Promising alloys for intermediate-temperature solid oxide fuel cell interconnect application

The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn₂O₃/TiO₂ surface layer and/or a (Mn, Cr)₃O₄ spinel outer layer atop a Cr₂O₃ inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr₂O₃ inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys.     

A promising NiCo2O4 protective coating for metallic interconnects of solid oxide fuel cells

The NiCo₂O₄ spinel coating is applied onto the surfaces of the SUS 430 ferritic stainless steel by the sol-gel process; and the coated alloy, together with the uncoated as a comparison, is cyclically oxidized in air at 800 °C for 200 h. The oxidation behavior and oxide scale microstructure as well as the electrical property are characterized. The results indicate that the oxidation resistance is significantly enhanced by the protective coating with a parabolic rate constant of 8.1 × 10⁻¹⁵ g² cm⁻⁴ s⁻¹, while the electrical conductivity is considerably improved due to inhibited growth of resistive Cr₂O₃ and the formation of conductive spinel phases in the oxide scale.     

Metallic interconnects for solid oxide fuel cell: A review on protective coating and deposition techniques

With the reduction of solid oxide fuel cells (SOFCs) operating temperature to the range of 600 °C–800 °C, metallic alloy with high oxidation resistance are used to replace traditional ceramic interconnects. Metallic interconnects is advantageous over ceramic interconnects; in terms of manufacturability, cost, mechanical strength, and electrical conductivity. To date, promising candidates for metallic interconnects are all Cr-containing alloys, which are susceptible to volatile Cr migration that causes cell degradation. As such, protective coatings have been developed to effectively inhibit Cr migration; as well as maintain excellent electrical conductivity and good oxidation resistance. This article reviews the progress and technical challenges in developing metallic interconnects; different types of protective coatings and deposition techniques for metallic interconnects for intermediate-temperature SOFC applications.     

Investigation of MnCu0.5Co1.5O4 spinel coated SUS430 interconnect alloy for preventing chromium vaporization in intermediate temperature solid oxide fuel cell

The MnCu_0.5Co_1.5O₄ spinel coating is proposed as a protective coating for SUS430 alloy to improve its oxidation resistance and prevent chromium vaporization. The coated alloy is exposed to dual atmosphere (Air/H₂–3%H₂O) at 750 °C for 200 h, exhibiting a stable spinel structure on the air side, but reduced to MnO, Cu and Co on the fuel side. The coating layer could maintain integrated and dense with a thickness of 13–14 μm. The experiment results shown that the MnCu_0.5Co_1.5O₄ coating is an effective diffusion barrier that can inhibit oxidation and chromium vaporization of metallic interconnect. The relatively low amount of Cr deposition on LSM cathode on coated condition is considered associating with the stable electrochemical performance under current density of 400 mA cm^?2. The above results indicate that MnCu_0.5Co_1.5O₄ spinel is a promising coating for interconnect alloy of solid oxide fuel cell.     

Life prediction of coated and uncoated metallic interconnect for solid oxide fuel cell applications

In this paper, we present an integrated experimental and modeling methodology in predicting the life of coated and uncoated metallic interconnect (IC) for solid oxide fuel cell (SOFC) applications. The ultimate goal is to provide cell designer and manufacture with a predictive methodology such that the life of the IC system can be managed and optimized through different coating thickness to meet the overall cell designed life. Crofer 22 APU is used as the example IC material system. The life of coated and uncoated Crofer 22 APU under isothermal cooling was predicted by comparing the predicted interfacial strength and the interfacial stresses induced by the cooling process from the operating temperature to room temperature, together with the measured oxide scale growth kinetics. It was found that the interfacial strength between the oxide scale and the Crofer 22 APU substrate decreases with the growth of the oxide scale, and that the interfacial strength for the oxide scale/spinel coating interface is much higher than that of the oxide scale/Crofer 22 APU substrate interface. As expected, the predicted life of the coated Crofer 22 APU is significantly longer than that of the uncoated Crofer 22 APU.     

