Performance of CoNiO spinel oxide coating on AISI 430 stainless steel as interconnect for intermediate temperature solid oxide fuel cell

In order to decrease oxide growth kinetics, maintain suitable conductivity and prevent Cr-volatilization of AISI 430 stainless steels (430 SS) as the interconnect for intermediate temperature solid oxide fuel cells (SOFCs), a CoNiO spinel oxide protective coating has been successfully fabricated on the 430 SS specimen using a simple and cheap process with two steps: 1) electroplation of CoNi alloy layer and 2) pre-oxidation treatment to convert the CoNi alloy into spinel oxide. The CoNiO spinel layer on the 430 SS (CoNiO 430 SS) is dense and uniform with 8–10 μm thickness. And the CoNiO spinel oxide protective coating consists of a main face-centered-cubic (fcc) NiCo₂O₄ spinel phase and a minor fcc NiO phase. Compared with bare 430 SS, the oxidation resistance and the conductivity of the CoNiO 430 SS have been improved remarkably under simulated typical SOFC operating cathode conditions (at 800 °C in air). After an isothermal oxidation test at 800 °C, the area specific resistance (ASR) of CoNiO 430 SS is much lower and stable (0.1 Ω cm² for 100 h and 0.9 Ω cm² for 600 h) than that of bare 430 SS (1.2 Ω cm² for 100 h and 2.4 Ω cm² for 600 h). These performances of CoNiO 430 SS imply that it can be a promising candidate interconnect for solid oxide fuel cell.     

Electrodeposited Ni/CeO2 mulriple coating on SUS 430 steel interconnect

Ni/CeO₂ mulriple coating has been fabricated on SUS 430 steel via electrodepositing approach. 100-h initial and 3-week long-term thermal exposing to air at 800 °C has enunciated that the oxide scale grown on the Ni/CeO₂ coated steel contains an external oxide layer of NiFe₂O₄ spinel, a middle oxide layer of NiO and an internal oxide layer of Cr₂O₃. Simultaneously, dispersive CeO₂ particles embed in the oxide scale. Compared to the Ni coated steel on which the same tri-layer oxide structure without discrete CeO₂ particles grows in the same exposing environment, growth rate of the internal Cr₂O₃ layer on the Ni/CeO₂ coated steel has been profoundly suppressed, which subsequently lowers the oxide scale area specific resistance (ASR). Enhancement of the oxidation resistance and reduction of the oxide scale ASR are attributed to the presence of CeO₂.     

Influence of preoxidation on high temperature behavior of NiFe2 coated SOFC interconnect steel

NiFe₂O₄ spinel coating is promising for solid oxide fuel cell (SOFC) steel interconnects application. In this work, NiFe₂ alloy coating was sputtered on bare steel and preoxidized steel (100 h in air at 800 °C), respectively, followed by exposing in air at 800 °C for up to 15 weeks in order to investigate the influence of steel preoxidation on high temperature behaviors of the coated steels. The results indicated that an outer NiFe₂O₄ spinel layer atop an inner Cr₂O₃ layer formed on the coated samples after oxidation. The preoxidation enhanced the oxidation resistance of the coated sample and reduced Cr out-migration to NiFe₂O₄ spinel layer. After 15 weeks, the area specific resistance (ASR) of surface scale on the coated preoxidized steel was much lower than that on the coated bare steel. The mechanisms of the preoxidation influence on oxidation behavior and surface scale electrical property of the coated steels were discussed.     

