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.     

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.     

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.     

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.     

Effect of annealing conditions on in situ formation of Cr2O3 diffusion barrier

The previous investigation suggested the approach for an in situ formation of Cr₂O₃ diffusion barrier by annealing the cold-sprayed Ni coatings on 310SS. In this paper, the influences of annealing conditions on the growth kinetics of Cr₂O₃ and substrate microstructure were investigated. Results show that Cr₂O₃ formed at the selected annealing temperatures of 850, 900 and 950°C for different durations of 4, 8 and 20?h. Increasing temperature enhanced the growth kinetics of Cr₂O₃ and the Mn content in the oxide layer. The annealing process for the growth of Cr₂O₃ improves the coating adhesion compared to the as-deposited coating. However, annealing at 950°C resulted in the precipitation of chromium carbides and enhanced the element inter-diffusion across the substrate/coating interface.     

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.     

Efficiencies of cobalt- and copper-based coatings applied by different deposition processes for applications in intermediate-temperature solid oxide fuel cells

Solid Oxide Fuel Cells (SOFCs) are electrochemical conversion devices that produce electricity directly by oxidising a fuel. The interconnects between the individual cells need to be coated to limit Cr(VI) evaporation from the steel and to preserve electrical conductivity. Physical Vapour Deposition (PVD)-coated samples with Ce/Co, Ce/Cu, and Ce/MnCu, and Thermal Spray (TS)-coated Mn/Co, Cu and Mn/Cu and AISI 441 steel samples were exposed at 650 °C for up to 1000 h. The PVD Ce/Co and Ce/Cu coatings, as well as the TS Mn/Co coating, exhibited the formation of a thin protective Cr₂O₃ scales underneath the coating. These samples also exhibited the lowest area-specific resistance (ASR) values. The remainder of the samples exhibited much higher mass gains and higher ASR values. Cr(VI) evaporation measurements showed that all the coatings behaved approximately the same despite the PVD coatings being only about one-tenth of the thickness of the TS coatings.     

High-temperature oxidation process analysis of MnCo2O4 coating on Fe-21Cr alloy

Even though the operation temperature of solid oxide fuel cells (SOFCs) stacks has been reduced (∼750 °C), stainless steel interconnect within the stacks still requires protection by high conductive coatings to delay the growth of oxide scales and reduce chromium evaporation. Manganese cobaltite spinel protective coating with a nominal composition of MnCo₂O₄ was produced on Fe-21Cr stainless steel. Electrical, microstructural and compositional analysis were performed to investigate the interfacial reaction of MnCo₂O₄ protective coating with the stainless steel substrate during 750 °C oxidation process. The spinel coating not only acts as a barrier to Cr outward transport, but also improves the electrical conductivity of the alloy interconnect during long-term oxidation. The coated alloy demonstrates good electrical conductivity with an area specific resistance (ASR) of about 5 mOhm cm² after oxidation for 1000 h at 750 °C, which is about 1/4 of the ASR of bare Fe-21Cr alloy. The reduction of ASR might be caused by the fact that Cr migrated from the steel substrate interact with MnCo₂O₄ coating and generated Mn-Co-Cr spinel phase, which has higher electrical conductivity than that of Cr₂O₃.     

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 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.     

Ferrite/zirconia-coated foam device prepared by spin coating for solar demonstration of thermochemical water-splitting

A Ferrite/zirconia foam device in which reticulated ceramic foam was coated with zirconia-supported Fe₃O₄ or NiFe₂O₄ as a reactive material was prepared by a spin-coating method. The spin-coating method can shorten the preparation period and reduce the coating process as compared to the previous wash-coating method. The foam devices were examined for hydrogen productivity and cyclic reactivity in thermochemical two-step water-splitting. The reactivity of these foam devices were studied for the thermal reduction of ferrite on a laboratory scale using a sun simulator to simulate concentrated solar radiation, while the thermally reduced foam devices were reacted with steam in another quartz reactor under homogeneous heating in an infrared furnace. The most reactive foam device, NiFe₂O₄/m-ZrO₂/MPSZ, was tested for successive two-step water-splitting in a windowed single reactor using solar-simulated Xe-beam irradiation with a power input of 0.4-0.7 kW_th. The production of hydrogen continued successfully in the 20 cycles that were demonstrated using the NiFe₂O₄/m-ZrO₂/MPSZ foam device. The NiFe₂O₄/m-ZrO₂/MPSZ foam device produced hydrogen at a rate of 1.1-4.6 cm³ per gram of device through 20 cycles and reached a maximum ferrite conversion of 60%.     

