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Comparative Molecular Dynamics Study of the Roles of Anion–Cation and Cation–Cation Correlation in Cation Diffusion in Li2B12H12 and LiCB11H12

  • Kartik Sau*
    Kartik Sau
    Mathematics for Advanced Materials Open Innovation Laboratory (MathAM−OIL), National Institute of Advanced Industrial Science and Technology (AIST), c/o Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980−8577, Japan
    *Email: [email protected]
    More by Kartik Sau
  • Tamio Ikeshoji
    Tamio Ikeshoji
    Mathematics for Advanced Materials Open Innovation Laboratory (MathAM−OIL), National Institute of Advanced Industrial Science and Technology (AIST), c/o Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980−8577, Japan
  • Sangryun Kim
    Sangryun Kim
    Institute for Materials Research (IMR), Tohoku University, Sendai 980-8577, Japan
    More by Sangryun Kim
  • Shigeyuki Takagi
    Shigeyuki Takagi
    Institute for Materials Research (IMR), Tohoku University, Sendai 980-8577, Japan
  • , and 
  • Shin-ichi Orimo
    Shin-ichi Orimo
    Institute for Materials Research (IMR), Tohoku University, Sendai 980-8577, Japan
    Advanced Institute for Materials Research (AIMR), Tohoku University, Sendai 980-8577, Japan
Cite this: Chem. Mater. 2021, 33, 7, 2357–2369
Publication Date (Web):March 19, 2021
https://doi.org/10.1021/acs.chemmater.0c04473
Copyright © 2021 American Chemical Society

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    Abstract

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    Complex hydrides are potential candidates for the solid electrolyte of all-solid-state batteries owing to their high ionic conductivities in which icosahedral anion reorientational motion plays an essential role in high cation diffusion. Herein, we report molecular dynamics (MD) simulations based on a refined force field and first-principles calculations of the two complex hydride systems Li2B12H12 and LiCB11H12 to investigate their structures, order–disorder phase-transition behavior, anion reorientational motion, and cation conductivities. For both systems, force-field-based MD successfully reproduced the structural and dynamical behavior reported in experiments. Remarkably, it showed an entropy-driven order–disorder phase transition associated with high anion reorientational motion. Furthermore, we obtained comparative insights into the cation around the anion, cation site occupancy in the interstitial space provided by anions, cation diffusion route, role of cation vacancies, anion reorientation, and effect of cation–cation correlation on cation diffusion. We also determined the factors responsible for lowering phase transition temperature. These findings are of fundamental importance in fast ion-conducting solids to diminish the transition temperature for practical applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c04473.

    • (Figure S1) RDFs for structural comparison of the MD structure and reported X-ray structure in the LCBH system; (Figure S2) power spectrum comparison from MD and first-principles MD; (Figure S3) cell volume from different constrained MD simulations for both LBH and LCBH systems; (Figure S4) time evolution of the distinct van Hove correlation function for both LBH and LCBH systems; (Figure S5) time evolution of self-part of van Hove correlation for the LCBH system (PDF)

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    Cited By

    This article is cited by 17 publications.

    1. Alexey P. Maltsev, Ilya V. Chepkasov, Artem R. Oganov. Order–Disorder Phase Transition and Ionic Conductivity in a Li2B12H12 Solid Electrolyte. ACS Applied Materials & Interfaces 2023, 15 (36) , 42511-42519. https://doi.org/10.1021/acsami.3c07242
    2. Egon Campos dos Santos, Ryuhei Sato, Kazuaki Kisu, Kartik Sau, Xue Jia, Fangling Yang, Shin-ichi Orimo, Hao Li. Explore the Ionic Conductivity Trends on B12H12 Divalent Closo-Type Complex Hydride Electrolytes. Chemistry of Materials 2023, 35 (15) , 5996-6004. https://doi.org/10.1021/acs.chemmater.3c00975
    3. Ryo Asakura Arndt Remhof Corsin Battaglia . Hydroborate-Based Solid Electrolytes for All-Solid-State Batteries. , 353-393. https://doi.org/10.1021/bk-2022-1413.ch014
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    15. Matthew Green, Hovnan Simonyan, Katty Kaydanik, Joseph A. Teprovich. Influence of Solvent System on the Electrochemical Properties of a closo-Borate Electrolyte Salt. Applied Sciences 2022, 12 (5) , 2273. https://doi.org/10.3390/app12052273
    16. A. Akrouchi, H. Benzidi, A. Al-Shami, A. El kenz, A. Benyoussef, A. El Kharbachi, O. Mounkachi. First-principles study of closo -dodecaborates M 2 B 12 H 12 (M = Li, Na, K) as solid-state electrolyte materials. Physical Chemistry Chemical Physics 2021, 23 (47) , 27014-27023. https://doi.org/10.1039/D1CP03215A
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