LaCrO3-based coatings deposited by high-energy micro-arc alloying process on a ferritic stainless steel interconnect material

Currently used ferritic stainless steel interconnects are unsuitable for practical applications in solid oxide fuel cells operated at intermediate temperatures due to chromium volatility, poisoning of the cathode material, rapidly decreasing electrical conductivity and a low oxidation resistance. To overcome these problems, a novel, simple and cost-effective high-energy micro-arc alloying (HEMAA) process is proposed to prepare LaCrO₃-based coatings for the type 430 stainless steel interconnects. However, it is much difficult to deposit an oxide coating by HEMAA than a metallic coating due to the high brittleness of oxide electrodes for deposition. Therefore, a Cr-alloying layer is firstly obtained on the alloy surface by HEMAA using a Cr electrode rod, followed by a LaCrO₃-based coating using an electrode rod of LaCrO₃-20 wt.%Ni, with a metallurgical bonding between the coating and the substrate. The preliminary oxidation tests at 850 °C in air indicate that the LaCrO₃-based coatings showed a three-layered microstructure with a NiFe₂O₄ outer layer, a thick LaCrO₃ sub-layer and a thin Cr₂O₃-rich inner layer, which thereby possesses an excellent protectiveness to the substrate alloy and a low electrical contact resistance.     

Evaluation of Ni80Cr20/(La0.75Sr0.25)0.95MnO3 dual layer coating on SUS 430 stainless steel used as metallic interconnect for solid oxide fuel cells

Ni₈₀Cr₂₀/(La_0.75Sr_0.25)_0.95MnO₃ dual-layer coating is deposited on SUS 430 alloy by plasma spray for solid oxide fuel cell (SOFC) interconnect application. The phase structure, area specific resistance (ASR), and morphology of the coating are studied. A two-cell stack is also assembled and tested to evaluate coating performance in an actual SOFC stack. The NiCr/LSM coating adheres well to the SUS 430 alloy after oxidation in air at 800 °C for 2800 h. The ASR and its increasing rate of coated alloy are 25 mΩ cm² and 0.0017 mΩ cm²/h, respectively. In an actual stack test, the maximum output power density of the stack repeating unit increases from 0.32 W cm⁻² to 0.45 W cm⁻² because of the application of NiCr/LSM coating. The degradation rate of the stack repeating unit with no coating is 4.4%/100 h at a current density of 0.36 A cm⁻², whereas the stack repeating unit with NiCr/LSM coating exhibits no degradation. Ni₈₀Cr₂₀/(La_0.75Sr_0.25)_0.95MnO₃ dual-layer coating can remarkably improve the thermal stability and electrical performance of metallic interconnects for SOFCs.     

Development of a Fe-Cr alloy for interconnect application in intermediate temperature solid oxide fuel cells

The oxidation behavior and electrical property of a newly designed Fe-Cr alloy with addition of 1.05 wt.% Mn, 0.52 wt.% Ti, 2.09 wt.% Mo and other elements, such as La, Y and Zr have been investigated isothermally or cyclically at 750 °C in air for up to 1000 h. With a coefficient of thermal expansion matched to SOFC cell components, the alloy demonstrates excellent oxidation resistance and low area specific resistance of the oxide scale. The thermally grown oxide scale presents a multi-layered structure with conductive Mn-Cr spinel in-between the underneath Cr₂O₃ and the top Mn₂O₃. The oxidation rate constants obtained under both isothermal and cyclic oxidation condition are in the range of 5.1 × 10⁻¹⁴ to 7.6 × 10⁻¹⁴ g² cm⁻⁴ s⁻¹, and the measured area specific resistance at 750 °C after 1000 h oxidation is around 10 mΩ cm², lower than that of the conventional Fe-Cr stainless steels and comparable with that of the Ni-based alloys. Thermal cycling seems to improve the oxide scale adherence and promotes the formation of the highly conductive Mn₂O₃, and in turn, to enhance the oxidation resistance and electrical property.     

NiO/NiFe2O4 dual-layer coating on pre-oxidized SUS 430 steel interconnect

A Ni/NiFe₂ dual-layer coating is deposited on 50-h pre-oxidized SUS 430 steel by magnetron sputtering for solid oxide fuel cell (SOFC) interconnects application, followed by thermal exposure in air at 800 °C for 1680 h. The thermally grown oxide scales exhibit tri-layer structure with inner Cr₂O₃ layer, middle NiO layer and outer NiFe₂O₄ spinel layer. The oxide coating converted from Ni/NiFe₂ coating not only inhibit the growth of Cr₂O₃ and the outward diffusion of Cr species but also improve the electrical performance of the surface scale. In addition, pre-oxidation treatment for the steel before Ni/NiFe₂ coating deposition prevents the interdiffusion between steel substrate and coating in the oxidation process.     