Post-mortem evaluation of oxidized atmospheric plasma sprayed Mn–Co–Fe oxide spinel coatings on SOFC interconnectors

Interconnects employed in solid oxide fuel cells require electrically conductive protective coatings such as those based on manganese cobalt oxide spinels in order to prevent evaporation of volatile Cr(VI)-compounds and to minimize high temperature corrosion. MnCo_2−xFe_xO₄ based (where x = 0.1 and 0.3) oxide spinel protective coatings were manufactured by the atmospheric plasma spraying process on Crofer 22 APU substrates. The coated substrates were oxidized at 700 °C in air for 1000 h and post-mortem analyses were conducted to study the performance of the thermal sprayed coatings. During the high temperature oxidation, a four-point on-line measurement technique was used for area specific resistance studies. The MnCo_1.7Fe_0.3O₄ coating was tested together with the La_0.85Sr_0.15Mn_1.1O₃-spacer.     

Performance of stainless steel interconnects with (Mn,Co)3O4-Based coating for solid oxide electrolysis

Mixed transition-metal oxide coatings are commonly applied to stainless steel interconnects for solid oxide cell stacks. Such coatings reduce oxidation and Cr evaporation rates, leading to improved degradation rate and stack lifetime. Here, the ChromLok? MCO-based composition (Mn,Co)₃O₄ is applied to Crofer 22 APU stainless steel and evaluated specifically for application in solid oxide electrolyzer stacks operating around 800 °C and utilizing oxygen-ion-conducting solid oxide cells. The MCO coating is found to decrease the stainless steel oxidation rate by about one order of magnitude, and decrease the Cr evaporation rate by fourfold. The coating also dramatically lowers the rate of area-specific resistance increase for stainless steel coupons oxidized for 500 h with constant current applied, from 33 mΩ1cm² kh^?1 for an uncoated coupon to less than 4 mΩ1cm² kh^?1 for coated coupons. The coating is demonstrated on full-scale interconnects for single-cells, where the coating dramatically reduces degradation rate, and for a stack, which displays stable operation for 700 h.     

Hydrogen permeation properties of CrxCy@Cr2O3/Al2O3 composite coating derived from selective oxidation of a CrC alloy and atomic layer deposition

Metal oxides and carbides are promising tritium permeation barrier coatings for fusion reactors. However, the thermomechanical mismatch between the coating and substrate poses a threat to their interface's integrity during fabrication and operation. To address this issue, a metallic interlayer coating was introduced followed by selective oxidation in which a compact and uniform CrC amorphous alloy coating was successfully deposited on the stainless steel substrate by pulsed electrochemical deposition. A new composite coating of Cr_xC_y@Cr₂O₃/Al₂O₃ was formed by subsequent controlled oxidation conversion and atomic layer deposition. The phase, morphology, chemical state and defects of the films were analyzed and compared both before and after hydrogen exposure at 300 °C. The results show that this new kind of composite coating, based on the principles of grain boundary pinning of chromic oxide with carbide and defect healing of alumina, can remarkably improve the hydrogen permeation barrier performance of these materials.     

Investigation of Mn/Co coated T441 alloy as SOFC interconnect by on-cell tests

T441 has been identified as the candidate for SOFC interconnect material because it is assumed that with the addition of Nb, Ti in T441, the formation of continuous silica sub-layer could be avoided or delayed due to Nb and Si rich secondary phase formation stabilizing silicon migration. Previously, electrodeposition Mn/Co alloys followed by oxidation has been proved as a simple and cost effective method to fabricate (Mn, Co)₃O₄ coatings. In this work, Mn/Co coated T441 interconnects were tested as the cathode current collector of solid oxide fuel cells. For comparison, uncoated and 500 h pre-oxidized T441 interconnects were tested as well. The cell with coated interconnect shows stable performance during total 850 h test, even after severe thermal cycles (heating rate 26.7 °C/min). The coating shows good adhesion with substrate and it can prevent Cr poisoning on SOFC cathode. While the cell with uncoated and pre-oxidized T441 interconnects degrade rapidly. XRD results show the coating peaks shifted from mainly Co₃O₄ with some little Mn before test to MnCo₂O₄ after test due to Mn diffusion from substrate. No Cr penetrated to the coating layer, as further proved by EDX linescan. The effect of laves phase on the Cr₂O₃ sub-layer formation and coating thickness was further discussed.     

