High oxide ion and proton conductivity in a disordered hexagonal perovskite

Fop, Sacha; McCombie, Kirstie S.; Wildman, Eve J.; Skakle, Janet M. S.; Irvine, John T. S.; Connor, Paul A.; Savaniu, Cristian; Ritter, C.; Mclaughlin, Abbie C.

doi:10.1038/s41563-020-0629-4

Cited by 138 publications

(222 citation statements)

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“…The results demonstrate that above 300 C the crystal structure rearranges, resulting in an increase in the percentage of (W,Nb)O4 tetrahedra within the average structure. The same structural rearrangement has been reported for Ba3MoNbO8.5 22 and results in an enhancement of the bulk ionic conductivity. 22 Ba3W1.2Nb0.8O8.6 is ~ 13.0% and increases to ~ 41.8% at 500 °C and ~ 45.5% at 600 °C.…”

Section: Electrical Characterisationsupporting

confidence: 84%

“…The same structural rearrangement has been reported for Ba3MoNbO8.5 22 and results in an enhancement of the bulk ionic conductivity. 22 Ba3W1.2Nb0.8O8.6 is ~ 13.0% and increases to ~ 41.8% at 500 °C and ~ 45.5% at 600 °C. In contrast there are ~ 51.3% tetrahedra within the average structure of Ba3MoNbO8.5 at 300…”

Section: Electrical Characterisationsupporting

confidence: 84%

“…C which increases to ~ 64.5% at 500 °C and ~ 64.9% at 600 °C 22 . This shows that the rate of increase of the (W,Nb)O4 tetrahedra upon heating from 300 C to 600 C is faster in Ba3W1.2Nb0.8O8.6 than in Ba3MoNbO8.5 enhancing the bulk conductivity at 600 C (Figure 1 Figure S5).…”

Section: Electrical Characterisationmentioning

confidence: 91%

“…The thermal evolution of the bond lengths and angles are comparable to those previously described for Ba3MoNbO8.5. 22 The Ba3M'1+xM''1-xO8.5+x/2 (M' = W, Mo; M'' = Nb) phases all exhibit a second order Jahn-Teller distortion (SOJT) 32 (Table S2).…”

Section: Electrical Characterisationmentioning

confidence: 99%

“…21 It has been suggested that the same structural rearrangement previously reported for Ba3MoNbO8.5 occurs in these compounds, preserving the high-temperature ionic conductivity. 21,22 In the work reported here, we examine further the relationship between the ratio of (W/Nb)O4 tetrahedra to (W/Nb)O6 octahedra, temperature and conductivity. The W/Nb ratio was altered so as to adjust the oxygen stoichiometry according to Nb 5+ -> W 6+ + ½ O 2-resulting in the synthesis of Ba3W1.2Nb0.8O8.6.…”

Section: Introductionmentioning

confidence: 99%

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Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

et al. 2018

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The oxide ionic conductor BaWNbO has been synthesized as part of an investigation into the new class of BaM'M''O (M' = W, Mo; M'' = Nb) oxide-ion conducting hexagonal perovskite derivatives. The substitution of W for Nb in BaWNbO leads to an increase in the oxygen content, which enhances the low-temperature ionic conductivity. However, at 400 °C, the ionic conductivity of BaWNbO is still significantly lower than the molybdenum compound BaMoNbO. Remarkably, at 600 °C the bulk oxide ionic conductivities of BaMoNbO, BaWNbO, and BaWNbO are very similar (σ = 0.0022, 0.0017, and 0.0016 S cm, respectively). The variable-temperature neutron diffraction results reported here demonstrate that BaWNbO undergoes a similar structural rearrangement to BaMoNbO above 300 °C, but the ratio of (W/Nb)O tetrahedra to (W/Nb)O octahedra rises at a faster rate upon heating between 300 and 600 °C. There is a clear relationship between the ionic conductivity of BaM'M''O (M' = W, Mo; M'' = Nb) phases and the number of tetrahedrally coordinated M' and M ″ cations present within the crystal structure.

