Enhanced ionic conductivity and lack of paddle-wheel effect in pseudohalogen-substituted Li argyrodites

Sun, Yingzhi; Ouyang, Bin; Wang, Yan; Zhang, Yaqian; Sun, Shuo; Cai, Zijian; Lacivita, Valentina; Guo, Yinsheng; Ceder, Gerbrand

doi:10.1016/j.matt.2022.08.029

Enhanced ionic conductivity and lack of paddle-wheel effect in pseudohalogen-substituted Li argyrodites

Journal Article · Tue Dec 06 23:00:00 EST 2022 · Matter (Online)

DOI:https://doi.org/10.1016/j.matt.2022.08.029· OSTI ID:2246875

Sun, Yingzhi ^[1]; Ouyang, Bin ^[2]; Wang, Yan ^[3]; Zhang, Yaqian ^[4]; Sun, Shuo ^[5]; Cai, Zijian ^[1]; Lacivita, Valentina ^[3]; Guo, Yinsheng ^[5]; Ceder, Gerbrand ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Florida State Univ., Tallahassee, FL (United States)
Samsung Advanced Institute of Technology (United States); Samsung Semiconductor, Inc., Cambridge, MA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Univ. of Nebraska, Lincoln, NE (United States)

Superionic conductors are key to the development of safe and high-energy-density, all-solid-state batteries. Using a combined theoretical and experimental approach, we explore the feasibility of increasing the ionic conductivity through pseudohalogen substitution in the Li argyrodite structure. Under the guidance of calculated thermodynamic stability, BH₄-substituted Li argyrodite, Li_5.91PS_4.91(BH₄)_1.09, was successfully synthesized via a mechanochemical method. As-synthesized BH_4-substituted Li argyrodite displays an ionic conductivity of 4.8 mS/cm at 25°C. Ab initio molecular dynamics simulation trajectory analysis was used to investigate how BH₄ facilitates Li-ion diffusion and indicates only a weak correlation with the B–H bond motion. Here, we find that the enhanced conductivity mainly originates from the weak interaction between Li and BH₄ and find no evidence of a paddle-wheel effect from the polyanion. This work provides insight into how cluster ions enhance Li diffusion and systematically describes how to explore superionic conductors with pseudohalogen substitution.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2246875

Journal Information:: Matter (Online), Journal Name: Matter (Online) Journal Issue: 12 Vol. 5; ISSN 2590-2385

