First-principles study of the morphology and surface structure of LaCoO3 and La0.5Sr0.5Fe0.5Co0.5O3 perovskites as air electrodes for solid oxide fuel cells

Nakayama, Masanobu; Nishii, Katsuya; Watanabe, Kentaro; Tanibata, Naoto; Takeda, Hiromasa; Itoh, Takanori; Asaka, Toru

doi:10.1080/27660400.2021.1909871

Cited by 3 publications

(3 citation statements)

References 64 publications

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“…The Structural Model of Li 1−y Ni 2/3 Nb 1/3 O 2 Used for Computation. The genetic algorithm (GA) approach 63 was used to explore energetically favorable cation arrangements for LiNb 1/3 Ni 2/3 O 2 and the delithiated phases Li 1−x Nb 1/3 Ni 2/3 O 2 (x = 0.17, 0.33, 0.50, 0.67, and 1.00). Details of the GA approach are described in Supporting Section S2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System

et al. 2022

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Dependence on lithium-ion batteries for automobile applications is rapidly increasing. The emerging use of anionic redox can boost the energy density of batteries, but the fundamental origin of anionic redox is still under debate. Moreover, to realize anionic redox, many reported electrode materials rely on manganese ions through π-type interactions with oxygen. Here, through a systematic experimental and theoretical study on a binary system of Li 3 NbO 4 −NiO, we demonstrate for the first time the unexpectedly large contribution of oxygen to charge compensation for electrochemical oxidation in Ni-based materials. In general, for Ni-based materials, e.g., LiNiO 2 , charge compensation is achieved mainly by Ni oxidation, with a lower contribution from oxygen. In contrast, for Li 3 NbO 4 −NiO, oxygen-based charge compensation is triggered by structural disordering and σ-type interactions with nickel ions, which are associated with a unique environment for oxygen, i.e., a linear Ni−O−Ni configuration in the disordered system. Reversible anionic redox with a small hysteretic behavior was achieved for LiNi 2/3 Nb 1/3 O 2 with a cation-disordered Li/Ni arrangement. Further Li enrichment in the structure destabilizes anionic redox and leads to irreversible oxygen loss due to the disappearance of the linear Ni−O−Ni configuration and the formation of unstable Ni ions with high oxidation states. On the basis of these results, we discuss the possibility of using σ-type interactions for anionic redox to design advanced electrode materials for highenergy lithium-ion batteries.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System

et al. 2022

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“…We use genetic algorithm (GA) 16 Figure 3 shows the calculated voltage profile, where the potentials are 2.70 and 2.95 V for eq 3 and eq 4, respectively.…”

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“…We use genetic algorithm (GA) assisted density functional theory (DFT) calculations to investigate the electrochemical delithiation for both Li 2 O and P-doped Li 2 O. For this purpose, we assume the Li 11/8 P 1/8 O composition to be the P-doped Li 2 O in this study, where the oxidation states of Li, P, and O ions are +1, + 5, and −2, respectively, satisfying the octet-rule.…”

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Toward Cost-Effective High-Energy Lithium-Ion Battery Cathodes: Covalent Bond Formation Empowers Solid-State Oxygen Redox in Antifluorite-Type Lithium-Rich Iron Oxide

Kobayashi,

Nakamura,

Yokoyama

et al. 2024

ACS Materials Lett.

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Affordable and high-energy lithium-ion batteries are pivotal for advances in sustainability. To this end, antifluorite-type Li 5 FeO 4 cathodes have recently gained attention due to their costeffectiveness and theoretical capacity exceeding 300 mAh g −1 . Notably, metastable cubic Li 5 FeO 4 has achieved a reversible capacity of 346 mAh g −1 , utilizing cationic iron and anionic oxygen redox reactions. However, the cyclability of solid-state oxygen redox in this system is hindered by concurrent, irreversible, and simultaneous evolution of the O 2 gas evolution. In this study, we enhance the cyclability through the incorporation of earthabundant p-block elements into cubic Li 5 FeO 4 . We find that the covalent bonding between the oxygen species and the p-block element elevates the oxidation potential of the O 2 gas release without altering the solid-state oxygen redox potential.

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Computational studies on Mg ion conductivity in Mg2xHf1-x Nb(PO4)3 using neural network potential

Makino,

Tanibata,

Takeda

et al. 2024

J Solid State Electrochem

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Low Mg diffusivity in solid-state oxides is an obstacle for the development of materials for Mg ion batteries, which are expected to have high capacity. In this study, we focused on NASICON-type and β-iron sulfate-type Mg2xHf1-xNb(PO4)3 that exhibit relatively high Mg ionic conductivity and investigated the Hf/Nb configuration and composition dependence of phase stability and ion conductivity by atomistic simulation using neural network potentials. The calculations show that the NASICON-type structure is slightly more stable and has higher Mg ionic conductivity than that of the β-iron sulfate-type. The effect of the Hf/Nb configuration was investigated and showed that the ordered stable structure had much lower ionic conductivity than the disordered structure. Furthermore, as the Mg ion concentration increased, the ionic conductivity increased monotonically at low concentrations but tended to converge to a constant value above a certain concentration. The saturation of the ionic conductivity despite increasing the Mg concentration may be due to the trapping effect of the Mg ions caused by the Hf vacancies as well as the Hf/Nb arrangement. Graphical Abstract

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First-principles study of the morphology and surface structure of LaCoO₃ and La_0.5Sr_0.5Fe_0.5Co_0.5O₃ perovskites as air electrodes for solid oxide fuel cells

Abstract: 2021) First-principles study of the morphology and surface structure of LaCoO 3 and La 0.5 Sr 0.5 Fe 0.5 Co 0.5 O 3 perovskites as air electrodes for solid oxide fuel cells,

Cited by 3 publications

References 64 publications

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System

Toward Cost-Effective High-Energy Lithium-Ion Battery Cathodes: Covalent Bond Formation Empowers Solid-State Oxygen Redox in Antifluorite-Type Lithium-Rich Iron Oxide

Computational studies on Mg ion conductivity in Mg2xHf1-x Nb(PO4)3 using neural network potential

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First-principles study of the morphology and surface structure of LaCoO3 and La0.5Sr0.5Fe0.5Co0.5O3 perovskites as air electrodes for solid oxide fuel cells

Abstract: 2021) First-principles study of the morphology and surface structure of LaCoO 3 and La 0.5 Sr 0.5 Fe 0.5 Co 0.5 O 3 perovskites as air electrodes for solid oxide fuel cells,

Cited by 3 publications

References 64 publications

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li3NbO4–NiO Binary System

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li3NbO4–NiO Binary System

Toward Cost-Effective High-Energy Lithium-Ion Battery Cathodes: Covalent Bond Formation Empowers Solid-State Oxygen Redox in Antifluorite-Type Lithium-Rich Iron Oxide

Computational studies on Mg ion conductivity in Mg2xHf1-x Nb(PO4)3 using neural network potential

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First-principles study of the morphology and surface structure of LaCoO₃ and La_0.5Sr_0.5Fe_0.5Co_0.5O₃ perovskites as air electrodes for solid oxide fuel cells

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System

Unexpectedly Large Contribution of Oxygen to Charge Compensation Triggered by Structural Disordering: Detailed Experimental and Theoretical Study on a Li₃NbO₄–NiO Binary System