The Effect of Jump Attempt Frequencies on the Ionic Conductivity of Doped Ceria

Koettgen, Julius; Martin, Manfred

doi:10.1021/acs.jpcc.9b06946

Cited by 9 publications

(3 citation statements)

References 97 publications

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“…Here, we only consider the vibration frequency of the hopping Li ion. This method can provide good approximation results and will not affect our qualitative conclusions. ,,, …”

Section: Results and Discussionmentioning

confidence: 91%

“…This method can provide good approximation results and will not affect our qualitative conclusions. 38,39,64,65 The calculated attempt frequency, migration entropy, and prefactor in Li 3 OCl 1−x Br x are shown in Figure 4. Figure 4a shows that the attempt frequency, calculated by the activation barrier and jump distance, increases with activation energy.…”

Section: Resultsmentioning

confidence: 99%

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Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Chen

Lin

et al. 2021

ACS Appl. Energy Mater.

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The antiperovskite superionic conductors Li 3 OCl and Li 3 OBr show great differences in ionic conductivity. The more polarizable Li 3 OBr shows a lower ionic conductivity than Li 3 OCl, contradicting the idea that a more polarizable framework is beneficial for ionic conduction. In this work, we study the influence of substituting Cl with Br on the local structure, lattice dynamics, and Li-ion conductivity of Li 3 OCl 1−x Br x , based on first-principles calculations. We find that the incorporation of Br does soften the overall lattice stiffness of Li 3 OCl 1−x Br x , but the accompanying local structural distortion plays a dominant role in changing the activation energy for Li-ion diffusion, which could increase the site energy as well as the Li-ion vibration frequency. We suggest that more distorted initial octahedral sites and less distorted saddle trigonal-plane sites can lead to better ionic transport. In addition, the correlation between activation energy and the pre-exponential factor of diffusivity extracted from the Arrhenius plot of Li 3 OCl 1−x Br x is found to be nonlinear, which is due to the decreasing migration entropy with increasing activation energy.

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“…Here, we only consider the vibration frequency of the hopping Li ion. This method can provide good approximation results and will not affect our qualitative conclusions. ,,, …”

Section: Results and Discussionmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Chen

Lin

et al. 2021

ACS Appl. Energy Mater.

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“…However, there is no study in the literature in which the equivalence of the Eyring method and the Vineyard method is shown without restrictions to the Γ point. The generalized Vineyard formula was derived by Martin et al to calculate the attempt frequency in the full Brillouin zone , where v q,i and v m,j are the normal frequencies of atomic vibrations in the initial state (numerator) and the transition state (denominator) at the full Brillouin zone, respectively. The lowercase indices i , j are the phonon band and q and m are the wave vector for the initial and transition states, respectively.…”

Section: Results and Discussionmentioning

confidence: 99%

Design Principles for Rotational Cluster Anion [BH₄]⁻ Promote Superionic Conductivity in Sodium-Rich Antiperovskite Na₃OBH₄

Zhao

Guo

et al. 2022

J. Phys. Chem. C

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The ionic conductivity is determined by the activation energies and the jump attempt frequencies of carrier migrations between adjacent sites. However, few works in the past have considered the influence of the attempt frequency. In this work, the attempt frequencies of carrier migrations in Na3OBH4 and Na3OBr are calculated using density functional theory and written as the contribution of each element using frequency analysis, which can be used to calculate the conductivity of a carrier in combination with the defect concentration, migration barrier of carrier migration in equilibrium. The results show that the conductivity of sodium cations can be greatly improved by substituting Br− with the [BH4]− tetrahedral anion in an antiperovskite structure due to two reasons: (1) the paddle-wheel mechanism (PWM) of the [BH4]− anionic groups can effectively reduce the activation energy and (2) the [BH4]− anionic groups with a high vibration frequency undoubtedly improve the carrier jump attempt frequency by the buffering effect. The quasi-harmonic approximation (QHA) is used to describe the isobaric behavior of Na3OBH4 and Na3OBr, and the results show that carriers have a higher jump attempt frequency in the zero-pressure compared with the constant volume. The ionic conductivity (σ) in Na3OBr and Na3OBH4 are obtained from the Arrhenius equation. The results show that the calculated sodium ionic conductivity of Na3OBH4 is 3–4 orders of magnitude higher than that of Na3OBr at room temperature. The calculated sodium ionic conductivity is lower than the experimental measurement, and the discrepancy is attributed to the overestimation of the calculated migration barrier and the underestimation of the defect concentration.

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Enhanced Hydrogen Production in Microwave‐Driven Water‐Splitting Redox Cycles by Engineering Ceria Properties

Domínguez‐Saldaña,

Navarrete,

Balaguer

et al. 2024

Advanced Energy Materials

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Sustainable hydrogen, produced from renewable sources such as solar or wind, plays a decisive role in driving industrial decarbonization. Among hydrogen production technologies, steam electrolysis, and solar‐driven thermochemical cycles using reducible solid oxides show promise but face challenges due to high operation temperatures. Microwave‐driven redox chemical looping enables the direct, contactless electrification of the process, reducing the operation temperature and complexity. Previous works showed that microwaves can efficiently drive reduction/water‐splitting cycles using Gd‐doped ceria at low temperatures (<250 °C), but adjustment of material properties is needed. Here, the key properties of materials are explored that affect the redox mechanism by screening a series of doped ceria materials to enhance microwave‐driven hydrogen production. Evaluation of trivalent dopants (La3+, Gd3+, Y3+, Yb3+, Er3+, and Nd3+) reveals that reduction correlates with lattice and electronic properties. The composition Ce0.9La0.1O2‐δ achieves 1.41 mL g−1, the highest hydrogen production among the studied series. Its narrower bandgap allows for reaching higher conductivity upon microwave‐driven reduction at lower temperatures, while a larger ionic lattice size boosts solid‐state oxygen diffusion. Overall, this research remarks on the critical properties of ceria‐based materials that enhance hydrogen production in microwave‐driven water‐splitting cycles, supporting the design of more efficient materials for sustainable chemical production technology.

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The Effect of Jump Attempt Frequencies on the Ionic Conductivity of Doped Ceria

Cited by 9 publications

References 97 publications

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Design Principles for Rotational Cluster Anion [BH₄]⁻ Promote Superionic Conductivity in Sodium-Rich Antiperovskite Na₃OBH₄

Enhanced Hydrogen Production in Microwave‐Driven Water‐Splitting Redox Cycles by Engineering Ceria Properties

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The Effect of Jump Attempt Frequencies on the Ionic Conductivity of Doped Ceria

Cited by 9 publications

References 97 publications

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li3OCl1–xBrx Superionic Conductors

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li3OCl1–xBrx Superionic Conductors

Design Principles for Rotational Cluster Anion [BH4]− Promote Superionic Conductivity in Sodium-Rich Antiperovskite Na3OBH4

Enhanced Hydrogen Production in Microwave‐Driven Water‐Splitting Redox Cycles by Engineering Ceria Properties

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Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Influence of Structural Distortion and Lattice Dynamics on Li-Ion Diffusion in Li₃OCl_1–xBr_x Superionic Conductors

Design Principles for Rotational Cluster Anion [BH₄]⁻ Promote Superionic Conductivity in Sodium-Rich Antiperovskite Na₃OBH₄