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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

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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
    Click to copy article linkArticle link copied!

    • 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
      More by Tamio Ikeshoji
    • Sangryun Kim
      Sangryun Kim
      Institute for Materials Research (IMR), Tohoku University, Sendai 980-8577, Japan
      More by Sangryun Kim
      Orcidhttp://orcid.org/0000-0001-8617-3022
    • Shigeyuki Takagi
      Shigeyuki Takagi
      Institute for Materials Research (IMR), Tohoku University, Sendai 980-8577, Japan
      More by Shigeyuki Takagi
    • 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
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    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 7, 2357–2369
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    https://doi.org/10.1021/acs.chemmater.0c04473
    Published March 19, 2021
    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.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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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

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    This article is cited by 19 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
    4. Emily A. Cheung, Han Nguyen, Hanmei Tang, Anton P. J. Stampfl, Maxim Avdeev, Ying Shirley Meng, Neeraj Sharma, Nicolas R. de Souza. Structure and Dynamics in Mg2+-Stabilized γ-Na3PO4. Journal of the American Chemical Society 2021, 143 (41) , 17079-17089. https://doi.org/10.1021/jacs.1c06905
    5. Kartik Sau, Shigeyuki Takagi, Tamio Ikeshoji, Kazuaki Kisu, Ryuhei Sato, Egon Campos dos Santos, Hao Li, Rana Mohtadi, Shin-ichi Orimo. Unlocking the secrets of ideal fast ion conductors for all-solid-state batteries. Communications Materials 2024, 5 (1) https://doi.org/10.1038/s43246-024-00550-z
    6. Ming Zeng, Carlos Escorihuela‐Sayalero, Tamio Ikeshoji, Shigeyuki Takagi, Sangryun Kim, Shin‐ichi Orimo, María Barrio, Josep‐Lluís Tamarit, Pol Lloveras, Claudio Cazorla, Kartik Sau. Colossal Reversible Barocaloric Effects in a Plastic Crystal Mediated by Lattice Vibrations and Ion Diffusion. Advanced Science 2024, 11 (26) https://doi.org/10.1002/advs.202306488
    7. Steffen R. H. Jensen, Mathias Jørgensen, Thi Phuong Thao Nguyen, Greg Nolan, Craig E. Buckley, Torben R. Jensen, Mark Paskevicius. Ionic conduction in ammonia functionalised closo -dodecaborates MB 12 H 11 NH 3 (M = Li and Na). Dalton Transactions 2024, 53 (17) , 7619-7627. https://doi.org/10.1039/D4DT00801D
    8. Sanja Burazer, Jasminka Popović. Mechanochemical Synthesis of Solid-State Electrolytes. Inorganics 2024, 12 (2) , 54. https://doi.org/10.3390/inorganics12020054
    9. Thomas A. Hales, Kasper T. Møller, Terry D. Humphries, Anita M. D’Angelo, Craig E. Buckley, Mark Paskevicius. Stannaborates: tuning the ion conductivity of dodecaborate salts with tin substitution. Physical Chemistry Chemical Physics 2023, 25 (45) , 31249-31256. https://doi.org/10.1039/D3CP03725H
    10. Kartik Sau, Shigeyuki Takagi, Tamio Ikeshoji, Kazuaki Kisu, Ryuhei Sato, Shin-ichi Orimo. The role of cation size in the ordered–disordered phase transition temperature and cation hopping mechanism based on LiCB 11 H 12. Materials Advances 2023, 4 (10) , 2269-2280. https://doi.org/10.1039/D2MA00936F
    11. Ryuhei Sato, Kazuto Akagi, Shigeyuki Takagi, Kartik Sau, Kazuaki Kisu, Hao Li, Shin-ichi Orimo. Topological Data analysis of Ion Migration Mechanism. The Journal of Chemical Physics 2023, 158 (14) https://doi.org/10.1063/5.0143387
    12. Kartik Sau, Tamio Ikeshoji. Insights of cationic diffusion in nickel-based honeycomb layered tellurates using molecular dynamics simulation. Solid State Ionics 2022, 383 , 115982. https://doi.org/10.1016/j.ssi.2022.115982
    13. Fermin Cuevas, Mads B Amdisen, Marcello Baricco, Craig E Buckley, Young Whan Cho, Petra de Jongh, Laura M de Kort, Jakob B Grinderslev, Valerio Gulino, Bjørn C Hauback, Michael Heere, Terry Humphries, Torben R Jensen, Sangryun Kim, Kazuaki Kisu, Young-Su Lee, Hai-Wen Li, Rana Mohtadi, Kasper T Møller, Peter Ngene, Dag Noréus, Shin-ichi Orimo, Mark Paskevicius, Marek Polanski, Sabrina Sartori, Lasse N Skov, Magnus H Sørby, Brandon C Wood, Volodymyr A Yartys, Min Zhu, Michel Latroche. Metallic and complex hydride-based electrochemical storage of energy. Progress in Energy 2022, 4 (3) , 032001. https://doi.org/10.1088/2516-1083/ac665b
    14. Mayanak Kumar Gupta, Sajan Kumar, Ranjan Mittal, Samrath L. Chaplot. Soft-phonon anharmonicity, floppy modes, and Na diffusion in Na 3 F Y   ( Y = S , Se , Te ) : Ab initio and machine-learned molecular dynamics simulations. Physical Review B 2022, 106 (1) https://doi.org/10.1103/PhysRevB.106.014311
    15. Matthew Green, Katty Kaydanik, Miguel Orozco, Lauren Hanna, Maxwell A. T. Marple, Kimberly Alicia Strange Fessler, Willis B. Jones, Vitalie Stavila, Patrick A. Ward, Joseph A. Teprovich. Closo ‐Borate Gel Polymer Electrolyte with Remarkable Electrochemical Stability and a Wide Operating Temperature Window. Advanced Science 2022, 9 (16) https://doi.org/10.1002/advs.202106032
    16. Kartik Sau, Tamio Ikeshoji. Ring mechanism of fast Na + ion transport in Na 2 LiFeTeO 6 : Insight from molecular dynamics simulation. Physical Review Materials 2022, 6 (4) https://doi.org/10.1103/PhysRevMaterials.6.045406
    17. 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
    18. 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
    19. Brandon C. Wood, Joel B. Varley, Kyoung E. Kweon, Patrick Shea, Alex T. Hall, Andrew Grieder, Michael Ward, Vincent P. Aguirre, Dylan Rigling, Eduardo Lopez Ventura, Chimara Stancill, Nicole Adelstein. Paradigms of frustration in superionic solid electrolytes. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 2021, 379 (2211) https://doi.org/10.1098/rsta.2019.0467
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    Chemistry of Materials

    Cite this: Chem. Mater. 2021, 33, 7, 2357–2369
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.0c04473
    Published March 19, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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