MnCo2 O4 (1)
enough to hinder X-ray penetration [27,28]. The trans- A dense and consecutive spinel coating with good adhe-
formation process of MnCo2O4 is complex according to Cher- sion to the substrate can be obtained after pre-oxidation
epin's report [29]. In General, Mn and O have a preferential (Fig. 4d). According to the EDS results, the Fe and Cr ele-
affinity to Co under high temperature and high oxygen partial ments are high in the substrate, but then they are gradually
pressure to form MnO. Meanwhile, Co2O3 is formed due to the depleted in the oxide layer. In contrast, the MnCo2O4 spinel
combination of Co and O. The dispersed distribution of MnO layer has been measured to have high Co, Mn, and O content.
and Co2O3 is arrayed with optimum structural principle into Combined with the XRD results, the MnCo2O4 spinel coating is
the spinel phase. The generated process of MnCo2O4 can be formed after the pre-oxidation process to effectively suppress
finally expressed as the following reaction: the out-diffusion of Cr.
Fig. 4 e The MnCo2O4 spinel sample after pre-oxidation (a) surface morphology, (b) mapping analysis, (c) XRD pattern, (d)
cross-section morphology and corresponding EDS analysis.
16052 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 0 4 8 e1 6 0 5 6
Fig. 5 e (a) The weight gain and (b) oxidation kinetics for uncoated and coated samples at 800 C for 800 h.
Oxidation behavior (Fig. 5b). Based on Wagner's oxidation theory [30], if the curve
is parabolic, the parabolic rate kinetic equation is satisfied by
Fig. 5 studies the oxidation weight gain and oxidation kinetics Eq. (2):
of the samples oxidized at 800 C for 800 h, respectively. The 2
oxidation weight gain of uncoated and coated sample in- △M
=kP $t (2)
creases parabolically with the increasing oxidation time. The A
weight gain of uncoated sample possesses a high growth rate where DM is the mass gain, A is the sample surface area, kp is
during the initial 300 h, and the rate of growth slows down the parabolic rate constant, and t is the oxidation time. One of
subsequently (Fig. 5a). This behavior is characteristic of the important factors affecting oxidation kinetics is the con-
oxidation kinetics governed by a combination of diffusion tent of oxides formed by outward diffusion of metal cations
controlled (parabolic) oxide scale growth and linear (time and inward diffusion of anions [31]. In this experiment, the
invariant) oxide scale evaporation. Under this regime, the formation of Cr2O3 and the evaporation of Cr are accelerated
oxide scale grows until a certain thickness is reached where by the outward diffusion of Cr in the substrate during high-
evaporation and oxidation proceed at the same rate. The temperature oxidation. The kp of coated sample is signifi-
thickness of the oxide scale will remain constant as the cantly lower than that of uncoated one during the oxidation
oxidation continues, but mass loss will be recorded. The weight process, indicating that the MneCoeO spinel coating can
gain of coated sample increases rapidly within 375 h, and then significantly suppress the inward diffusion of oxygen in the
tends to be gentle (Fig. 5a), which is due to the formation of simulated cathode environment. It is further demonstrated
spinel inhibiting the growth of Cr2O3 oxide scale. In addition, that MneCoeO spinel can effectively suppress the growth of
the oxidation weight gain of the coated sample (0.608 mg cm2) Cr2O3 oxide layer and improve the antioxidant properties of
is lower than that of uncoated (1.586 mg cm2). It is proved that AISI430.
the spinel coating can effectively improve the oxidation resis- Fig. 6 is the surface morphology of uncoated and coated
tance of sample at high temperature. samples after long-term isothermal oxidation (800 C, 800 h).
To explain the oxidation kinetics principle of samples The surface of the uncoated sample is covered with poly-
more specifically, the relationship between the square of area hedral grains, loosely packed (Fig. 6a). Analogous surface
specific surface weight gain and oxidation time is researched morphology appears in previous reference [28]. The coated
Fig. 6 e Surface morphology for (a) uncoated and (b) coated samples after oxidation.
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Fig. 7 e Cross-section morphology and corresponding EDS analysis (a) uncoated and (b) coated samples after oxidation test
at 800 C for 800 h.
Fig. 8 e XRD pattern (a) uncoated and (b) coated samples after oxidation test at 800 C for 800 h.
sample has a dense morphology on surface with a diameter of of Cr elements is effectively inhibited by the MneCoeO
particles about 0.2e1 mm (Fig. 6b). spinel coating. After a long period of high-temperature
Fig. 7 shows the cross-section morphology and EDS anal- oxidation, the protective spinel coating remains compact
ysis of the uncoated and coated samples, respectively, after and retains good adhesion to the substrate without cracking.
the isothermal oxidation test. The oxide layer with a thickness
of about 11e13 mm can be observed in the uncoated sample
(Fig. 7a). According to the EDS analysis in Fig. 7a, the oxide
layer has high O, Cr, and Fe content. The high content of Cr in
the oxide layer is observed due to the combination of outward
diffusion of Cr and inward diffusion of O, resulting in the
formation of Cr2O3 at high temperatures. The closer to the air,
the greater oxygen partial pressure in the oxide layer It is
easily oxidized into volatile Cr species in the outer layer, and
the volatile Cr species are easily diffused from the oxide layer
into the air. These volatile Cr species will diffuse to the cath-
ode and poison the active reaction site, leading to severe
degradation of the SOFC stack in output power.