CuFe2O4/CuO coating for solid oxide fuel cell steel interconnects

CuFe_0.8 (Fe:Cu = 0.8:1, atomic ratio) alloy layer is fabricated on both bare and pre-oxidized SUS 430 steels by direct current magnetron sputtering, followed by exposing at 800 °C in air to obtain a protective coating for solid oxide fuel cell (SOFC) steel interconnects. The CuFe_0.8 alloy layer is thermally converted to CuFe₂O₄/CuO coating, which effectively suppresses the out-migration of Cr. Pre-oxidation treatment not only initially accelerates the formation of CuFe₂O₄/CuO coating but also further inhibits the Cr and Fe outward diffusion. Suppressing outward diffusion of Cr could improve electrical property of oxide scale and decrease the risk of cathode Cr-poisoning. Blocking out-diffusion of Fe is beneficial to stabilize the CuO layer. After 2520 h oxidation, the scale ASR at 800 °C is 66.9 mΩ cm² for coated bare steel, 43.4 mΩ cm² for the coated pre-oxidized steel.     

Electrophoretic deposition and low-temperature densification of Cu1.35Mn1.65O4 spinel for an interconnect protective coating in solid oxide fuel cells

As a protective coating of the interconnects in solid oxide fuel cells, spinel-structured Cu_1.35Mn_1.65O₄ powder was coated onto 460FC stainless steel by using the electrophoretic deposition method. A suitable amount of iodine was added to ethanol to charge the spinel powder with a high zeta potential value. Stainless steel substrates were immersed in a slurry, and a DC voltage in the range of 20–60 V was applied for 30–120 s. Because a low-temperature densification of the coated film is crucial for minimizing Cr out-diffusion from the stainless steel substrate, the coated spinel was decomposed into Cu and MnO by applying a heat treatment at 800 °C in a 5% H₂/95% N₂ atmosphere. Then, it was oxidized at 700 °C in air, leading to appropriate densification. The area-specific resistance of the films was 15–29 mΩ cm² after 1000 h at 700 °C in air.     

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.     

Investigation of iron–chromium–niobium–titanium ferritic stainless steel for solid oxide fuel cell interconnect applications

As part of an effort to develop cost-effective ferritic stainless steel-based interconnects for solid oxide fuel cell (SOFC) stacks, both bare AISI441 and AISI441 coated with (Mn,Co)₃O₄ protection layers were studied in terms of its metallurgical characteristics, oxidation behavior, and electrical performance. The addition of minor alloying elements, in particular Nb, led to formation of Laves phases both inside grains and along grain boundaries. In particular, the Laves phase which precipitated out along grain boundaries during exposure at intermediate SOFC operating temperatures was found to be rich in both Nb and Si. The capture of Si in the Laves phase minimized the Si activity in the alloy matrix and prevented formation of an insulating silica layer at the scale/metal interface, resulting in a reduction in area-specific electrical resistance (ASR). However, the relatively high oxidation rate of the steel, which leads to increasing ASR over time, and the need to prevent volatilization of chromium from the steel necessitates the application of a conductive protection layer on the steel. In particular, the application of a Mn_1.5Co_1.5O₄ spinel protection layer substantially improved the electrical performance of the 441 by reducing the oxidation rate.     

Highly conductive and stable Mn1.35Co1.35Cu0.2Y0.1O4 spinel protective coating on commercial ferritic stainless steels for intermediate-temperature solid oxide fuel cell interconnect applications

Chromia scale growth and Cr evaporation of ferritic stainless steel interconnects are known to be major causes of serious degradation of the solid oxide fuel cell (SOFC) stack. The development of suitable ceramic coating materials on the metallic interconnects has been demonstrated as an effective way to address these challenges. Herein, we developed a Mn_1.35Co_1.35Cu_0.2Y_0.1O₄ (MCCY) spinel material via a facile glycine-nitrate process as a protective coating on a metallic interconnect (SUS 441). Crystal structure and surface charge state analysis of the MCCY material revealed that co-doping of Y and Cu into the (Mn,Co)₃O₄ spinel resulted in redistribution of the Mn ions (Mn³⁺ and Mn⁴⁺) into the octahedral site, which increased the electrical conduction by enhanced small polaron hopping. Accordingly, the MCCuY-coated interconnect exhibited ∼8 times lower area specific resistance (ASR) than that of the undoped Mn_1.5Co_1.5O₄ (MCO) coated interconnect. Moreover, time-dependent ASR behavior of MCCuY-coated sample was monitored in-situ using electrochemical impedance spectroscopy at 650 °C, showing excellent stability with no observable change for >1000 h, while the ASR of the MCO-coated sample was raised by ∼71%. After 1000 h operation, we found strong adhesion between the MCCuY coating and the metallic interconnect as well as remarkably restricted Cr diffusion into the coating layer. Furthermore, the parabolic constant associated with the oxidation kinetics of the MCCuY-coated substrate (8.25 × 10⁻¹¹ mg² cm⁻⁴ s⁻¹) was ∼1 order of magnitude lower than that of the MCO-coated one (7.34× 10⁻¹⁰ mg² cm⁻⁴ s⁻¹) at 650 °C after 1000 h measurement. These results demonstrate that the MCCuY is a highly promising coating material of metallic interconnects for intermediate-temperature SOFC applications.     