Publisher:: Cell Press/ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Computation‐Guided Synthesis of New Garnet‐Type Solid‐State Electrolytes via an Ultrafast Sintering Technique Wang, Ruiliu; Ping, Weiwei; Wang, Chengwei Advanced Materials, Vol. 32, Issue 46 https://doi.org/10.1002/adma.202005059	journal	October 2020
Lithium Fast-Ionic Conduction in Complex Hydrides: Review and Prospects Matsuo, Motoaki; Orimo, Shin-ichi Advanced Energy Materials, Vol. 1, Issue 2 https://doi.org/10.1002/aenm.201000012	journal	January 2011
Understanding Li‐Ion Dynamics in Lithium Hydroxychloride (Li ₂ OHCl) Solid State Electrolyte via Addressing the Role of Protons Song, Ah‐Young; Turcheniuk, Kostiantyn; Leisen, Johannes Advanced Energy Materials, Vol. 10, Issue 8 https://doi.org/10.1002/aenm.201903480	journal	January 2020
Tailoring the Cation Lattice for Chloride Lithium‐Ion Conductors Liu, Yunsheng; Wang, Shuo; Nolan, Adelaide M. Advanced Energy Materials, Vol. 10, Issue 40 https://doi.org/10.1002/aenm.202002356	journal	September 2020
Lithium Oxide Superionic Conductors Inspired by Garnet and NASICON Structures Xiao, Yihan; Jun, KyuJung; Wang, Yan Advanced Energy Materials, Vol. 11, Issue 37 https://doi.org/10.1002/aenm.202101437	journal	September 2021
Boosting Solid‐State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution Adeli, Parvin; Bazak, J. David; Park, Kern Ho Angewandte Chemie, Vol. 131, Issue 26 https://doi.org/10.1002/ange.201814222	journal	May 2019
Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂ Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781 https://doi.org/10.1002/anie.200701144	journal	October 2007
Li6PS5X: A Class of Crystalline Li-Rich Solids With an Unusually High Li+ Mobility Deiseroth, Hans-Jörg; Kong, Shiao-Tong; Eckert, Hellmut Angewandte Chemie International Edition, Vol. 47, Issue 4 https://doi.org/10.1002/anie.200703900	journal	January 2008
LiBH4 a new hydrogen storage material Züttel, A.; Wenger, P.; Rentsch, S. Journal of Power Sources, Vol. 118, Issue 1-2 https://doi.org/10.1016/S0378-7753(03)00054-5	journal	May 2003
Enhanced ion conduction by enforcing structural disorder in Li-deficient argyrodites Li6−xPS5−xCl1+x Feng, Xuyong; Chien, Po-Hsiu; Wang, Yan Energy Storage Materials, Vol. 30 https://doi.org/10.1016/j.ensm.2020.04.042	journal	September 2020
Innovative Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State Lithium Batteries Zhou, Laidong; Minafra, Nicolò; Zeier, Wolfgang G. Accounts of Chemical Research, Vol. 54, Issue 12 https://doi.org/10.1021/acs.accounts.0c00874	journal	May 2021
Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li ₂ OHCl Wang, Fei; Evans, Hayden A.; Kim, Kwangnam Chemistry of Materials, Vol. 32, Issue 19 https://doi.org/10.1021/acs.chemmater.0c02602	journal	September 2020
Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li _{6– x} PS _{5– x} ClBr _x : An Unusual Compositional Space Patel, Sawankumar V.; Banerjee, Swastika; Liu, Haoyu Chemistry of Materials, Vol. 33, Issue 4 https://doi.org/10.1021/acs.chemmater.0c04650	journal	February 2021
Diffusion Mechanism of Li Argyrodite Solid Electrolytes for Li-Ion Batteries and Prediction of Optimized Halogen Doping: The Effect of Li Vacancies, Halogens, and Halogen Disorder de Klerk, Niek J. J.; Rosłoń, Irek; Wagemaker, Marnix Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b03630	journal	October 2016
Computational Prediction and Evaluation of Solid-State Sodium Superionic Conductors Na ₇ P ₃ X ₁₁ (X = O, S, Se) Wang, Yan; Richards, William D.; Bo, Shou-Hang Chemistry of Materials, Vol. 29, Issue 17 https://doi.org/10.1021/acs.chemmater.7b02476	journal	August 2017
Computational Investigation of Halogen-Substituted Na Argyrodites as Solid-State Superionic Conductors Ouyang, Bin; Wang, Yan; Sun, Yingzhi Chemistry of Materials, Vol. 32, Issue 5 https://doi.org/10.1021/acs.chemmater.9b04541	journal	February 2020
Fast Ion Conduction and Its Origin in Li _{6– x} PS _{5– x} Br _{1+ x} Wang, Pengbo; Liu, Haoyu; Patel, Sawankumar Chemistry of Materials, Vol. 32, Issue 9 https://doi.org/10.1021/acs.chemmater.9b05331	journal	April 2020
Wet-Milling Synthesis of Superionic Lithium Argyrodite Electrolytes with Different Concentrations of Lithium Vacancy Wu, Liping; Zhang, Zhichao; Liu, Gaozhan ACS Applied Materials & Interfaces, Vol. 13, Issue 39 https://doi.org/10.1021/acsami.1c13031	journal	September 2021
Sodium Superionic Conductors Based on Clusters Fang, Hong; Jena, Puru ACS Applied Materials & Interfaces, Vol. 11, Issue 1 https://doi.org/10.1021/acsami.8b19003	journal	December 2018
Solvent-Engineered Design of Argyrodite Li ₆ PS ₅ X (X = Cl, Br, I) Solid Electrolytes with High Ionic Conductivity Zhou, Laidong; Park, Kern-Ho; Sun, Xiaoqi ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b01997	journal	November 2018
Mechanochemically Prepared Li ₂ S–P ₂ S ₅ –LiBH ₄ Solid Electrolytes with an Argyrodite Structure Sakuda, Atsushi; Yamauchi, Akihiro; Yubuchi, So ACS Omega, Vol. 3, Issue 5 https://doi.org/10.1021/acsomega.8b00377	journal	May 2018