Synthesis of magnetic Ag3PO4/Ag/NiFe2O4 composites towards super photocatalysis and magnetic separation

The synthesis of Ag₃PO₄/Ag was performed through in-situ deposition and photo-reduction processes with magnetic NiFe₂O₄ nanofibers towards enhanced photocatalysis performance and stability. NiFe₂O₄ inhibit the photoreduction of Ag₃PO₄ into Ag and resulted in high stability. The photocatalytic activity of Ag₃PO₄/Ag/NiFe₂O₄ samples was studied by methylene blue degrading under visible light irradiation. The Ag₃PO₄/Ag/NiFe₂O₄ photocatalyst with NiFe₂O₄ loading of 3% revealed good photocatalytic performance, high stability and quick degradation after 5 cycles. Photoluminescence spectra and photocurrent tests demonstrated that the formation of hetero-junction facilitated the separation of photo-generated carriers. The trapping experiments confirmed that h⁺ and ?OH were active species during the degradation process.     

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.     

Electroplated Ni–Fe2O3 composite coating for solid oxide fuel cell interconnect application

Ni–Fe₂O₃ composite coating was applied onto ferritic stainless steel using the cost-effective method of electroplating for intermediate temperature solid oxide fuel cell (SOFC) interconnects application. By comparison, the coated and bare steels were evaluated at 800 °C in air corresponding to the cathode environment of SOFC. The oxidation investigations indicated that the oxidation rate of the coated steel was close to that of the bare steel after initially rapid mass gain. The mass gain of the coated steel was higher than that of the bare steel owing to the formation of double-layer oxide structure with an outer layer of (Ni,Fe)₃O₄/NiO atop an inner layer of Cr₂O₃. The area specific resistance (ASR) of the double-layer oxide scale was lower than that of the Cr₂O₃ scale thermally grown on the bare steel.     

Synergistic effect of PANI and NiFe2O4 for photocatalytic hydrogen evolution under visible light

As an effective photocatalyst, PANI/NiFe₂O₄ nanocomposite was prepared by in situ polymerization of aniline. The physicochemical properties of the composite were characterized by TEM, XRD, FT-IR spectra, UV–vis spectroscopy, XPS and Photoelectrochemical Measurements. Compared with NiFe₂O₄ and PANI, PANI/NiFe₂O₄ nanocomposite has a better photocatalytic activity, which exhibited the remarkable property of hydrogen production under visible light. The photocatalytic mechanism was also discussed. The heterojunction of PANI and NiFe₂O₄ promoted the separation of photogenerated e^? and h⁺ on the surface of PANI/NiFe₂O₄. Besides, the structure of PANI/NiFe₂O₄ in the polymerization was detected by FT-IR. NiFe₂O₄ was proved that in favor of the formation of nucleate phenazine-like structure in the progress of in situ polymerization. Then the chain structure of conductive PANI was formed, which leading to the promotion of photocatalytic activity.     

High-temperature sulfuric acid decomposition over complex metal oxide catalysts

Activity and stability of FeTiO₃, MnTiO₃, NiFe₂O₄, CuFe₂O₄, NiCr₂O₄, 2CuO·Cr₂O₃, CuO and Fe₂O₃ for the atmospheric decomposition of concentrated sulfuric acid in sulfur-based thermochemical water splitting cycles are presented. Catalyst activity was determined at temperatures from 725 to 900 °C. Catalytic stability was examined at 850 °C for up to 1 week of continuous operation. The results were compared to a 1.0 wt% Pt/TiO₂ catalyst. Surface area by nitrogen physisorption, X-ray diffraction analyses, and temperature programmed desorption and oxidation were used to characterize fresh and spent catalyst samples.Over the temperature range, the catalyst activity of the complex oxides followed the general trend: 2CuO·Cr₂O₃ > CuFe₂O₄ > NiCr₂O₄ ≈ NiFe₂O₄ > MnTiO₃ ≈ FeTiO₃. At temperatures less than 800 °C, the 1.0 wt% Pt/TiO₂ catalyst had higher activity than the complex oxides, but at temperatures above 850 °C, the 2CuO·Cr₂O₃ and CuFe₂O₄ samples had the highest activity.Surface area was found to decrease for all of the metal oxides after exposure to reaction conditions. In addition, the two complex metal oxides that contained chromium were not stable in the reaction environment; both leached chromium into the acid stream and decomposed into their individual oxides. The FeTiO₃ sample also produced a discoloration of the reactor due to minor leaching and converted to Fe₂TiO₅. Fe₂O₃, MnTiO₃ and NiFe₂O₄ were relatively stable in the reaction environment. In addition, CuFe₂O₄ catalyst appeared relatively promising due to its high activity and lack of any leaching issues; however it deactivated in week-long stability experiments.Complex metal oxides may provide an attractive alternative to platinum-based catalyst for the decomposition of sulfuric acid; however, the materials examined in this study all displayed shortcomings including material sintering, phase changes, low activity at moderated temperatures due to sulfate formation, and decomposition to their individual oxides. More effort is needed in this area to discover metal oxide materials that are less expensive, more active and more stable than platinum catalysts.