Anharmonic Cation–Anion Coupling Dynamics Assisted Lithium‐Ion Diffusion in Sulfide Solid Electrolytes

Xu, Zhenming; Chen, Xi; Zhu, Hong; Li, Xin

doi:10.1002/adma.202207411

Anharmonic Cation–Anion Coupling Dynamics Assisted Lithium‐Ion Diffusion in Sulfide Solid Electrolytes

Journal Article · 31 October 2022 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202207411· OSTI ID:2424757

Xu, Zhenming ^[1]; Chen, Xi ^[2]; Zhu, Hong ^[3]; ^[2]

John A. Paulson School of Engineering and Applied Sciences Harvard University Cambridge MA 02138 USA; University of Michigan–Shanghai Jiao Tong University Joint Institute Shanghai Jiao Tong University 800 Dongchuan Road Shanghai 200240 P. R. China
John A. Paulson School of Engineering and Applied Sciences Harvard University Cambridge MA 02138 USA
University of Michigan–Shanghai Jiao Tong University Joint Institute Shanghai Jiao Tong University 800 Dongchuan Road Shanghai 200240 P. R. China

Abstract

Sulfide‐based lithium superionic conductors often show higher Li‐ion conductivity than other types of electrolyte materials. This work unveils a unique Li‐ion conductive behavior in these materials through the perspective of anharmonic coupling assisted Li‐ion diffusion. Li hopping events can happen simultaneously with various types of lattice dynamics, while only a statistically important synchronization of motions may indicate coupling. This method enables a direct evaluation of the coupling strength between these motions, which more fundamentally decides if a specific type of lattice motion is really anharmonically coupled to the Li hopping event and whether the coupling can facilitate the Li diffusion. By a new ab initio computational approach, this work unveils a unique phenomenon in prototype sulfide electrolytes in comparison with typical halide ones, that Li‐ion conduction can be boosted by the anharmonic coupling of low‐frequency Li phonon modes with high‐frequency anion stretching or flexing phonon modes, rather than the low‐frequency rotational modes. The coupling pushes Li ions toward the diffusion channels for reduced diffusion barriers. The result from the lower temperature range (≈0–300 K) of simulation can also be more relevant to the application of solid‐state batteries.

Research Organization:: Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE

OSTI ID:: 2424757

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 49 Vol. 34; ISSN 0935-9648

Publisher:: Wiley

Country of Publication:: United States

Language:: English

References (58)

