Hydrogen Oxidation Mechanisms on Perovskite Solid Oxide Fuel Cell Anodes

Zhu, Tenglong; Fowler, Daniel E.; Poeppelmeier, Kenneth R.; Han, Min−Koo; Barnett, Scott A.

doi:10.1149/2.1321608jes

Cited by 59 publications

(76 citation statements)

References 43 publications

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“…The power law-type dependence, Ri  CH2 n , was obtained with n= -0.45, -0.31, and -0.16 at 450 ˚C, 500 ˚C, and 550 ˚C, respectively. Similar power law dependence of anodic polarization resistance on the H2 partial pressure has been observed in several studies on solid oxide fuel cells 14,24. According to the model Zhu et al developed, a power law exponent of -1 corresponded to dissociative adsorption of H2 as the rate-limiting…”

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confidence: 76%

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Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

Jiang

2017

ACS Appl. Mater. Interfaces

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A planar mixed-potential type sensor consisting of LaSrCrFeO sensing electrode, yttria-stabilized zirconia solid electrolyte, and Pt reference electrode was developed for H detection. The sensor showed high and repeatable response with a value of -143.6 mV for 1000 ppm of H at 450 °C. The sensor response varied linearly or logarithmically with the hydrogen concentration in the range of 20-100 ppm and 100-1000 ppm of H, respectively. The response/recovery time generally decreased with increasing concentration and temperature, and reached almost steady above 300 ppm of H. Response time as short as 4 s and recovery time of 24 s were attained at 450 °C for 500 ppm. The sensor exhibited excellent selectivity to hydrogen against interference of CH, CH, CO, NO, and NH. The mixed-potential mechanism was assessed by electrochemical measurements, and the sensing behavior was discussed in relation to the reaction kinetics. The excellent H sensing performance for concentrations above 100 ppm is ascribed to the high electrocatalytic activity of the perovskite electrode to H oxidation. The inferior performance for lower H concentrations may be related with slow gas diffusion in the electrode.

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confidence: 76%

“…As shown in Figure 10 step, whilst a value of -0.5 corresponded to the charge-transfer reaction limit. 24 If this model also holds for the present case, the much smaller n value obtained here relative to -1 would exclude a significant role of gas diffusion or dissociative adsorption limit.…”

Section: Electrochemical Processesmentioning

confidence: 53%

Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

Jiang

2017

ACS Appl. Mater. Interfaces

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“…47 closest to the present conditions -750 100 mbar H 2 , and 30 mbar H 2 O. From the electrochemical data of the thin film, the ASR of a porous electrode can be calculated by using a transmission line circuit model 51 and microstructural data from 3D tomography: 47 …”

Section: Resultsmentioning

confidence: 73%

“…It was further shown in Ref. 47 that a catalytic metal on the oxide surface promotes hydrogen dissociative adsorption, with subsequent "spillover" of H atoms from the metal onto the oxide surface. A spillover mechanism can also explain why the 5 nm Ti adhesion layer does not strongly impede the TPB effect.…”

Section: Resultsmentioning

confidence: 99%

The Electrochemical Properties of Sr(Ti,Fe)O_3-δfor Anodes in Solid Oxide Fuel Cells