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Section: Electrical Characterisationsupporting

confidence: 84%

Section: Electrical Characterisationsupporting

confidence: 84%

Section: Electrical Characterisationmentioning

confidence: 91%

Section: Electrical Characterisationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

et al. 2018

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High Proton Conductivity in β‐Ba₂ScAlO₅ Enabled by Octahedral and Intrinsically Oxygen‐Deficient Layers

Murakami

Avdeev

Morikawa

et al. 2022

Adv Funct Materials

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Proton conductors are promising materials for clean energy, but most available materials exhibit sufficient conductivity only when chemically substituted to create oxygen vacancies, which often leads to difficulty in sample preparation and chemical instability. Recently, proton conductors based on hexagonal perovskite‐related oxides have been attracting attention as they exhibit high proton conductivity even without the chemical substitutions. However, their conduction mechanism has been elusive so far. Herein, taking three types of oxides with different stacking patterns of oxygen‐deficient layers (β‐Ba2ScAlO5, α‐Ba2Sc0.83Al1.17O5, and BaAl2O4) as examples, the roles of close‐packed double‐octahedral layers and oxygen‐deficient layers in proton conduction are shown. It is found that “undoped” β‐Ba2ScAlO5, which adopts a structure having alternating double‐octahedral layer and double‐tetrahedral layer with intrinsically oxygen‐deficient hexagonal BaO (h') layer, shows high proton conductivity (≈10−3 S cm−1 above 300 °C), comparable to representative proton conductors. In contrast, the structurally related oxides α‐Ba2Sc0.83Al1.17O5 and BaAl2O4 exhibit lower conductivity. Ab initio molecular dynamics simulations revealed that protons in β‐Ba2ScAlO5 migrate through the double‐octahedral layer, while the h′ layer plays the role of a “proton reservoir” that supplies proton carriers to the proton‐conducting double‐octahedral layers. The distinct roles of the two layers in proton conduction provide a strategy for developing high‐performance proton conductors.

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High Oxide‐Ion Conductivity through the Interstitial Oxygen Site in Sillén Oxychlorides

Yaguchi

Morikawa

Tsuda

et al. 2023

Adv Funct Materials

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Oxide-ion conductors are gaining attention as future materials in energy applications, such as solid oxide fuel cells. Many Bi-containing compounds exhibit high oxide-ion conductivity via conventional vacancy mechanism. However, interstitial oxide-ion conduction is rare in Bi-containing materials. Herein, high oxide-ion conductivity is reported through interstitial oxygen sites in Sillén oxychlorides, LaBi 2−x Te x O 4+x/2 Cl (Bi 2 LaO 4 Cl-based oxychlorides). Oxide-ion conductivity of LaBi 1.9 Te 0.1 O 4.05 Cl is 20 mS cm −1 at 702 °C, and higher than best oxide-ion conductors as Bi 2 V 0.9 Cu 0.1 O 5.35 below 201 °C. Despite of the presence of Bi and Te species, LaBi 1.9 Te 0.1 O 4.05 Cl shows extremely high chemical and electrical stability at 400 °C from oxygen partial pressure 10 −25 to 0.2 atm and high chemical stability under CO 2 flow, wet 5% H 2 in N 2 flow, and air with natural humidity. Neutron scattering length density analysis, DFT calculations, and ab initio molecular dynamics simulations indicate that the extremely high oxide-ion conduction is attributed to cooperative diffusion through interstitial oxygen sites (interstitialcy diffusion mechanism) in triple fluorite-like layers. The present findings demonstrate the ability of LaBi 2−x Te x O 4+x/2 Cl as superior oxide-ion conductors, which can open new horizons for oxide-ion conductors.

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High oxide ion and proton conductivity in a disordered hexagonal perovskite

Cited by 138 publications

References 50 publications

Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

High Proton Conductivity in β‐Ba₂ScAlO₅ Enabled by Octahedral and Intrinsically Oxygen‐Deficient Layers

High Oxide‐Ion Conductivity through the Interstitial Oxygen Site in Sillén Oxychlorides

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High oxide ion and proton conductivity in a disordered hexagonal perovskite

Cited by 138 publications

References 50 publications

Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6

Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba3W1.2Nb0.8O8.6

High Proton Conductivity in β‐Ba2ScAlO5 Enabled by Octahedral and Intrinsically Oxygen‐Deficient Layers

High Oxide‐Ion Conductivity through the Interstitial Oxygen Site in Sillén Oxychlorides

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Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

Relationship between the Crystal Structure and Electrical Properties of Oxide Ion Conducting Ba₃W_1.2Nb_0.8O_8.6

High Proton Conductivity in β‐Ba₂ScAlO₅ Enabled by Octahedral and Intrinsically Oxygen‐Deficient Layers