Dramatic Enhancement of Long-Term Stability of Erbia-Stabilized Bismuth Oxides via Quadrivalent Hf Doping

Yun, Byung-Hyun; Lee, Chan‐Woo; Jeong, Incheol; Lee, Jun Young

doi:10.1021/acs.chemmater.7b03894

Cited by 23 publications

(5 citation statements)

References 23 publications

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“…Doping with highly charged cations Hf 4+ at a level of 1 % gives a little effect on conductivity. 15 When doping 3 % or more, non-conductive clusters are inevitably formed. Therefore, minor doping in the development of a solid electrolyte was limited to 2 %.…”

Section: Existence Area Of the Tetragonal Phasementioning

confidence: 99%

“…7) are positioned in the literature as the best solid electrolytes, which possess the conductivity of Bi0.8Er0.2O1.50 ceramics while maintaining the structure of disordered fluorite and conductive properties after 1000 hours of annealing at 600 °C due to hafnium doping. 15 For the fluorite structure degradation, only nuclei of the tetragonal phase are needed, which did not appear in dense homogenized ceramics due to prolonged firing during synthesis and sintering (16 h at 890 °C). 16 When creating oxygen membranes based on δ-Bi2O3, such sintering conditions cannot be realized.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

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Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Zyryanov

Petrov

2022

JSCS

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Bismuth oxide kinetically stabilized by doping with a metastable structure of disordered fluorite ?-Bi2O3 has a unique conductivity. Oxygen selective membranes at intermediate temperatures ~550 ?C on the base of cermet ?-Bi2O3/Ag have the highest potential for air separation and can be used to produce oxygen for distributed multigeneration by burning fossil carbon fuels. When searching for the optimal composition of ?-Bi2O3, the degradation of fluorite into a new tetragonal phase was discovered in ceramics synthesized using mechanical activation. The tetragonal phase is formed and exists in a topotaxial composite with the fluorite structure. For a relatively stable over a wide temperature range tetragonal phase with a = 0.3854, c = 0.88905 nm, S.G. P-4, crystal structure and atomic coordinates have been proposed. In samples of fluorite and topotaxial composite, the Raman and M?ssbauer spectra were recorded and discussed. The discovery of a new tetragonal phase of doped bismuth oxide and its existence area makes it possible to optimize the composition and the synthesis of a more stable solid electrolyte ?-Bi2O3 with high conductivity.

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Section: Existence Area Of the Tetragonal Phasementioning

confidence: 99%

Section: Accepted Manuscriptmentioning

confidence: 99%

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Zyryanov

Petrov

2022

JSCS

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“…[ 15 ] Our previous study suggested that substituting Bi 3+ with an aliovalent element (e.g., Hf 4+ ) is effective to suppress the undesired phase transition at 600 °C by decreasing the cation diffusivity within the fluorite lattice. [ 16 ] On the other hand, the isovalent doping elements cause lattice contraction due to their smaller ionic radius compared to Bi, subsequently lowering the oxygen ion conductivity of pure Bi 2 O 3 . In this regard, a double doping strategy for isovalent elements has been employed to enhance ionic conductivity by lowering total dopant concentration compared to ESB.…”

Section: Introductionmentioning

confidence: 99%

Lowering the Temperature of Solid Oxide Electrochemical Cells Using Triple‐Doped Bismuth Oxides

Yu,

Jeong,

Jang

et al. 2023

Advanced Materials

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Despite the great potential of solid oxide electrochemical cells (SOCs) as highly efficient energy conversion devices, the undesirable high operating temperature has limited their wider applicability. Herein, a novel approach to developing high‐performance low‐temperature SOCs (LT‐SOCs) is presented through the use of an Er, Y, and Zr triple‐doped bismuth oxide (EYZB). This study demonstrates that EYZB exhibits >147 times higher ionic conductivity of 0.44 S/cm at 600°C compared to commercial Y‐stabilized zirconia electrolyte with excellent stability over 1000 h. By rationally incorporating EYZB in composite electrodes and bilayer electrolytes, the zirconia‐based electrolyte LT‐SOC achieves the unprecedentedly high performance of 3.45 and 2.02 W/cm2 in the fuel cell mode and 2.08 and 0.95 A/cm2 in the electrolysis cell mode at 700 and 600°C, respectively. Further, a distinctive microstructural feature of EYZB that largely extends triple phase boundary at the interface is revealed through digital twinning. This work provides insights for developing high‐performance LT‐SOCs.This article is protected by copyright. All rights reserved

