Dopant arrangements in Y-doped BaZrO3 under processing conditions and their impact on proton conduction: a large-scale first-principles thermodynamics study

Kasamatsu, Shusuke; Sugino, Osamu; Ogawa, T.; Kuwabara, Akihide

doi:10.1039/d0ta01741h

Cited by 35 publications

(35 citation statements)

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“…This simple assumption is only based on the high sintering temperature of BaZrO3 above 1873 K. In addition, supercells with random distribution of Y-Y pairs were also employed in one of the previous reports [18] to roughly estimate the association effect of Y dopants [20] on the proton diffusivity. Kasamatsu et al have recently reported the thermal equilibrium configurations of Y dopants and O vacancies in the wide temperature range (600-2500 K), which were determined by a first-principles thermodynamic sampling simulation based on the replica exchange Monte Carlo (RXMC) method [21]. They claimed that the Y configuration in Y-doped BaZrO3 does not reach the random configuration even at the highest temperature, suggesting that the above assumption concerning the Y configuration in the crystal could be too simple.…”

Section: Toyoura Et Al Theoretically Clarified the Detailed Interactmentioning

confidence: 99%

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Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Fujii¹,

Toyoura²,

Uda³

et al. 2020

Preprint

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We theoretically revisit the proton diffusivity in yttrium-doped barium zirconate (Y-doped BaZrO3) with realistic dopant configurations under processing conditions. In a recent study employing the replica exchange Monte Carlo method, the equilibrium Y configurations at typical sintering temperatures were shown to deviate from the random configuration assumed in earlier theoretical studies. In the present study, we took this observation into account and evaluated the effect of the Y configuration on the proton diffusivity. Using the master equation approach based on local diffusion barriers calculated from first principles, the proton diffusivities under realistic Y configurations were estimated to be higher than those in the random configuration. This is explained by the fact that realistic Y configurations have fewer trap sites with deep potential wells compared to the random configuration due to the isolation trend of Y dopants. In addition, the effects of proton-proton interaction and the abundance of preferential conduction pathways are discussed; it is found that both are relatively minor factors compared to the trap site effect in determining the dependence of the proton diffusivity on the Y configurations.

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Section: Toyoura Et Al Theoretically Clarified the Detailed Interactmentioning

confidence: 99%

“…This was repeated twice corresponding to the two independent RXMC runs in Ref. [21]. This means that 72 supercell models consisting of 9×9×9 unit cells were prepared for each (xY, Tsinter) pair to be used in diffusivity calculations.…”

Section: Y Configurationsmentioning

confidence: 99%

Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Fujii¹,

Toyoura²,

Uda³

et al. 2020

Preprint

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“…[20]. On the other hand, Kasamatsu et al have recently reported the thermal equilibrium configurations of Y dopants and O vacancies in the wide temperature range (600-2500 K), which were determined by a first-principles thermodynamic sampling simulation based on the replica exchange Monte Carlo (RXMC) method [21]. They claimed that the Y configuration in Y-doped BaZrO 3 does not reach the random configuration even at the highest temperature, suggesting that the above assumption concerning the Y configuration in the crystal could be too simple.…”

Section: Toyoura Et Al Theoretically Clarified the Detailed Interactmentioning

confidence: 99%

“…As noted above, RXMC sampling of Y dopants on Zr sites and O vacancies configurations were performed in Ref. [21] by one of the authors. The sampling was performed within a 3×3×3 cubic perovskite supercell at varying Y concentrations (x Y = 0.07, 0.15, 0.22, 0.30) and at 16 temperatures between T = 600 K and T = 2500 K. The calculations were repeated twice resulting in two independent equilibrium ensembles of 1400 configurations for each (x Y , T) pair.…”

Section: Y Configurationsmentioning

confidence: 99%

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Theoretical study on proton diffusivity in Y-doped BaZrO₃ with realistic dopant configurations

Fujii

Toyoura

Uda

et al. 2021

Phys. Chem. Chem. Phys.

