Li-Ion Diffusion Correlations in LiAlGeO4: Quasielastic Neutron Scattering and Ab Initio Simulation

Kumar, Sajan; Gupta, Mayanak K.; Mittal, Ranjan; Jalarvo, Niina H.; Mukhopadhyay, Sanghamitra; Shukla, Rakesh; Achary, Srungarpu N.; Kolesnikov, Alexander I.; Tyagi, Avesh K.; Chaplot, Samrath L.

doi:10.1021/acsaem.2c02663

Title: Li-Ion Diffusion Correlations in LiAlGeO₄: Quasielastic Neutron Scattering and Ab Initio Simulation

Journal Article · Fri Oct 21 00:00:00 EDT 2022 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.2c02663· OSTI ID:1906559

Kumar, Sajan ^[1]; Gupta, Mayanak K. ^[1];

^[1];

^[2];

^[3]; Shukla, Rakesh ^[4];

^[1];

^[2];

^[1]; Chaplot, Samrath L. ^[1]

Bhabha Atomic Research Centre, Mumbai (India); Homi Bhabha National Institute, Mumbai (India)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Laboratory, ISIS Neutron Source
Bhabha Atomic Research Centre, Mumbai (India)

Here, we investigated the impact of Li stoichiometry and host flexibility on Li⁺ diffusion processes in LiAlGeO₄ at the microscopic level using quasielastic neutron scattering (QENS) and ab initio molecular dynamics (AIMD) simulations. Using sufficiently long AIMD trajectories, we could simulate the observed QENS signal and identify the localized dynamics of Li in crystalline LiAlGeO₄. Such information is vital to identify the bottleneck of diffusion processes and design materials for battery application. Our AIMD simulations in LiAlGeO₄ reveal that the Li⁺ conductivity can be significantly improved by manipulating the Li stoichiometry and/or host flexibility via amorphization. We determined that excess Li stoichiometry enhances the Coulomb repulsion of neighboring Li sites and softens the host structure to enable faster Li⁺ diffusion along the hexagonal c-axis. In the amorphous structure, random orientations of AlO₄ and GeO₄ polyhedral units create a wide distribution of intersite distances and significantly soften the host structure, greatly enhancing the Li⁺ diffusion. The simulations are used to understand the nature of diffusion, especially the role of the host structure, the possible hopping pathways, and the diffusion behavior in various structures of LiAlGeO₄.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Indian National Science Academy (INSA)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1906559

Journal Information:: ACS Applied Energy Materials, Vol. 5, Issue 11; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (63)