The spinel outer layer is uniform and dense with a thick-
ness of 9e11 mm in Fig. 7b, thinner than that of uncoated. This
result is corresponding with the comparison of previous
oxidation weight gain between the uncoated and coated
samples (Fig. 5a). EDS analysis shows a high Mn and Co con-
tent in the oxide layer, but almost no Cr elements can be Fig. 9 e Weight gain of uncoated and coated samples
detected. This evidence demonstrates that the out-diffusion versus the cycle number.
16054 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 0 4 8 e1 6 0 5 6
Fig. 10 e Surface morphology of (a) uncoated and (b) coated samples after cyclic oxidation test.
Fig. 8 shows the XRD of uncoated and coated samples after will combine with Mn and Co to form a spinel structure, which
isothermal oxidation measurement. After 800 h of oxidation, can improve the performance of the coated sample.
the oxide layer of uncoated sample is composed of MnCr2O4 To study the thermal cracking resistance of spinel coating
and Cr2O3 (Fig. 8a), which is consistent with the study of on AISI430 against spallation and cracking, the coated sample
Zhou's report [26]. The XRD pattern of the coated sample is subjected to cyclic oxidation test (800 C) in a simulated
oxidized at 800 C for 800 h is shown in Fig. 8b. Combining the starting and stopping SOFC condition, using the uncoated
results in Fig. 7c, the oxide layer consists of an inner layer of sample as a comparison. Fig. 9 shows the weight gain of the
MnFe2O4, CoFe2O4 and an outer layer of MnCo2O4. The con- uncoated and coated samples with the number of cycles. For
ductivity and thermal expansion coefficient of MnFe2O4 are both samples, the weight gain increases with the number of
8.0 S cm1 and 1.25 106/ C. The conductivity and thermal cycles. In addition, the uncoated sample consistently has a
expansion coefficient of CoFe2O4 are 0.93 S cm1 and higher weight gain value than the coated one. The weight gain
1.21 106/ C [20]. The continuous outward diffusion of Fe of uncoated sample is 2.315 mg cm2, higher than that of
Fig. 11 e ASR result of uncoated and coated samples at (a) (b) different oxidation temperatures, (c) different oxidation times.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 6 0 4 8 e1 6 0 5 6 16055
coated (0.726 mg cm2) after 100 heating and cooling cycles. sample has a dense and homogeneous surface with good
This indicates that the coated sample still has excellent adhesion to the substrate and no cracks. The protective spinel
resistance to oxidation after cyclic oxidation testing. coating demonstrates excellent performance in suppressing
Fig. 10 shows the surface morphology of the coated and the outward diffusion of Cr since no Cr element can be
uncoated samples after cyclic oxidation testing. Extensive measured in spinel layer after long-term oxidation. The
cracking and spallation can be observed on the uncoated MneCoeO spinel coating can reduce the growth rate of Cr2O3
surface in Fig. 10a. According to the related report, the for- (kp ¼ 5.01 104 mg2 cm4 h1) and improve the electrical
mation of cracking and peeling relates to the large disparity of conductivity of stainless steel (ASR ¼ 17.69 mU cm2). After
coefficient of thermal expansion (CTE) between the substrate cyclic oxidation measurements, the antistrip property of
and oxide layer [32]. The exfoliated part can enhance the MnCo2O4 coating is improved due to the matching of its
migration of cations and accelerate the growth of the oxide thermal expansion coefficient with that of substrate. The
layer at high temperatures. The surface of the coated sample combined results show that the MnCo2O4 spinel coating can
is uniform and dense, without crack and peeling (Fig. 10b). meet the stability and durability requirements of the SOFC
This result indicates that the spinel coating is well resistant to metallic interconnect.
spallation and cracking, which can be attributed to the com-
parable CTE of the spinel coating with the AISI430.
Declaration of competing interest
Electrical property
The authors declare that they have no known competing
An important requirement for the interconnect is to maintain financial interests or personal relationships that could have
a low and stable electrical resistance during SOFC operation. appeared to influence the work reported in this paper.
In this experiment, the electrical properties of the intercon-
nect are evaluated by the method of measuring the ASR of
samples. Fig. 11a presents the dependence of testing tem-
perature (from 450 C to 850 C) with ASR for the coated and Acknowledgments
uncoated samples. The ASR decreases with the increasing
temperature for both samples. A linear relationship between The authors gratefully acknowledge the Fundamental
Log (ASR/T) and 1/T is shown in Fig. 11b, demonstrating an Research Funds for the Central Universities (3132020157) and
electrical characteristic of semiconductors. The activation the Projects for Dalian Youth Star of Science and Technology
energy can be calculated from the slope of the curve described (2018RQ53).
by the Arrhenius equation:
ASR Ea references
¼ A$exp (3)
T KT
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