MnCo1.9Fe0.1O4 spinel protection layer on commercial ferritic steels for interconnect applications in solid oxide fuel cells

In solid oxide fuel cells (SOFC) for operating temperatures of 800 °C or below, the interconnection plates can be made from stainless steel. This is a big economic advantage, but energy losses can be caused by undesirable reactions between the alloys and other SOFC components. The use of coatings on interconnect stainless steels can reduce this degradation. A MnCo_1.9Fe_0.1O₄ (MCF) spinel not only significantly decreases the contact resistance between a La_0.8Sr_0.2FeO₃ cathode and a stainless steel interconnect, but also acts as a diffusion barrier to prevent Cr outward migration through the coating. The level of improvement in electrical performance depends on the ferritic substrate composition. For Crofer22APU and F18TNb, with a Mn concentration of 0.4 and 0.12 wt%, respectively, the reduction in contact resistance is significant. In comparison, limited improvement is achieved by application of MCF on IT-11 and E-Brite containing no Mn. No influence of the minor additions of Si or Al is observed on contact resistance. The MCF protection layer bonds well to the stainless steel substrates under thermal cycling, but the thermal expansion difference is too large between the La_0.8Sr_0.2Co_0.75Fe_0.25O₃ contact layer used and Crofer22APU and IT-11.     

Stable LSM/LSTM bi-layer interconnect for flat-tubular solid oxide fuel cells

A bi-layer interconnect with La_0.8Sr_0.2MnO₃ and La_0.4Sr_0.6Ti_0.6Mn_0.4O₃ (LSM/LSTM) is applied to anode-supported button cells and flat-tubular cells. Using a button cell, SEM images and gas permeation tests confirm that the bi-layer possesses a dense microstructure. The area specific resistance (ASR) of the LSM/LSTM remains nearly constant under oxidizing/reducing atmospheres with varying gas concentrations. For comparison, an LSM/LST with the same thickness is prepared; an increase in the ASR is observed as the concentration of H₂ feed to the LST side decreases. The difference in the ASR of LSM/LST can be explained by exposure to a relatively high oxygen partial pressure and partial destruction of the interfacial LST layer region where oxygen diffuses from the LSM layer. Flat-tubular cells with the LSM/LSTM bi-layer interconnect achieve a maximum power density (MPD) of 463 mW cm^?2 using humidified H₂ fuel and air at 800 °C. With decreasing H₂ concentration in the fuel, the polarization resistance increases rather than the ohmic resistance, implying that the LSM/LSTM interconnect provides stable conduction property. In comparison with the conventional LSM/LST interconnect cell, it shows improved stability and performance as the concentration of H₂ in the fuel decreases.     

CoFe2O4 spinel protection coating thermally converted from the electroplated Co-Fe alloy for solid oxide fuel cell interconnect application

CoFe₂O₄ has been demonstrated as a potential spinel coating for protecting the Cr-containing ferritic interconnects. This spinel had an electrical conductivity of 0.85 S cm⁻¹ at 800 °C in air and an average coefficient of thermal expansion (CTE) of 11.80 × 10⁻⁶ K⁻¹ from room temperature to 800 °C. A series of Co-Fe alloys were co-deposited onto the Crofer 22 APU ferritic steel via electroplating with an acidic chloride solution. After thermal oxidation in air at 800 °C, a CoFe₂O₄ spinel layer was attained from the plated Co_0.40Fe_0.60 film. Furthermore, a channeled Crofer 22 APU interconnect electrodeposited with a 40-μm Co_0.40Fe_0.60 alloy film as a protective coating was evaluated in a single-cell configuration. The presence of the dense, Cr-free CoFe₂O₄ spinel layer was effective in blocking the Cr migration/transport and thus contributed to the improvement in cell performance stability.     

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.     