Oxidation behavior of nickel coating on ferritic stainless steel interconnect for SOFC application

The oxidation behavior of nickel coated ferritic stainless steel SS441 has been investigated. A nickel coating layer is deposited on the steel which is employed in a solid oxide fuel cell stack as interconnect. The nickel film is about 8 μm thick and is topped by an additional 4 μm thick La_0.67Sr_0.33MnO₃ (LSM) film on the interconnect cathode-contacting surface for the prevention of chromium evaporation from the steel substrate. A 10,000-h 800 °C isothermal ageing on 10 × 10 mm² steel coupons shows a continuous growth of oxide scales up to ∼200 μm in thickness on the surface, consisting of a 100 μm thick iron oxide layer followed by a complex Fe–Ni–Cr spinel structure. A single-cell stack is tested at 800 °C for up to 1226 h and an average degradation rate of 7.5% kh⁻¹ is observed. Oxidation characteristics of the coating system are analyzed after testing. A Fe–Ni spinel phase is found covering most of the surface area. This is attributed to the intensive interdiffusion of iron and nickel during the stack operation and the high intersolubility of the two elements. In both the tests of the steel coupons and the stack, LSM film structures are damaged by the thermally grown Fe–Ni oxides, and the expected Cr-preventing function is limited. The Fe–Ni spinel layer initially forms an effective obstacle against Cr out-migration. However, the increasing content of iron in the spinel phase induces oxide scale spallation afterwards. Though the fast grown Fe–Ni oxide scale can serve as an effective barrier against chromium out-migration, the iron-enriched scale structure is susceptible to corrosion attacks after an extended stack operation period.     

Evaluation of electrodeposited Fe-Ni alloy on ferritic stainless steel solid oxide fuel cell interconnect

Fe-Ni alloy is electrodeposited on ferritic stainless steel for intermediate-temperature solid oxide fuel cell (SOFC) interconnects application. The oxidation behavior of Fe-Ni alloy coated steel has been investigated at 800 °C in air corresponding to the cathode environment of SOFC. It is found that the oxidation rate of the Fe-Ni alloy coated steel becomes similar to that of the uncoated steel after the first week thermal exposure, although the mass gain of the coated steel is higher than that of the uncoated steel. Oxide scale formed on the uncoated steel mainly consists of Cr₂O₃ with (Mn,Cr)₃O₄ spinel. However, a double-layer oxide structure with a Cr-free outer layer of Fe₂O₃/NiFe₂O₄ and an inner layer of Cr₂O₃ is developed on the Fe-Ni alloy coated steel. The scale area specific resistance (ASR) for the Fe-Ni alloy coated steel is lower than that of the scale for the uncoated steel.     

Evaluation of pulse electroplated cobalt/yttrium oxide composite coating on the Crofer 22 APU stainless steel interconnect

Ferritic stainless steels have been evaluated as favorable materials for utilization in SOFC interconnects. However, there are difficulties in utilizing these metallic interconnects, including the quick decrease of their electrical conductivity and cathode poisoning due to the evaporation of Cr species. In this work, Co and Co/Y₂O₃ composite coatings have been deposited onto Crofer 22 APU stainless steels by the pulse current electrodeposition method and the oxidation and electrical properties of uncoated and coated steels have been evaluated. Cyclic oxidation was performed in air at 800 °C for 500 h, oxidation rates were calculated, and oxide layer microstructures were examined. SEM–EDS and XRD investigations exhibited the created oxide layer on both coated samples made up of two scale after oxidation. The internal thin scale was composed of Cr and O and the external scale comprised of Co, Mn, Cr, Fe, and O. Y₂O₃ was observed as dispersed particles in the external oxide scale after the cyclic oxidation test. The thicknesses of internal oxide scale were reduced and oxidations rates also were meaningfully decreased for Co/Y₂O₃-coated steels relative to uncoated and Co-coated steels. Finally the ASR values of coated and uncoated substrates was also tested as a function of temperature and time in air. Results showed that the ASR value of the Co/Y₂O₃-coated steel was 13.1 mΩ cm² after 500 h of cyclic oxidation at 800 °C, which was significantly lower than that of bare steel and the Co-coated sample.     