Nenning

Volgger

Miller

et al. 2017

J. Electrochem. Soc.

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Reduction-stable mixed ionic and electronic conductors such as Sr(Ti,Fe)O 3-δ (STF) are promising materials for application in anodes of solid oxide fuel cells. The defect chemistry of STF and its properties as solid oxide fuel cell (SOFC) cathode have been studied thoroughly, while mechanistic investigations of its electrochemical properties as SOFC anode material are still scarce. In this study, thin film model electrodes of STF with 30% and 70% Fe content were investigated in H 2 +H 2 O atmosphere by electrochemical impedance spectroscopy. Lithographically patterned thin film Pt current collectors were applied on top or beneath the STF thin films to compensate for the low electronic conductivity under reducing conditions. Oxygen exchange resistances, electronic and ionic conductivities and chemical capacitances were quantified and discussed in a defect chemical model. Increasing Fe content increases the electro-catalytic activity of the STF surface as well as the electronic and ionic conductivity. Current collectors on top also increase the electrochemical activity due to a highly active Pt-atmosphere-STF triple phase boundary. Furthermore, the electrochemical activity depends decisively on the H 2 :H 2 O mixing ratio and the polarization. Acceptor-doped mixed ionic and electronic conductors are a promising class of materials for application in solid oxide fuel cell (SOFC) electrodes and they are widely investigated as SOFC cathodes due to their low polarization resistance.1-3 Some of these materials are chemically stable and mixed conducting also in humidified hydrogen atmosphere, 4 which makes them applicable in SOFC anodes. Several mixed conductors, such as acceptor doped (La,Sr)(Cr,Mn)O 3 , [5][6][7][8] donor-doped SrTiO 3 9,10 and Sr(Ti,Fe)O 3-δ -Ce 0.9 Gd 0.1 O 2-δ (STF-GDC) composites 11 were investigated in form of porous SOFC anodes. Most of these studies revealed moderately low polarization resistances. In STF-GDC composites, for example, the anode polarization resistance was <0.2 cm 2 at 800• C, and the overall performance increased with increasing Fe content. However, the usually ill-defined geometry of porous electrodes makes the analysis of specific materials parameters such as electronic and ionic conductivity or oxygen exchange activity very challenging.Thin film model electrodes have well defined and controllable geometry and comparatively simple pathways of electron and oxygen ion migration. This strongly facilitates identification of reaction pathways and quantification of the oxygen exchange activity of the material's surface. [12][13][14][15][16][17][18] Mechanistic studies using thin film model electrodes have so far been performed mainly in oxidizing atmosphere. Thorough studies of the mechanisms of electrochemical oxygen exchange in reducing atmospheres are still largely missing, not only for STF, but for most reduction stable mixed conductors, except for (Gd or Sm) doped ceria [19][20][21][22][23][24] and a study on (La,Sr)FeO 3-δ. 25 The typically low electronic conductivity of accep...

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“…[83] To address that problem, perovskite oxidesh ave been found to exhibit ah igherp olarization resistance as compared with Ni-based anodes. [84] Hence, ase xcellent candidate anode materials potentially combining the best attributes of all of these materials,N i-based perovskite oxide composites have been reported. Specifically,c lasses of Fe-and Ni-doped LaSrCrO 3 [60] Electrochemical data have shown that the maximum power density and maximum current density performance metrics of af uel cell incorporating these different anodesi ncreased in the order of LSCFe (i.e.,3 60 mW cm À2 and 1000 mA cm À2 ) < LSCNi (i.e.,4 60 mW cm À2 and 1300 mA cm À2 ) < LSCNi-Fe (i.e., 560 mW cm À2 and 1700mAcm À2 ).…”

Section: Solid Oxide Fuel Cells (Sofc): Hydrogen Oxidation Reactionatmentioning

confidence: 99%

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

Tan

Salvatore

et al. 2019

Chemistry A European J

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With the ultimate goal of simultaneously finding cost‐effective, more earth‐abundant, and high‐performance alternatives to commercial Pt/Pd‐based catalysts for electrocatalysis, this review article highlights advances in the use of perovskite metal oxides as both catalysts and catalyst supports towards the oxygen reduction reaction (ORR) and the methanol oxidation reaction (MOR) within a direct methanol fuel cell (DMFC) configuration. Specifically, perovskite metal oxides are promising as versatile functional replacements for conventional platinum‐group metals, in part because of their excellent ionic conductivity, overall resistance to corrosion, good proton‐transport properties, and potential for interesting acidic surface chemistry, all of which contribute to their high activity and reasonable stability, especially within an alkaline electrolytic environment.

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Hydrogen Oxidation Mechanisms on Perovskite Solid Oxide Fuel Cell Anodes

Cited by 59 publications

References 43 publications

Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

The Electrochemical Properties of Sr(Ti,Fe)O_3-δfor Anodes in Solid Oxide Fuel Cells

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

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Hydrogen Oxidation Mechanisms on Perovskite Solid Oxide Fuel Cell Anodes

Cited by 59 publications

References 43 publications

Fast Response, Highly Sensitive and Selective Mixed-Potential H2 Sensor Based on (La, Sr)(Cr, Fe)O3-δ Perovskite Sensing Electrode

Fast Response, Highly Sensitive and Selective Mixed-Potential H2 Sensor Based on (La, Sr)(Cr, Fe)O3-δ Perovskite Sensing Electrode

The Electrochemical Properties of Sr(Ti,Fe)O3-δfor Anodes in Solid Oxide Fuel Cells

Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells

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Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

Fast Response, Highly Sensitive and Selective Mixed-Potential H₂ Sensor Based on (La, Sr)(Cr, Fe)O_3-δ Perovskite Sensing Electrode

The Electrochemical Properties of Sr(Ti,Fe)O_3-δfor Anodes in Solid Oxide Fuel Cells