Lithium Insertion into Li ₂ MoO ₄ : Reversible Formation of (Li ₃ Mo)O ₄ with a Disordered Rock-Salt Structure Mikhailova, D.; Voss, A.; Oswald, S. Chemistry of Materials, Vol. 27, Issue 12 https://doi.org/10.1021/acs.chemmater.5b01633	journal	June 2015
Solid-State Sodium Batteries Zhao, Chenglong; Liu, Lilu; Qi, Xingguo Advanced Energy Materials, Vol. 8, Issue 17 https://doi.org/10.1002/aenm.201703012	journal	February 2018
Optimizing Li+ conductivity in a garnet framework Li, Yutao; Han, Jian- Tao; Wang, Chang- An Journal of Materials Chemistry, Vol. 22, Issue 30 https://doi.org/10.1039/c2jm31413d	journal	January 2012
Fast Na diffusion and anharmonic phonon dynamics in superionic Na ₃ PS ₄ Gupta, Mayanak K.; Ding, Jingxuan; Osti, Naresh C. Energy & Environmental Science, Vol. 14, Issue 12 https://doi.org/10.1039/D1EE01509E	journal	January 2021
Enhancing Fast Lithium Ion Conduction in Li₄GeO₄–Li₃PO₄ Solid Electrolytes Zhao, Guowei; Suzuki, Kota; Yonemura, Masao ACS Applied Energy Materials, Vol. 2, Issue 9 https://doi.org/10.1021/acsaem.9b01152	journal	August 2019
Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments Arnold, O.; Bilheux, J. C.; Borreguero, J. M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029	journal	November 2014
Neutron Scattering from a Liquid on a Jump Diffusion Model Chudley, C. T.; Elliott, R. J. Proceedings of the Physical Society, Vol. 77, Issue 2 https://doi.org/10.1088/0370-1328/77/2/319	journal	February 1961
Liquidlike Cu atom diffusion in weakly ionic compounds ${Cu}_{2} S$ and ${Cu}_{2} Se$ Zhuo, Keenan; Wang, Jing; Gao, Jianping Physical Review B, Vol. 102, Issue 6 https://doi.org/10.1103/PhysRevB.102.064201	journal	August 2020
Disordered LiZnVO₄with a phenacite structure Azrour, Mohamed; Elouadi, Brahim; El Ammari, Lahcen Acta Crystallographica Section E Structure Reports Online, Vol. 66, Issue 5 https://doi.org/10.1107/S1600536810013358	journal	April 2010
Review on solid electrolytes for all-solid-state lithium-ion batteries Zheng, Feng; Kotobuki, Masashi; Song, Shufeng Journal of Power Sources, Vol. 389 https://doi.org/10.1016/j.jpowsour.2018.04.022	journal	June 2018
Thermal behavior of germanates with olivine structure Koseva, I.; Nikolov, V.; Petrova, N. Thermochimica Acta, Vol. 646 https://doi.org/10.1016/j.tca.2016.11.004	journal	December 2016
Ab-initio simulations of materials using VASP: Density-functional theory and beyond Hafner, Jürgen Journal of Computational Chemistry, Vol. 29, Issue 13 https://doi.org/10.1002/jcc.21057	journal	October 2008
Review on Polymer-Based Composite Electrolytes for Lithium Batteries Yao, Penghui; Yu, Haobin; Ding, Zhiyu Frontiers in Chemistry, Vol. 7 https://doi.org/10.3389/fchem.2019.00522	journal	August 2019
Ionic conductivity of fluorite type crystals CaF2, SrF2, BaF2, and SrCl2 at high temperatures Voronin, B. M.; Volkov, S. V. Journal of Physics and Chemistry of Solids, Vol. 62, Issue 7 https://doi.org/10.1016/S0022-3697(01)00036-1	journal	July 2001
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
A lithium superionic conductor Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro Nature Materials, Vol. 10, Issue 9, p. 682-686 https://doi.org/10.1038/nmat3066	journal	July 2011
Hydride-based antiperovskites with soft anionic sublattices as fast alkali ionic conductors Gao, Shenghan; Broux, Thibault; Fujii, Susumu Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-020-20370-2	journal	January 2021
Synthesis and characterization of argyrodite solid electrolytes for all-solid-state Li-ion batteries Zhang, Zhixia; Zhang, Long; Liu, Yanyan Journal of Alloys and Compounds, Vol. 747 https://doi.org/10.1016/j.jallcom.2018.03.027	journal	May 2018
Phonons and lithium diffusion in LiAlO2 Gupta, Mayanak K.; Mittal, Ranjan; Singh, Baltej Physical Review B, Vol. 103, Issue 17 https://doi.org/10.1103/PhysRevB.103.174109	journal	May 2021
Alkali-Rich Antiperovskite M ₃ FCh (M = Li, Na; Ch = S, Se, Te): The Role of Anions in Phase Stability and Ionic Transport Fujii, Susumu; Gao, Shenghan; Tassel, Cédric Journal of the American Chemical Society, Vol. 143, Issue 28 https://doi.org/10.1021/jacs.1c04260	journal	July 2021
Microwave Dielectric Properties of Li2WO4 Ceramic with Ultra-Low Sintering Temperature Zhou, Di; Randall, Clive A.; Pang, Li-Xia Journal of the American Ceramic Society, Vol. 94, Issue 2 https://doi.org/10.1111/j.1551-2916.2010.04312.x	journal	January 2011
Solidlike to liquidlike behavior of Cu diffusion in superionic Cu2X (X=S, Se) : An inelastic neutron scattering and ab initio molecular dynamics investigation Kumar, Sajan; Gupta, M. K.; Goel, Prabhatasree Physical Review Materials, Vol. 6, Issue 5 https://doi.org/10.1103/PhysRevMaterials.6.055403	journal	May 2022