Oxidation behavior and electrical property of ferritic stainless steel interconnects with a Cr-La alloying layer by high-energy micro-arc alloying process

Chromium volatility, poisoning of the cathode material and rapidly decreasing electrical conductivity are the major problems associated with the application of ferritic stainless steel interconnects of solid oxide fuel cells operated at intermediate temperatures. Recently, a novel and simple high-energy micro-arc alloying (HEMAA) process is proposed to prepare LaCrO₃-based coatings for the type 430 stainless steel interconnects using a LaCrO₃-Ni rod as deposition electrode. In this work, a Cr-La alloying layer is firstly obtained on the alloy surface by HEMAA using Cr and La as deposition electrode, respectively, followed by oxidation treatment at 850 °C in air to form a thermally grown LaCrO₃ coating. With the formation of a protective scale composed of a thick LaCrO₃ outer layer incorporated with small amounts of Cr-rich oxides and a thin Cr₂O₃-rich sub-layer, the oxidation rate of the coated steel is reduced remarkably. A low and stable electrical contact resistance is achieved with the application of LaCrO₃-based coatings, with a value less than 40 mΩ cm² during exposure at 850 °C in air for up to 500 h.     

The effect of Mn on the oxidation behavior and electrical conductivity of Fe-17Cr alloys in solid oxide fuel cell cathode atmosphere

Four Fe-17Cr alloys with various Mn contents between 0.0 and 3.0 wt.% are prepared for investigation of the effect of Mn content on the oxidation behavior and electrical conductivity of the Fe-Cr alloys for the application of metallic interconnects in solid oxide fuel cells (SOFCs). During the initial oxidation stage (within 1 min) at 750 °C in air, Cr is preferentially oxidized to form a layer of Cr₂O₃ type oxide in all the alloys, regardless the Mn content, with similar oxidation rate and oxide morphology. The subsequent oxidation of the Mn containing alloys is accelerated caused by the fast outward diffusion of Mn ions across the Cr₂O₃ type oxide layer to form Mn-rich (Mn, Cr)₃O₄ and Mn₂O₃ oxides on the top. After 700 h oxidation a multi-layered oxide scale is observed in the Mn containing alloys, which corresponds to a multi-stage oxidation kinetics in the alloys containing 0.5 and 1.0 wt.% of Mn. The oxidation rate and ASR of the oxide scale increase with the Mn content in the alloy changes from 0.0 to 3.0 wt.%. For the application of metallic interconnects in SOFCs, Mn-free Fe-17Cr alloy with conducting Cr free spinel coatings is preferred.     

NiMn2O4 spinel as an alternative coating material for metallic interconnects of intermediate temperature solid oxide fuel cells

In an effort to improve the performance of SUS 430 alloy as a metallic interconnect material, a low cost and Cr-free spinel coating of NiMn₂O₄ is prepared on SUS 430 alloy substrate by the sol-gel method and evaluated in terms of the microstructure, oxidation resistance and electrical conductivity. A oxide scale of 3-4 μm thick is formed during cyclic oxidation at 750 °C in air for 1000 h, consisting of an inner layer of doped Cr₂O₃ and an outer layer of doped NiMn₂O₄ and Mn₂O₃; and the growth of Cr₂O₃ and formation of MnCr₂O₄ are depressed. The oxidation kinetics obeys the parabolic law with a rate constant as low as 4.59 × 10⁻¹⁵ g² cm⁻⁴ s⁻¹. The area specific resistance at temperatures between 600 and 800 °C is in the range of 6 and 17 mΩ cm². The above results indicate that NiMn₂O₄ is a promising coating material for metallic interconnects of the intermediate temperature solid oxide fuel cells.     