Dynamics in superionic lithium sulphate lattice: paddle wheel versus percolation mechanism Satheesan Babu, C.; Tembe, Bhalachandra L. Chemical Physics Letters, Vol. 194, Issue 4-6 https://doi.org/10.1016/0009-2614(92)86063-N	journal	July 1992
Influence of lattice dynamics on lithium-ion conductivity: A first-principles study Sagotra, Arun K.; Chu, Dewei; Cazorla, Claudio Physical Review Materials, Vol. 3, Issue 3 https://doi.org/10.1103/PhysRevMaterials.3.035405	journal	March 2019
A picture of pseudogap phase related to charge fluxes Chen, Xi; Dong, Jiahao; Li, Xin npj Computational Materials, Vol. 6, Issue 1 https://doi.org/10.1038/s41524-020-00373-9	journal	July 2020
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
High-Throughput Screening of Solid-State Li-Ion Conductors Using Lattice-Dynamics Descriptors Muy, Sokseiha; Voss, Johannes; Schlem, Roman iScience, Vol. 16 https://doi.org/10.1016/j.isci.2019.05.036	journal	June 2019
Enhancement of cation mobility in some sulphate phases due to a paddle-wheel mechanism Lundén, Arnold Solid State Ionics, Vol. 28-30 https://doi.org/10.1016/S0167-2738(88)80026-2	journal	September 1988
Progress, challenges and perspectives of computational studies on glassy superionic conductors for solid-state batteries Xu, Zhenming; Xia, Yongyao Journal of Materials Chemistry A, Vol. 10, Issue 22 https://doi.org/10.1039/D2TA02321K	journal	January 2022
Lithium Conductivity and Meyer-Neldel Rule in Li ₃ PO ₄ –Li ₃ VO ₄ –Li ₄ GeO ₄ Lithium Superionic Conductors Muy, Sokseiha; Bachman, John C.; Chang, Hao-Hsun Chemistry of Materials, Vol. 30, Issue 16 https://doi.org/10.1021/acs.chemmater.8b01504	journal	July 2018
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes Kweon, Kyoung E.; Varley, Joel B.; Shea, Patrick Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02902	journal	October 2017
Low-temperature paddlewheel effect in glassy solid electrolytes Smith, Jeffrey G.; Siegel, Donald J. Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15245-5	journal	March 2020
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Selective breakdown of phonon quasiparticles across superionic transition in CuCrSe2 Niedziela, Jennifer L.; Bansal, Dipanshu; May, Andrew F. Nature Physics, Vol. 15, Issue 1 https://doi.org/10.1038/s41567-018-0298-2	journal	October 2018
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
Anharmonic lattice dynamics and superionic transition in AgCrSe ₂ Ding, Jingxuan; Niedziela, Jennifer L.; Bansal, Dipanshu Proceedings of the National Academy of Sciences, Vol. 117, Issue 8 https://doi.org/10.1073/pnas.1913916117	journal	February 2020
Superionic Diffusion through Frustrated Energy Landscape Di Stefano, Davide; Miglio, Anna; Robeyns, Koen Chem, Vol. 5, Issue 9 https://doi.org/10.1016/j.chempr.2019.07.001	journal	September 2019
Tuning mobility and stability of lithium ion conductors based on lattice dynamics Muy, Sokseiha; Bachman, John C.; Giordano, Livia Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03364H	journal	January 2018
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Anion Reorientations in the Superionic Conducting Phase of Na ₂ B ₁₂ H ₁₂ Verdal, Nina; Udovic, Terrence J.; Stavila, Vitalie The Journal of Physical Chemistry C, Vol. 118, Issue 31 https://doi.org/10.1021/jp506252c	journal	July 2014
A Two-Parameter Space to Tune Solid Electrolytes for Lithium Dendrite Constriction Wang, Yichao; Ye, Luhan; Chen, Xi JACS Au, Vol. 2, Issue 4 https://doi.org/10.1021/jacsau.2c00009	journal	March 2022
Introduction to Lattice Dynamics Dove, Martin T. Cambridge Topics in Mineral Physics and Chemistry https://doi.org/10.1017/CBO9780511619885	book	February 2010
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
The structure of the high-temperature solid electrolyte lithium sulphate at 908K Nilsson, L.; Thomas, J. O.; Tofield, B. C. Journal of Physics C: Solid State Physics, Vol. 13, Issue 35 https://doi.org/10.1088/0022-3719/13/35/004	journal	December 1980
Analysis of Diffusion in Solid-State Electrolytes through MD Simulations, Improvement of the Li-Ion Conductivity in β-Li ₃ PS ₄ as an Example de Klerk, Niek J. J.; van der Maas, Eveline; Wagemaker, Marnix ACS Applied Energy Materials, Vol. 1, Issue 7 https://doi.org/10.1021/acsaem.8b00457	journal	June 2018
Effects of temperature and pressure on phonons in FeSi 1 − x Al x Delaire, O.; Al-Qasir, I. I.; Ma, J. Physical Review B, Vol. 87, Issue 18 https://doi.org/10.1103/PhysRevB.87.184304	journal	May 2013
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Nanoconfined LiBH ₄ as a Fast Lithium Ion Conductor Blanchard, Didier; Nale, Angeloclaudio; Sveinbjörnsson, Dadi Advanced Functional Materials, Vol. 25, Issue 2 https://doi.org/10.1002/adfm.201402538	journal	October 2014
Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries Zhang, Qing; Cao, Daxian; Ma, Yi Advanced Materials, Vol. 31, Issue 44 https://doi.org/10.1002/adma.201901131	journal	August 2019
The chemical origin of temperature-dependent lithium-ion concerted diffusion in sulfide solid electrolyte Li10GeP2S12 Fu, Zhong-Heng; Chen, Xiang; Yao, Nan Journal of Energy Chemistry, Vol. 70 https://doi.org/10.1016/j.jechem.2022.01.018	journal	July 2022
Crystal Structural Framework of Lithium Super‐Ionic Conductors He, Xingfeng; Bai, Qiang; Liu, Yunsheng Advanced Energy Materials, Vol. 9, Issue 43 https://doi.org/10.1002/aenm.201902078	journal	October 2019
A New Superionic Plastic Polymorph of the Na ⁺ Conductor Na ₃ PS ₄ Famprikis, Theodosios; Dawson, James A.; Fauth, François ACS Materials Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsmaterialslett.9b00322	journal	October 2019
A dynamic stability design strategy for lithium metal solid state batteries Ye, Luhan; Li, Xin Nature, Vol. 593, Issue 7858 https://doi.org/10.1038/s41586-021-03486-3	journal	May 2021
