Hiromasa Shiiba*, Michihisa Koyama, Nobuyuki Zettsu* and Katsuya Teshima,
{"title":"石榴石 Li7-xLa3Zr2-xNbxO12(0 ≤ x ≤ 2)晶界处的锂离子传导特性","authors":"Hiromasa Shiiba*, Michihisa Koyama, Nobuyuki Zettsu* and Katsuya Teshima, ","doi":"10.1021/acs.chemmater.3c03097","DOIUrl":null,"url":null,"abstract":"<p >Understanding and control of atomic-scale materials design for both bulk and grain boundaries (GBs) of solid electrolytes are essential for developing solid-state batteries. However, the in-depth insight into ion transport characteristics in the GB region is still far from understood. The ionic conductivity of solid electrolytes is often experimentally measured by electrochemical impedance spectroscopy and computationally evaluated by atomic scale modeling. However, there is a large gap in conductivity between experiment and simulation, and one of the factors is the difficulty of modeling to accurately understand the relationship between disturbed atomic arrangement and ionic conduction in the GB region. Therefore, to minimize technological gaps, we have demonstrated that molecular dynamics (MD) calculations of tilted GBs with various symmetries are a very powerful approach to understanding the ion conduction behavior specific to GB having an amorphous phase-like disturbance atomic arrangement. We extend this approach to investigate the effect of Nb-substitution on ionic conduction in the GB region. In this study, the effect of Nb-substitution on the ion conduction behavior at GBs of garnet-type solid electrolytes of Li<sub>7–<i>x</i></sub>La<sub>3</sub>Zr<sub>2–<i>x</i></sub>Nb<sub><i>x</i></sub>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 2) is evaluated via MD calculations and multivariate analyses. Higher Li-ion conductivity observed in the thermodynamically stable Σ3 (2 – 1 – 1) = (1 – 21) GB structure (relatively lower GB formation energy) is characterized by both a high Nb concentration in the GB region and a partial rotation of the Zr/NbO<sub>6</sub> octahedron. Further, the analysis of the atomic arrangement and corresponding Li trajectories reveals that the Nb substitution promoted the formation of new Li conduction paths through partial rotation of the Zr/NbO<sub>6</sub> octahedron and enhanced the ionic conductivity. The results reported here enhance our understanding of new material design strategies, including conductivity enhancement of LLZO-based solid electrolytes and element substitution at Zr sites.</p>","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Li-Ion Conduction Characteristics at Grain Boundaries in Garnet Li7–xLa3Zr2–xNbxO12 (0 ≤ x ≤ 2)\",\"authors\":\"Hiromasa Shiiba*, Michihisa Koyama, Nobuyuki Zettsu* and Katsuya Teshima, \",\"doi\":\"10.1021/acs.chemmater.3c03097\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Understanding and control of atomic-scale materials design for both bulk and grain boundaries (GBs) of solid electrolytes are essential for developing solid-state batteries. However, the in-depth insight into ion transport characteristics in the GB region is still far from understood. The ionic conductivity of solid electrolytes is often experimentally measured by electrochemical impedance spectroscopy and computationally evaluated by atomic scale modeling. However, there is a large gap in conductivity between experiment and simulation, and one of the factors is the difficulty of modeling to accurately understand the relationship between disturbed atomic arrangement and ionic conduction in the GB region. Therefore, to minimize technological gaps, we have demonstrated that molecular dynamics (MD) calculations of tilted GBs with various symmetries are a very powerful approach to understanding the ion conduction behavior specific to GB having an amorphous phase-like disturbance atomic arrangement. We extend this approach to investigate the effect of Nb-substitution on ionic conduction in the GB region. In this study, the effect of Nb-substitution on the ion conduction behavior at GBs of garnet-type solid electrolytes of Li<sub>7–<i>x</i></sub>La<sub>3</sub>Zr<sub>2–<i>x</i></sub>Nb<sub><i>x</i></sub>O<sub>12</sub> (0 ≤ <i>x</i> ≤ 2) is evaluated via MD calculations and multivariate analyses. Higher Li-ion conductivity observed in the thermodynamically stable Σ3 (2 – 1 – 1) = (1 – 21) GB structure (relatively lower GB formation energy) is characterized by both a high Nb concentration in the GB region and a partial rotation of the Zr/NbO<sub>6</sub> octahedron. Further, the analysis of the atomic arrangement and corresponding Li trajectories reveals that the Nb substitution promoted the formation of new Li conduction paths through partial rotation of the Zr/NbO<sub>6</sub> octahedron and enhanced the ionic conductivity. The results reported here enhance our understanding of new material design strategies, including conductivity enhancement of LLZO-based solid electrolytes and element substitution at Zr sites.</p>\",\"PeriodicalId\":33,\"journal\":{\"name\":\"Chemistry of Materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-06-18\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemistry of Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.chemmater.3c03097\",\"RegionNum\":2,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry of Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.chemmater.3c03097","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Li-Ion Conduction Characteristics at Grain Boundaries in Garnet Li7–xLa3Zr2–xNbxO12 (0 ≤ x ≤ 2)
Understanding and control of atomic-scale materials design for both bulk and grain boundaries (GBs) of solid electrolytes are essential for developing solid-state batteries. However, the in-depth insight into ion transport characteristics in the GB region is still far from understood. The ionic conductivity of solid electrolytes is often experimentally measured by electrochemical impedance spectroscopy and computationally evaluated by atomic scale modeling. However, there is a large gap in conductivity between experiment and simulation, and one of the factors is the difficulty of modeling to accurately understand the relationship between disturbed atomic arrangement and ionic conduction in the GB region. Therefore, to minimize technological gaps, we have demonstrated that molecular dynamics (MD) calculations of tilted GBs with various symmetries are a very powerful approach to understanding the ion conduction behavior specific to GB having an amorphous phase-like disturbance atomic arrangement. We extend this approach to investigate the effect of Nb-substitution on ionic conduction in the GB region. In this study, the effect of Nb-substitution on the ion conduction behavior at GBs of garnet-type solid electrolytes of Li7–xLa3Zr2–xNbxO12 (0 ≤ x ≤ 2) is evaluated via MD calculations and multivariate analyses. Higher Li-ion conductivity observed in the thermodynamically stable Σ3 (2 – 1 – 1) = (1 – 21) GB structure (relatively lower GB formation energy) is characterized by both a high Nb concentration in the GB region and a partial rotation of the Zr/NbO6 octahedron. Further, the analysis of the atomic arrangement and corresponding Li trajectories reveals that the Nb substitution promoted the formation of new Li conduction paths through partial rotation of the Zr/NbO6 octahedron and enhanced the ionic conductivity. The results reported here enhance our understanding of new material design strategies, including conductivity enhancement of LLZO-based solid electrolytes and element substitution at Zr sites.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.