Effect of Ti addition on the electric and ionic property of the oxide scale formed on the ferritic stainless steel for SOFC interconnect

Ferritic stainless steels with Ti addition are considered as promising candidates for SOFC interconnect application. In this study, the effect of Ti addition on the electrical conductivity and Cr evaporation resistance was discussed in terms of microstructure and ionic property of the oxide scale by using TEM analysis and asymmetry polarization method. Ti addition induced the generation of ionic defects in the oxide layer and modified the growth kinetics of Cr₂O₃ and MnCr₂O₄, but in different manner depending on Ti amount. Ti content in a range of 0.05–0.07 wt% was effective for reducing the oxidation rate and electrical resistance. Addition of 1 wt% Ti promoted fast Cr₂O₃ growth due to the excess ionic defect in Cr₂O₃ matrix. However, the formation of the outermost MnCr₂O₄ layer was accelerated by Ti segregation near the scale/alloy interface and it reduced Cr evaporation effectively. Co-addition of a small amount of Ti and La enhanced Ti segregation without generation of excess ionic defect and improved both the electric conductivity and Cr evaporation resistance.     

Evaluation of the reactive-sintered (Mn,Co)3O4 spinel layer for SOFC cathode-side contact application

Simulated interconnect/contact/cathode cells are used to investigate the performance of different contact precursors that are reactively sintered into spinel contact layers with nominal compositions of Mn_1.5Co_1.5O₄ and MnCo₂O₄, respectively. Both bare and Mn_1.5Co_1.5O₄-coated interconnects are employed in this study, where the Mn_1.5Co_1.5O₄ interconnect coating is also prepared via reactive sintering. The isothermal area specific resistance (ASR) of the test cells is evaluated at 800 °C in air for 2000 h. All the test cells exhibited excellent electrical behavior with ASR values of less than 10 mΩ·cm² during the measurement. The presence of the dense Mn_1.5Co_1.5O₄ coating leads to a better ASR performance. Cross-sectional observation of the test cells is conducted to assess the compatibility of the contact layer with adjacent components as well as its effectiveness in suppressing chromia scale growth and blocking Cr migration from the interconnect to the cathode.     

The effects of temperature and oxygen pressure on the initial oxidation of stainless steel 441

The oxidation behavior of the stainless steel 441 in the initial 2 h was investigated gravimetrically at 600 °C–950 °C under various oxygen pressures. The morphology, composition and the growth stress of the scale on the oxidized alloy were analyzed by SEM/EDS and Raman spectra. It was found that the performances of the scale degraded with the temperature and oxygen pressure increasing. The oxidation of stainless steel 441 presented a multi-stages behavior. It was suggested that the first chemical reaction determining stage was the nonselective oxidation of steel surface. The following stage in pure oxygen ambient was the formation of chromium-oxide-mainly-containing layer. Kinetic mechanism of second stage oxidation changed from diffusion determining step (600–800 °C) to interface chemical reaction (900–950 °C) due to the decline of the protection of the oxides layer. Only linear rate law was obeyed in the lower oxygen pressure atmospheres at 800 and 900 °C within the initial 2 h.     

CuFe2O4 protective and electrically conductive coating thermally converted from sputtered CuFe alloy layer on SUS 430 stainless steel interconnect

An inexpensive CuFe alloy layer with an atomic ratio (1:2) of Cu to Fe is coated on SUS 430 stainless steels via magnetron sputtering for solid oxide fuel cells interconnect application. The coated steels are thermally exposed to air at 800 °C for 15 weeks. The CuFe alloy layer is converted to CuFe₂O₄ spinel layer atop Cr₂O₃ layer developed from steel substrate. The outer layer of CuFe₂O₄ spinel not only retards Cr outward migration and reduces oxidation rate but also significantly lowers area specific resistance of the surface scale which is predicted for solid oxide fuel cells lifetime by a parabolic law. The sputtered CuFe alloy layer demonstrates a promising prospect for the application of steel interconnects coatings.     