Co/LaCrO3 composite coatings for AISI 430 stainless steel solid oxide fuel cell interconnects

Rapidly decreasing electronic conductivity, chromium volatility and poisoning of the cathode material are the major problems associated with inevitable growth of chromia on ferritic stainless steel interconnects of solid oxide fuel cells (SOFC). This work evaluates the performance of a novel, electrodeposited composite Co/LaCrO₃ coating for AISI 430 stainless steel. The oxidation behaviour of the Co/LaCrO₃-coated AISI 430 substrates is studied in terms of scale microstructure and growth kinetics. Area-specific resistance (ASR) of the coated substrates has also been tested. The results showed that the Co/LaCrO₃ coating forms a triple-layer scale consisting of a chromia-rich subscale, a Co–Fe spinel mid-layer and a Co₃O₄ spinel top layer at 800 °C in air. This scale is protective, acts as an effective barrier against chromium migration into the outer oxide layer and exhibits a low, stable ASR of ∼0.02 Ω cm² after 900 h at 800 °C in air.     

Optimization of interconnect flow channels width in a planar solid oxide fuel cell

Finite element analysis is an effective method to investigate the uniformity of species distribution in solid oxide fuel cells. This paper presents a 3-D model with coupled mass transport, electron transfer and electrochemical reaction. Based on a working anode-supported SOFC with gas channels and porous electrodes, the model is validated by measured IV curves. The simulated results deviate no more than 3% from the measured data and indicate significant dependency of current density distribution on the gas composition distribution. Meanwhile, the simulated results also indicate that the ridges of the interconnect have negative effects on electrochemical reaction due to the limitation of mass transport. In further study, cases of various channel widths are calculated and analyzed, finding that the optimal width ratios for electrochemical in cathode and anode are 0.5.     

Effect of fabrication parameters on coating properties of tubular solid oxide fuel cell electrolyte prepared by vacuum slurry coating

The process of vacuum slurry coating for the fabrication of a dense and thin electrolyte film on a porous anode tube is investigated for application in solid oxide fuel cells. 8 mol% yttria stabilized zirconia is coated on an anode tube by vacuum slurry-coating process as a function of pre-sintering temperature of the anode tube, vacuum pressure, slurry concentration, number of coats, and immersion time. A dense electrolyte layer is formed on the anode tube after final sintering at 1400 °C. With decrease in the pre-sintering temperature of the anode tube, the grain size of the coated electrolyte layer increases and the number of surface pores in the coating layer decreases. This is attributed to a reduced difference in the respective shrinkage of the anode tube and the electrolyte layer. The thickness of the coated electrolyte layer increases with the content of solid powder in the slurry, the number of dip-coats, and the immersion time. Although vacuum pressure has no great influence on the electrolyte thickness, higher vacuum produces a denser coating layer, as confirmed by low gas permeability and a reduced number of defects in the coating layer. A single cell with the vacuum slurry coated electrolyte shows a good performance of 620 mW cm⁻² (0.7 V) at 750 °C. These experimental results indicate that the vacuum slurry-coating process is an effective method to fabricate a dense thin film on a porous anode support.     

Performance of cone-shaped tubular anode-supported segmented-in-series solid oxide fuel cell stack fabricated by dip coating technique

A simple and feasible technique is developed successfully to fabricate the cone-shaped tubular segmented-in-series solid oxide fuel cell (SOFC) stack. The cone-shaped tubular anode substrates and yttria-stabilized zirconia (YSZ) electrolyte films are fabricated by dip coating technique. After sintering at 1400 °C for 4 h, a dense and crack-free YSZ film with a thickness of about 35.9 μm is successfully obtained. The single cell, NiO–YSZ/YSZ/LSM–YSZ, provides a maximum power density of 1.08 and 1.35 W cm⁻² at 800 and 850 °C, respectively, using moist hydrogen (75 ml/min) as fuel and ambient air as oxidant.A two-cell-stack based on the above-mentioned cone-shaped tubular anode-supported SOFC was assembled and tested. The maximum total power at 800 °C was about 3.7 W.     

A review of recent progress in coatings, surface modifications and alloy developments for solid oxide fuel cell ferritic stainless steel interconnects

Ferritic stainless steels have become the standard material for solid oxide fuel cell (SOFC) interconnect applications. The use of commercially available ferritic stainless steels, not specifically designed for interconnect application, however, presents serious issues leading to premature degradation of the fuel cell stack, particularly on the cathode side. These problems include rapidly increasing contact resistance and volatilization of Cr from the oxide scales, resulting in cathode chromium poisoning and cell malfunction. To overcome these issues, a variety of conductive/protective coatings, surface treatments and modifications as well as alloy development have been suggested and studied over the past several years. This paper critically reviews the attempts performed thus far to mitigate the issues associated with the use of ferritic stainless steels on the cathode side. Different approaches are categorized and summarized and examples for each case are provided. Finally, directions and recommendations for the future studies are presented.