Single lithium-ion conducting solid polymer electrolytes: advances and perspectives Zhang, Heng; Li, Chunmei; Piszcz, Michal Chemical Society Reviews, Vol. 46, Issue 3 https://doi.org/10.1039/C6CS00491A	journal	January 2017
Incoherent neutron scattering functions for random jump diffusion in bounded and infinite media Hall, Peter L.; Ross, D. K. Molecular Physics, Vol. 42, Issue 3 https://doi.org/10.1080/00268978100100521	journal	February 1981
Li-rich anti-perovskite Li ₃ OCl films with enhanced ionic conductivity Lü, Xujie; Wu, Gang; Howard, John W. Chem. Commun., Vol. 50, Issue 78 https://doi.org/10.1039/C4CC05372A	journal	January 2014
A review of lithium-ion battery safety concerns: The issues, strategies, and testing standards Chen, Yuqing; Kang, Yuqiong; Zhao, Yun Journal of Energy Chemistry, Vol. 59 https://doi.org/10.1016/j.jechem.2020.10.017	journal	August 2021
An efficient multi-doping strategy to enhance Li-ion conductivity in the garnet-type solid electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Meesala, Yedukondalu; Liao, Yu-Kai; Jena, Anirudha Journal of Materials Chemistry A, Vol. 7, Issue 14 https://doi.org/10.1039/C9TA00417C	journal	January 2019
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS Mamontov, E.; Herwig, K. W. Review of Scientific Instruments, Vol. 82, Issue 8 https://doi.org/10.1063/1.3626214	journal	August 2011
Improving the alkali metal electrode/inorganic solid electrolyte contact via room-temperature ultrasound solid welding Wang, Xinxin; Chen, Jingjing; Wang, Dajian Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-27473-4	journal	December 2021
Superionic Conductivity in Lithium-Rich Anti-Perovskites Zhao, Yusheng; Daemen, Luke L. Journal of the American Chemical Society, Vol. 134, Issue 36 https://doi.org/10.1021/ja305709z	journal	August 2012
Two low-εr phenakite-structure LiAGeO4 (A = Al, Ga) microwave dielectric ceramics with different structure ordering Yang, Zijian; Tang, Ying; Li, Jie Ceramics International, Vol. 47, Issue 8 https://doi.org/10.1016/j.ceramint.2020.12.224	journal	April 2021
Origin of the Structural Phase Transition in ${Li}_{7} {La}_{3} {Zr}_{2} O_{12}$ Bernstein, N.; Johannes, M. D.; Hoang, Khang Physical Review Letters, Vol. 109, Issue 20 https://doi.org/10.1103/PhysRevLett.109.205702	journal	November 2012
Crystal structures of α-LiGaSiO₄, α-LiAlGeO₄, and α-LiGaGeO₄ Fleet, Michael E. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 180, Issue 1-4 https://doi.org/10.1524/zkri.1987.180.14.63	journal	November 1987
Transport in glassy fast-ion conductors Pechenik, Alexander; Whitmore, D. H.; Susman, S. Journal of Non-Crystalline Solids, Vol. 101, Issue 1 https://doi.org/10.1016/0022-3093(88)90368-7	journal	April 1988
γ-Li_{4 – 3x}Al_xGeO₄solid electrolytes: phase equilibria, conductivity and glass-transition-like behaviour Lee, Chnoong Kheng; West, Anthony R. J. Mater. Chem., Vol. 3, Issue 2 https://doi.org/10.1039/JM9930300191	journal	January 1993
Novel Li ₃ ClO based glasses with superionic properties for lithium batteries Braga, M. H.; Ferreira, J. A.; Stockhausen, V. J. Mater. Chem. A, Vol. 2, Issue 15 https://doi.org/10.1039/C3TA15087A	journal	January 2014
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025	journal	November 2009
Amorphous Na ₂ Si ₂ O ₅ as a fast Na ⁺ conductor: an ab initio molecular dynamics simulation Lei, Xueling; Jee, Youngseok; Huang, Kevin Journal of Materials Chemistry A, Vol. 3, Issue 39 https://doi.org/10.1039/C5TA04474J	journal	January 2015
Lithium diffusion in $L i_{2} X$ ( $X = O$ , S, and Se): Ab initio simulations and inelastic neutron scattering measurements Gupta, M. K.; Singh, Baltej; Goel, Prabhatasree Physical Review B, Vol. 99, Issue 22 https://doi.org/10.1103/PhysRevB.99.224304	journal	June 2019
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Ab initio molecular dynamics study of 1-D superionic conduction and phase transition in β-eucryptite Singh, Baltej; Gupta, Mayanak K.; Mittal, Ranjan Journal of Materials Chemistry A, Vol. 6, Issue 12 https://doi.org/10.1039/C7TA08541A	journal	January 2018
A new apparatus design for high temperature (up to 950 °C) quasi-elastic neutron scattering in a controlled gaseous environment al-Wahish, Amal; Armitage, D.; al-Binni, U. Review of Scientific Instruments, Vol. 86, Issue 9 https://doi.org/10.1063/1.4929580	journal	September 2015
