Oxyanion doping strategies to enhance the ionic conductivity in Ba2In2O5

Shin, Jongmoon; Orera, Alodia; Apperley, David C.; Slater, Peter R.

doi:10.1039/c0jm01978j

Cited by 66 publications

(66 citation statements)

References 32 publications

(45 reference statements)

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“…In particular, we have shown that the partial substitution of these oxyanions at the In/Sc site in Ba 2 (In/Sc) 2 O 5 leads to the introduction of disorder on the oxygen sublattice and a corresponding enhancement in the low temperature ionic conductivity [14][15][16][17][18]. In terms of electronic conducting materials, we have also reported the successful incorporation of silicate, phosphate and sulphate into SrMO 3 (M = Co, Mn), leading to a large enhancement in the electronic conductivity [19,20].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

et al. 2012

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In this paper we report the successful incorporation of borate and phosphate into CaMnO 3 and borate into La 1Ày Sr y MnO 3Àd . For CaMnO 3 , an increase in the electronic conductivity was observed, which can be correlated with electron doping due to the oxyanion doping favoring the introduction of oxide ion vacancies (as well as the higher valence of P 5+ compared to Mn 4+ in the case of phosphate doping). The highest conductivity at 800 C was observed for CaMn 0.95 P 0.05 O 3Àd , 43.0 S cm À1 , in comparison with 7.6 S cm À1 for undoped CaMnO 3 at the same temperature. For La 1Ày Sr y MnO 3Àd the conductivity suffers a decrease for all compositions on borate doping, attributed to a reduction in the hole (Mn 4+ ) concentration. In order to investigate the potential of these materials as SOFC cathodes, the chemical compatibility with Gd 0.1 Ce 0.9 O 1.95 (CGO10) has also been investigated. For the calcium manganites, the lowest temperature examined without reaction was 900 C, with minor amounts of Ca 4 Mn 3 O 10 observed at 1000 C. Composites of these cathode materials with 50% CGO10 were examined on dense CGO10 pellets and the area specific resistances (ASR) in symmetrical cells were determined. The ASR values, at 800 C, were 1.50, 0.37 and 0.30 U$cm 2 for CaMnO 3 , CaMn 0.95 B 0.05 O 3Àd and CaMn 0.95 P 0.05 O 3Àd , respectively. For the lanthanum strontium manganites, the B-doped compositions showed an improvement in the ASR values with respect to the parent compounds, despite the lower electronic conductivity. This may be due to an increase in ionic conductivity due to borate incorporation leading to the formation of oxide ion vacancies. Thus these preliminary results show that oxyanion doping has a beneficial effect on the performance of perovskite manganite cathode materials, and suggests that this doping strategy warrants further investigation in other perovskite cathode systems.

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Section: Introductionmentioning

confidence: 99%

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

et al. 2012

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“…26,30,33,34 In Ba 2 (In 0.6 Ti 0.2 Ln 0.2 ) 2 O 5 materials with Ln = Gd, Dy, Ho, Er, Yb, Lu-doped with cubic structure, 35 those materials that tended to show higher oxide ion conduction were also good proton conductors.…”

Section: F928mentioning

confidence: 99%

“…19,25,26,[29][30][31][32]45 The conductivity of nondoped Ba 2 In 2 O 5 was relatively low, although it significantly increased when δ was reduced to less than 0.4.…”

Section: Conductivity In Dry O 2 and 8% Humidified O 2 -mentioning

confidence: 99%

“…Journal of The Electrochemical Society, 162 (8) F927-F938 (2015) include (V, Mo, W), 25 Ti, 26 Zr, 27 Ce, 28 Si, 29 (P, S) 30 replaced with In and La 31 replaced with Ba, or (La, Si or La, P) 32 co-doped in both Ba and In.…”

Section: F928mentioning

confidence: 99%

“…20,25,26,29,30,32 Because the final goal is application of these electrolyte materials to fuel cells, evaluating the ionic conduction in both oxidizing atmosphere and reducing atmosphere is crucial. One way to separately investigate the temperature dependency of oxide ion transfer number t O 2− and proton transfer number t H + is to respectively observe the electromotive force (emf) of an oxygen concentration cell and a hydrogen concentration cell.…”

Section: F928mentioning

confidence: 99%

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Ionic Conduction and Power Generation Characteristics of Pr-Doped Ba₂In₂O₅for Proton-Conducting SOFCs