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A New Class of Proton Conductors with Dramatically Enhanced Stability and High Conductivity for Reversible Solid Oxide Cells

Luo

Zhou

et al. 2023

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ionic conductivity of proton conductors at intermediate temperatures (400-600 °C). [3] Currently, one of the key challenges for the commercialization of P-ReSOCs is obtaining electrolyte materials that possess high ionic conductivity and chemical stability simultaneously, which are critical for high efficiency and long operation life. [4] While the state-of-the-art proton conductor for P-ReSOCs, BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb1711) has high ionic conductivity, [5] its long-term stability against H 2 O or CO 2 may be inadequate under certain conditions. [6] Thus, development of novel electrolyte materials with better chemical stability while maintaining high ionic conductivity is crucial for advancing P-ReSOCs. [7] Recently, we have demonstrated the strategy of donor and acceptor codoping for obtaining Nb/Ta-doped electrolytes with high ionic conductivity and much improved durability than Zr-substituted ones. [8] Specifically, excess acceptor doping is found to be a necessity to compensate the blocking effect of donor doping in order to obtain high conductivity. In this work, we extend the doping chemistry to hexavalent donor Mo 6+ and W 6+ , which are predicted to be even more beneficial in enhancing the chemical stability of barium cerates than Nb 5+ and Ta 5+ , according to DFT-based calculations (Figure 1). [9] We have identified a series of proton-conducting electrolytes, BaMo/W x Ce 0.8-3x Yb 0.2+2x O 3-δ (BM/WCYb), with much enhanced chemical stability while maintaining high ionic conductivity. The improved properties is attributed mainly to Mo/W doping and careful modification of defect chemistry.For maximized conductivity, two extra Yb atoms are needed to balance the introduction of one Mo/W atom. Specifically, BaMo/W 0.03 Ce 0.71 Yb 0.26 O 3-δ (BM/WCYb037126) shows comparable conductivity to that of BZCYYb1711, while having superior chemical stability when exposed to high concentration of CO 2 or H 2 O. Upon exposure to wet CO 2 (with 3% H 2 O) at 600 °C for 200 h, for example, the resistance of BZCYYb1711 increased by 32.4%, while that of BMCYb037126 and BWCYb037126 increased by only 5.8% and 4.3%, respectively. Moreover, single cells based on the optimized compositions demonstrated high performance and excellent durability under typical conditions for fuel cell, water electrolysis, and reversible operations. These AbstractReversible solid oxide cells based on proton conductors (P-ReSOCs) have potential to be the most efficient and low-cost option for large-scale energy storage and power generation, holding promise as an enabler for the implementation of intermittent renewable energy technologies and the widespread utilization of hydrogen. Here, the rational design of a new class of hexavalent Mo/W-doped proton-conducting electrolytes with excellent durability while maintaining high conductivity is reported. Specifically, BaMo(W) 0.03 Ce 0.71 Yb 0.26 O 3-δ exhibits dramatically enhanced chemical stability against high concentrations of steam and carbon dioxide than the stateof-the-art ele...

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Dopant arrangements in Y-doped BaZrO₃ under processing conditions and their impact on proton conduction: a large-scale first-principles thermodynamics study

Abstract: The proton conductivity maximum in doped BaZrO3 is explained by a percolation vs. many-body trapping picture using first-principles thermodynamics calculations.

Cited by 35 publications

References 66 publications

Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Theoretical study on proton diffusivity in Y-doped BaZrO₃ with realistic dopant configurations

A New Class of Proton Conductors with Dramatically Enhanced Stability and High Conductivity for Reversible Solid Oxide Cells

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Dopant arrangements in Y-doped BaZrO3 under processing conditions and their impact on proton conduction: a large-scale first-principles thermodynamics study

Abstract: The proton conductivity maximum in doped BaZrO3 is explained by a percolation vs. many-body trapping picture using first-principles thermodynamics calculations.

Cited by 35 publications

References 66 publications

Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Theoretical Study on Proton Diffusivity in Y-Doped BaZrO3 with Realistic Dopant Configurations

Theoretical study on proton diffusivity in Y-doped BaZrO3 with realistic dopant configurations

A New Class of Proton Conductors with Dramatically Enhanced Stability and High Conductivity for Reversible Solid Oxide Cells

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Dopant arrangements in Y-doped BaZrO₃ under processing conditions and their impact on proton conduction: a large-scale first-principles thermodynamics study

Theoretical study on proton diffusivity in Y-doped BaZrO₃ with realistic dopant configurations