Phonons in aluminum at high temperatures studied by inelastic neutron scattering Kresch, M.; Lucas, M.; Delaire, O. Physical Review B, Vol. 77, Issue 2 https://doi.org/10.1103/PhysRevB.77.024301	journal	January 2008
Solid Halide Electrolytes with High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries Asano, Tetsuya; Sakai, Akihiro; Ouchi, Satoru Advanced Materials, Vol. 30, Issue 44 https://doi.org/10.1002/adma.201803075	journal	September 2018
Origin of fast ion diffusion in super-ionic conductors He, Xingfeng; Zhu, Yizhou; Mo, Yifei Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15893	journal	June 2017
A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries Seino, Yoshikatsu; Ota, Tsuyoshi; Takada, Kazunori Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE41655K	journal	January 2014
Deep potential generation scheme and simulation protocol for the Li ₁₀ GeP ₂ S ₁₂ -type superionic conductors Huang, Jianxing; Zhang, Linfeng; Wang, Han The Journal of Chemical Physics, Vol. 154, Issue 9 https://doi.org/10.1063/5.0041849	journal	March 2021
Recent advances in all-solid-state rechargeable lithium batteries Sun, Chunwen; Liu, Jin; Gong, Yudong Nano Energy, Vol. 33 https://doi.org/10.1016/j.nanoen.2017.01.028	journal	March 2017
Apical Charge Flux-Modulated In-Plane Transport Properties of Cuprate Superconductors Kim, Sooran; Chen, Xi; Fitzhugh, William Physical Review Letters, Vol. 121, Issue 15 https://doi.org/10.1103/PhysRevLett.121.157001	journal	October 2018
Paddle wheel mechanism in lithium sulfates: Arguments in defense and evidence against Secco, E. A. Journal of Solid State Chemistry, Vol. 96, Issue 2 https://doi.org/10.1016/S0022-4596(05)80270-1	journal	February 1992
Comparing the Descriptors for Investigating the Influence of Lattice Dynamics on Ionic Transport Using the Superionic Conductor Na ₃ PS _{4– x} Se _x Krauskopf, Thorben; Muy, Sokseiha; Culver, Sean P. Journal of the American Chemical Society, Vol. 140, Issue 43 https://doi.org/10.1021/jacs.8b09340	journal	October 2018
Coupled Cation–Anion Dynamics Enhances Cation Mobility in Room-Temperature Superionic Solid-State Electrolytes Zhang, Zhizhen; Roy, Pierre-Nicholas; Li, Hui Journal of the American Chemical Society, Vol. 141, Issue 49 https://doi.org/10.1021/jacs.9b09343	journal	November 2019
Anomalous High Ionic Conductivity of Nanoporous β-Li₃PS₄ Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew Journal of the American Chemical Society, Vol. 135, Issue 3, p. 975-978 https://doi.org/10.1021/ja3110895	journal	January 2013
Volume Effect or Paddle-Wheel Mechanism—Fast Alkali-Metal Ionic Conduction in Solids with Rotationally Disordered Complex Anions Jansen, Martin Angewandte Chemie International Edition in English, Vol. 30, Issue 12 https://doi.org/10.1002/anie.199115471	journal	December 1991
Structural and dynamic properties of lithium sulphate in its solid electrolyte form Impey, Roger W.; Klein, Michael L.; McDonald, Ian R. The Journal of Chemical Physics, Vol. 82, Issue 10 https://doi.org/10.1063/1.448678	journal	May 1985
Targeting Superionic Conductivity by Turning on Anion Rotation at Room Temperature in Fast Ion Conductors Zhang, Zhizhen; Li, Hui; Kaup, Kavish Matter, Vol. 2, Issue 6 https://doi.org/10.1016/j.matt.2020.04.027	journal	June 2020
A single-crystal neutron diffraction study of the structure of the high-temperature rotor phase of lithium sulphate Kaber, R.; Nilsson, L.; Andersen, N. H. Journal of Physics: Condensed Matter, Vol. 4, Issue 8 https://doi.org/10.1088/0953-8984/4/8/008	journal	February 1992
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
Phonon–Ion Interactions: Designing Ion Mobility Based on Lattice Dynamics Muy, Sokseiha; Schlem, Roman; Shao‐Horn, Yang Advanced Energy Materials, Vol. 11, Issue 15 https://doi.org/10.1002/aenm.202002787	journal	December 2020
Roles of phonon amplitude and low-energy optical phonons on superionic conduction Wakamura, Kunio Physical Review B, Vol. 56, Issue 18 https://doi.org/10.1103/PhysRevB.56.11593	journal	November 1997
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Nonlinear lattice dynamics as a basis for enhanced superconductivity in YBa2Cu3O6.5 Mankowsky, R.; Subedi, A.; Först, M. Nature, Vol. 516, Issue 7529 https://doi.org/10.1038/nature13875	journal	December 2014
Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li ₆ PS ₅ X (X = Cl, Br, I) Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b06327	journal	July 2017
Paddle-wheel versus percolation mechanism for cation transport in some sulphate phases☆ Andersen, N.; Bandaranayake, P.; Careem, M. Solid State Ionics, Vol. 57, Issue 3-4 https://doi.org/10.1016/0167-2738(92)90149-J	journal	October 1992
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
Design principles for solid-state lithium superionic conductors Wang, Yan; Richards, William Davidson; Ong, Shyue Ping Nature Materials, Vol. 14, Issue 10 https://doi.org/10.1038/nmat4369	journal	August 2015
Phonon thermodynamics and elastic behavior of GaN at high temperatures and pressures Herriman, Jane E.; Hellman, Olle; Fultz, Brent Physical Review B, Vol. 98, Issue 21 https://doi.org/10.1103/PhysRevB.98.214105	journal	December 2018

Similar Records

Strongly Anharmonic Phonons and Their Role in Superionic Diffusion and Ultralow Thermal Conductivity of Cu₇PSe₆

Journal Article · 2022 · Advanced Energy Materials · OSTI ID:1870203

Related Subjects

Chemistry
Materials Science
Physics
Science & Technology - Other Topics

Anharmonic Cation–Anion Coupling Dynamics Assisted Lithium‐Ion Diffusion in Sulfide Solid Electrolytes

Citation Formats

References (58)

Similar Records

Related Subjects