Effect of CeO2 on oxidation and electrical behaviors of ferritic stainless steel interconnects with NiFe coatings

Ferritic stainless steels are promising materials for application in interconnects of solid oxide fuel cells (SOFC). The present problems to be solved urgently for using ferritic stainless steels as interconnects are their rapid increase in electrical resistance and the cathode poisoning caused by evaporation of chromia. In the present study, the NiFe and NiFeCeO₂ alloy coatings have been electro-deposited onto 430 stainless steels (430SS). During oxidation at 800 °C in air, an outer dense NiFe₂O₄ layer and an inner protective Cr₂O₃ layer have thermally grown on the coated samples. The NiFe₂O₄ layer retards the outward migration of chromium effectively. The addition of CeO₂ reduces the growth rate of Cr₂O₃ and decreases the number of pores near the oxide scale/alloy interface. Moreover, a higher electrical conductivity has been achieved by the addition of CeO₂.     

Effects of applied current density and thermal cycling on the degradation of a solid oxide fuel cell cathode

Effects of applied current density and thermal cycles on the durability of a solid oxide fuel cell (SOFC) cathode have been studied. SOFC half-cells with and without a gadolinium-doped ceria (GDC) interlayer were fabricated and tested for 1000 h at 900 °C under various current densities and thermal cycles. Performance degradation of the half-cells was assessed by increment of the area specific resistance (ASR). Initially, the ASR of the half-cells without the GDC interlayer decreased for around 150 h due to cathode activation and thereafter increased. A rapid increase in the ASR was observed at higher applied current density, which is attributed to delamination of the electrolyte/cathode interface due to the formation of Sr zirconates, and microstructural change in the cathode. However, these adverse effects were prevented by the GDC interlayer. The half-cells with the GDC interlayer exhibited a smaller degradation rate as compared to that without the GDC interlayer. During the thermal cycling test, ASR values of all GDC interlayer thickness cells increased with an increasing number of thermal cycles. The thermally cycled cell with a GDC interlayer thickness of 3.4 μm showed a lower degradation rate due to the dense GDC interlayer, which resulted in less interfacial resistance and prevented elemental diffusion towards the electrolyte. However, the half-cells with GDC interlayer thickness of 2.4 and 4.5 μm showed a higher increase in the ASR due to relatively higher Sr diffusion and delamination of the cathode/GDC interlayer interface, respectively.     

Fabrication of stainless steel bipolar plates for fuel cells using dynamic loads for the stamping process and performance evaluation of a single cell

In this study, a dynamic load (square wave) is applied to bipolar plates in order to reduce forming defects from the stamping process. Four round (R) sizes of die (R 0.05, 0.1, 0.2, 0.3 mm) are applied to edges that ran from the channel to the rib of the stamping die. Fuel cell performance tests are carried out to analyse the depth and shape of bipolar plate channels formed according to the load conditions, and the effect of the die size on the fuel cell performance is evaluated. The depth of the bipolar plate channel increase with the round size of die regardless of the load type. The shape of the channel formed with a die of R 0.05 mm is trapezoidal, while that formed with a die of R 0.3 mm is triangular. Triangular channels have a higher current density than trapezoidal channels. A higher current density can be obtained with a square load than with a conventional straight load because the former produces a deeper and more uniform bipolar plate channel. The current density of a bipolar plate with a triangular channel formed by a square load with a die of R 0.3 mm is 531 mA cm⁻². After TiN coating, the current density is 784 mA cm⁻², which is about 58% of that of a graphite bipolar plate.