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“…Accordingly, in a fluorite unit cell with two formula units of Bi 2 O 3 , only six oxygen ions occupy the anion sublattice out of the 40 possible sites. Owing to the disordered nature of the anion sublattice, δ-Bi 2 O 3 -based materials exhibit remarkable ionic transport and oxygen surface exchange properties. ,,,, However, the cubic δ phase of pure Bi 2 O 3 is only allowed within a narrow temperature range (730–830°C). ,,− Below this temperature range, the cubic phase transforms to a monoclinic α phase, which shows an ionic conductivity ∼3 orders of magnitude lower than that of the δ phase. Therefore, cubic stabilization has been extensively studied and the need for a more detailed understanding of the atomic structure and thermodynamic stability of the cubic δ phase has been highlighted. ,,− …”

Section: Introductionmentioning

confidence: 99%

“…Owing to the disordered nature of the anion sublattice, δ-Bi 2 O 3 -based materials exhibit remarkable ionic transport and oxygen surface exchange properties. 8,23,24,27,28 However, the cubic δ phase of pure Bi 2 O 3 is only allowed within a narrow temperature range (730−830°C). 20,22,27−29 Below this temperature range, the cubic phase transforms to a monoclinic α phase, which shows an ionic conductivity ∼3 orders of magnitude lower than that of the δ phase.…”

Section: Introductionmentioning

confidence: 99%

Accurate and Efficient Prediction of Highly Disordered Bi₂O₃ with Optimum Structure Pool: Combined Approach of the Special Quasirandom Structure Method and Structure Sampling

Jeong

Yeon²,

Lee³

et al. 2022

J. Phys. Chem. C

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Materials exhibiting outstanding ion transport properties have been investigated for extensive applications, and there has been an increasing demand for the rational design of ion-conductive materials. δ-Bi2O3, which shows the highest reported oxygen ionic conductivity, possesses a notoriously defective and disordered structure, and this leads to make the initial guess of the atomic coordinates difficult. Therefore, there is a lack of fundamental understanding of the thermodynamic stability, doping effects, and surface reactions of δ-Bi2O3. Herein, we suggest an accurate and efficient way to describe the disordered nature of the δ-Bi2O3 oxygen sublattice, involving structure modeling and structure sampling processes. Using a special quasirandom structure method, we developed the disordered structure pool of δ-Bi2O3 and verified our modeling process by accurately predicting its material properties. Subsequently, we introduced a structure sampling process to efficiently determine the size of the Bi2O3 structure pool based on the convergence of the disorder variable while maintaining the prediction accuracy.

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Dramatic Enhancement of Long-Term Stability of Erbia-Stabilized Bismuth Oxides via Quadrivalent Hf Doping

Cited by 23 publications

References 23 publications

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Lowering the Temperature of Solid Oxide Electrochemical Cells Using Triple‐Doped Bismuth Oxides

Accurate and Efficient Prediction of Highly Disordered Bi₂O₃ with Optimum Structure Pool: Combined Approach of the Special Quasirandom Structure Method and Structure Sampling

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Dramatic Enhancement of Long-Term Stability of Erbia-Stabilized Bismuth Oxides via Quadrivalent Hf Doping

Cited by 23 publications

References 23 publications

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Transformation of fluorite δ-Bi2O3 into a new tetragonal phase

Lowering the Temperature of Solid Oxide Electrochemical Cells Using Triple‐Doped Bismuth Oxides

Accurate and Efficient Prediction of Highly Disordered Bi2O3 with Optimum Structure Pool: Combined Approach of the Special Quasirandom Structure Method and Structure Sampling

Contact Info

Product

Resources

About

Accurate and Efficient Prediction of Highly Disordered Bi₂O₃ with Optimum Structure Pool: Combined Approach of the Special Quasirandom Structure Method and Structure Sampling