Ihara

2015

J. Electrochem. Soc.

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Highly Pr-doped Ba 2 In 2 O 5 (PBI) was successfully fabricated and its ionic conduction and power generation characteristics were studied in this work. Two PBI materials of different concentration ratio were evaluated: Pr:Ba:In = 0.9:1.1:1 (PBI910) and Pr:Ba:In = 1:1:1 (PBI000). PBI910 material was confirmed as single phase with cubic perovskite structure. However, PBI000 had both cubic phase and impurity phase. In a hydrogen concentration cell, the measured proton transfer number t H + of PBI910 at 500 • C was 0.81 and then decreased with increasing temperature, whereas the oxide ion transfer number t O 2− was 0.07 and then increased with increasing temperature. Power generation experiments were evaluated at 500 • C to 900 • C using PBI as electrolyte and H 2 as fuel. Results revealed that t H + and t O 2− showed different dependency on temperature and significantly affected the power density. Proton conduction dominated from 500 • C∼600 • C, and power density increased with increasing operating temperature due to improved proton conductivities. However, at 600∼800 • C, proton conductivities decreased, which caused a decrease in power density. Further increase in temperature into the 800 • C∼900 • C range showed oxide ion conduction to then dominate, and the consequent improved oxide ion conductivity again increased the power density Currently used SOFCs operate at temperatures above 800• C because their Y 2 O 3 -stabilized ZrO 2 electrolyte (YSZ) requires high temperature to limit ohmic losses across the electrolyte. However, the goal in SOFC development of lowering the operating temperature can significantly improve the reliability, durability, and stability of SOFCs. One target of recent SOFC research is to develop intermediate temperature SOFC systems (IT-SOFCs), namely, operating at 500• C∼700• C. Operating at such intermediate temperature has several advantages. First, reactions between the cell components are suppressed 1 , thus improving the durability of the system. Second, the electrochemical reaction on an electrode is rapid compared with that at temperatures below 500• C, and thus the over potential is relatively low, which in turn enables a high power density. To develop IT-SOFCs, faster ionic conductors are needed to replace the conventional YSZ electrolyte. 2-6A recent strategy is the use of ceramic materials with high proton conductivities as electrolyte for Compared with oxide-ion-conducting SOFCs, proton-conducting SOFCs (PC-SOFCs) generate water at the cathode side. Theoretically, open current voltage (OCV) calculated by the Nernst equation should be kept high under high fuel utilization operation conditions in PCSOFCs and thus provide an opportunity to develop a system with both high power density and high fuel utilization.8 Among reported proton conductors, materials with perovskite structure show higher conductivities than other structures such as LaP 3 O 9 , 9 LaNbO 4 , 10 and LaBaGaO 4 .11 In perovskite-type materials, the highest conductivities have been achieved using BaCeO 3 doped w...

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Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

Zhu

Zhou

Sunarso

et al. 2016

Adv Funct Materials

286

216

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1 wileyonlinelibrary.com evolution reaction (OER) is currently the limiting factor on the water splitting due to its sluggish kinetics involving the complex four-electron oxidation process. [3] To this end, the presence of an efficient OER electrocatalyst is essential to obtain an accelerated reaction rate. At present, precious metal-based iridium and ruthenium oxides (i.e., IrO 2 and RuO 2 ) are regarded as the OER catalysts benchmarks, [4] but their scarcity and high cost have hindered their wide-scale applications. IrO 2 and RuO 2 catalysts additionally show poor stability during long-term operation in alkaline solutions. [5] As such, tremendous efforts have been devoted to develop low-cost and earth-abundant alternative OER catalysts with high activity and good stability.Over the past few decades, due to their compositional and structural flexibility, precious metal-free perovskitetype oxides with a general formula of ABO 3 (A = alkaline-earth or rare-earth metals and B = transition metals) have attracted interests in various applications, e.g., solid oxide fuel cells (SOFCs), oxygen permeation membranes, metalair batteries, and supercapacitors. [6] Most recently, they were reported to also exhibit high OER activity in an alkaline solution. [7] Rossmeisl group and Koper group theoretically calculated that SrCoO 3 parent oxide would deliver the highest OER activity among LaMO 3 and SrMO 3 (M = transition metals) parent oxides via density functional theory calculations. [8] Shao-Horn and co-workers reported that one of the Developing cost-effective and efficient electrocatalysts for oxygen evolution reaction (OER) is of paramount importance for the storage of renewable energies. Perovskite oxides serve as attractive candidates given their structural and compositional flexibility in addition to high intrinsic catalytic activity. In a departure from the conventional doping approach utilizing metal elements only, here it is shown that non-metal element doping provides an another attractive avenue to optimize the structure stability and OER performance of perovskite oxides. This is exemplified by a novel tetragonal perovskite developed in this work, i.e., SrCo 0.95 P 0.05 O 3-δ (SCP) which features higher electrical conductivity and larger amount of O 2 2− /O − species relative to the non-doped parent SrCoO 3-δ (SC), and thus shows improved OER activity. Also, the performance of SCP compares favorably to that of well-developed perovskite oxides reported. More importantly, an unusual activation process with enhanced activity during accelerated durability test (ADT) is observed for SCP, whereas SC delivers deactivation for the OER. Such an activation phenomenon for SCP may be primarily attributed to the in situ formation of active A-site-deficient structure on the surface and the increased electrochemical surface area during ADT. The concept presented here bolsters the prospect to develop a viable alternative to precious metal-based catalysts.

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Oxyanion doping strategies to enhance the ionic conductivity in Ba₂In₂O₅

Cited by 66 publications

References 32 publications

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

Ionic Conduction and Power Generation Characteristics of Pr-Doped Ba₂In₂O₅for Proton-Conducting SOFCs

Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

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Oxyanion doping strategies to enhance the ionic conductivity in Ba2In2O5

Cited by 66 publications

References 32 publications

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

Synthesis and characterisation of oxyanion-doped manganites for potential application as SOFC cathodes

Ionic Conduction and Power Generation Characteristics of Pr-Doped Ba2In2O5for Proton-Conducting SOFCs

Phosphorus‐Doped Perovskite Oxide as Highly Efficient Water Oxidation Electrocatalyst in Alkaline Solution

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Oxyanion doping strategies to enhance the ionic conductivity in Ba₂In₂O₅

Ionic Conduction and Power Generation Characteristics of Pr-Doped Ba₂In₂O₅for Proton-Conducting SOFCs