Stoichiometric tuning of lattice flexibility and Na diffusion in NaAlSiO₄: quasielastic neutron scattering experiment and ab initio molecular dynamics simulations Gupta, Mayanak K.; Mittal, Ranjan; Kumar, Sajan Journal of Materials Chemistry A, Vol. 9, Issue 29 https://doi.org/10.1039/D1TA03296H	journal	January 2021
Ring mechanism of fast Na+ ion transport in Na2LiFeTeO6 : Insight from molecular dynamics simulation Sau, Kartik; Ikeshoji, Tamio Physical Review Materials, Vol. 6, Issue 4 https://doi.org/10.1103/PhysRevMaterials.6.045406	journal	April 2022
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Introduction to Quasielastic Neutron Scattering Embs, Jan Peter; Juranyi, Fanni; Hempelmann, Rolf Zeitschrift für Physikalische Chemie, Vol. 224, Issue 1-2 https://doi.org/10.1524/zpch.2010.6090	journal	February 2010
Diffusion of sodium ions in amorphous $N a_{2} S i_{2} O_{5}$ : Quasielastic neutron scattering and ab initio molecular dynamics simulations Gupta, Mayanak K.; Mishra, Sanjay K.; Mittal, Ranjan Physical Review Materials, Vol. 4, Issue 4 https://doi.org/10.1103/PhysRevMaterials.4.045802	journal	April 2020
Review of electrical energy storage technologies, materials and systems: challenges and prospects for large-scale grid storage Gür, Turgut M. Energy & Environmental Science, Vol. 11, Issue 10 https://doi.org/10.1039/C8EE01419A	journal	January 2018
First-principles simulations to understand the structural and electrolyte properties of idealized Li7.5B10S18X1.5 (X=Cl, Br, I) Li, Yan; Holzwarth, N. A. W. Physical Review Materials, Vol. 6, Issue 4 https://doi.org/10.1103/PhysRevMaterials.6.045403	journal	April 2022
Promising All-Solid-State Batteries for Future Electric Vehicles Sun, Yang-Kook ACS Energy Letters, Vol. 5, Issue 10 https://doi.org/10.1021/acsenergylett.0c01977	journal	October 2020
A review of energy storage types, applications and recent developments Koohi-Fayegh, S.; Rosen, M. A. Journal of Energy Storage, Vol. 27 https://doi.org/10.1016/j.est.2019.101047	journal	February 2020
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Fundamentals of Electrolytes for Solid-State Batteries: Challenges and Perspectives Wang, Liguang; Li, Jun; Lu, Guolong Frontiers in Materials, Vol. 7 https://doi.org/10.3389/fmats.2020.00111	journal	July 2020
Fundamentals of inorganic solid-state electrolytes for batteries Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A. Nature Materials, Vol. 18, Issue 12 https://doi.org/10.1038/s41563-019-0431-3	journal	August 2019
In-operando high-speed tomography of lithium-ion batteries during thermal runaway Finegan, Donal P.; Scheel, Mario; Robinson, James B. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7924	journal	April 2015
Crystal Structure and Li-Ion Conductivity of LiGa₁₋_xAl_xGeO₄Phenacite Compounds with 0 ≤x≤ 1 Mukai, Kazuhiko; Nunotani, Naoyoshi Journal of The Electrochemical Society, Vol. 163, Issue 10 https://doi.org/10.1149/2.1111610jes	journal	January 2016
Synthesis and Crystallization of Atomic Layer Deposition β-Eucryptite LiAlSiO₄ Thin-Film Solid Electrolytes Sheil, Ryan; Perng, Ya-Chuan; Mars, Julian ACS Applied Materials & Interfaces, Vol. 12, Issue 51 https://doi.org/10.1021/acsami.0c11614	journal	December 2020
Fast-ionic conductivity of Li $^{+}$ in LiBH $_{4}$ Ikeshoji, Tamio; Tsuchida, Eiji; Morishita, Tetsuya Physical Review B, Vol. 83, Issue 14 https://doi.org/10.1103/PhysRevB.83.144301	journal	April 2011
Strongly Anharmonic Phonons and Their Role in Superionic Diffusion and Ultralow Thermal Conductivity of Cu ₇ PSe ₆ Gupta, Mayanak K.; Ding, Jingxuan; Bansal, Dipanshu Advanced Energy Materials, Vol. 12, Issue 23 https://doi.org/10.1002/aenm.202200596	journal	May 2022
Highly Mobile Ions: Low-Temperature NMR Directly Probes Extremely Fast Li ⁺ Hopping in Argyrodite-Type Li ₆ PS ₅ Br Epp, Viktor; Gün, Özgül; Deiseroth, Hans-Jörg The Journal of Physical Chemistry Letters, Vol. 4, Issue 13 https://doi.org/10.1021/jz401003a	journal	June 2013
Lithium Lanthanum Titanates: A Review Stramare, S.; Thangadurai, V.; Weppner, W. Chemistry of Materials, Vol. 15, Issue 21 https://doi.org/10.1021/cm0300516	journal	October 2003
Time-Dependent Correlations between Spins and Neutron Scattering in Ferromagnetic Crystals Van Hove, Léon Physical Review, Vol. 95, Issue 6 https://doi.org/10.1103/PhysRev.95.1374	journal	September 1954
Soft-phonon anharmonicity, floppy modes, and Na diffusion in Na3FY (Y=S,Se,Te) : Ab initio and machine-learned molecular dynamics simulations Gupta, Mayanak Kumar; Kumar, Sajan; Mittal, Ranjan Physical Review B, Vol. 106, Issue 1 https://doi.org/10.1103/PhysRevB.106.014311	journal	July 2022

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