First Principles Study of the Li₁₀GeP₂S₁₂ Lithium Super Ionic Conductor Material Mo, Yifei; Ong, Shyue Ping; Ceder, Gerbrand Chemistry of Materials, Vol. 24, Issue 1, p. 15-17 https://doi.org/10.1021/cm203303y	journal	December 2011
Li−Fe−P−O ₂ Phase Diagram from First Principles Calculations Ong, Shyue Ping; Wang, Lei; Kang, Byoungwoo Chemistry of Materials, Vol. 20, Issue 5 https://doi.org/10.1021/cm702327g	journal	February 2008
Data Mined Ionic Substitutions for the Discovery of New Compounds Hautier, Geoffroy; Fischer, Chris; Ehrlacher, Virginie Inorganic Chemistry, Vol. 50, Issue 2 https://doi.org/10.1021/ic102031h	journal	January 2011
Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations Dronskowski, Richard; Bloechl, Peter E. The Journal of Physical Chemistry, Vol. 97, Issue 33 https://doi.org/10.1021/j100135a014	journal	August 1993
Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li ₁₀ Ge _{1– x} Sn _x P ₂ S ₁₂ Culver, Sean P.; Squires, Alexander G.; Minafra, Nicolò Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10735	journal	December 2020
Fast Ion-Conducting Thioboracite with a Perovskite Topology and Argyrodite-like Lithium Substructure Kaup, Kavish; Bishop, Kevin; Assoud, Abdeljalil Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c00941	journal	April 2021
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
Rotational Cluster Anion Enabling Superionic Conductivity in Sodium-Rich Antiperovskite Na ₃ OBH ₄ Sun, Yulong; Wang, Yuechao; Liang, Xinmiao Journal of the American Chemical Society, Vol. 141, Issue 14 https://doi.org/10.1021/jacs.9b01746	journal	March 2019
New Family of Argyrodite Thioantimonate Lithium Superionic Conductors Zhou, Laidong; Assoud, Abdeljalil; Zhang, Qiang Journal of the American Chemical Society, Vol. 141, Issue 48 https://doi.org/10.1021/jacs.9b08357	journal	October 2019
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
Crystal Orbital Hamilton Population (COHP) Analysis As Projected from Plane-Wave Basis Sets Deringer, Volker L.; Tchougréeff, Andrei L.; Dronskowski, Richard The Journal of Physical Chemistry A, Vol. 115, Issue 21 https://doi.org/10.1021/jp202489s	journal	June 2011
Structural Phase Transitions of Mg(BH ₄ ) ₂ under Pressure George, Lyci; Drozd, Vadym; Saxena, Surendra K. The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp807842t	journal	December 2008
Technology: A solid future Motavalli, Jim Nature, Vol. 526, Issue 7575 https://doi.org/10.1038/526S96a	journal	October 2015
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
High magnesium mobility in ternary spinel chalcogenides Canepa, Pieremanuele; Bo, Shou-Hang; Sai Gautam, Gopalakrishnan Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01772-1	journal	November 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
Phase stability, electrochemical stability and ionic conductivity of the Li _10±1 MP ₂ X ₁₂ (M = Ge, Si, Sn, Al or P, and X = O, S or Se) family of superionic conductors Ong, Shyue Ping; Mo, Yifei; Richards, William Davidson Energy Environ. Sci., Vol. 6, Issue 1 https://doi.org/10.1039/C2EE23355J	journal	January 2013
Fast lithium-ionic conduction in a new complex hydride–sulphide crystalline phase Unemoto, Atsushi; Wu, Hui; Udovic, Terrence J. Chemical Communications, Vol. 52, Issue 3 https://doi.org/10.1039/C5CC07793A	journal	January 2016
Design of Li _1+2x Zn _1−x PS ₄ , a new lithium ion conductor Richards, William D.; Wang, Yan; Miara, Lincoln J. Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE02094A	journal	January 2016
Structural and Na-ion conduction characteristics of Na ₃ PS _x Se _4−x Bo, Shou-Hang; Wang, Yan; Ceder, Gerbrand Journal of Materials Chemistry A, Vol. 4, Issue 23 https://doi.org/10.1039/C6TA03027K	journal	January 2016
Compatibility issues between electrodes and electrolytes in solid-state batteries Tian, Yaosen; Shi, Tan; Richards, William D. Energy & Environmental Science, Vol. 10, Issue 5 https://doi.org/10.1039/C7EE00534B	journal	January 2017
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Li-rich antiperovskite superionic conductors based on cluster ions Fang, Hong; Jena, Puru Proceedings of the National Academy of Sciences, Vol. 114, Issue 42 https://doi.org/10.1073/pnas.1704086114	journal	October 2017
Oxidation energies of transition metal oxides within the GGA + U framework Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.195107	journal	May 2006
The thermodynamic scale of inorganic crystalline metastability Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping Science Advances, Vol. 2, Issue 11 https://doi.org/10.1126/sciadv.1600225	journal	November 2016
Predictive modeling and design rules for solid electrolytes Ceder, Gerbrand; Ong, Shyue Ping; Wang, Yan MRS Bulletin, Vol. 43, Issue 10 https://doi.org/10.1557/mrs.2018.210	journal	October 2018
Thirteen Ways to Look at the Correlation Coefficient Rodgers, Joseph Lee; Nicewander, W. Alan The American Statistician, Vol. 42, Issue 1 https://doi.org/10.2307/2685263	journal	February 1988

Similar Records

Argyrodite-type advanced lithium conductors and transport mechanisms beyond paddle-wheel effect

Journal Article · Tue Apr 19 00:00:00 EDT 2022 · Nature Communications · OSTI ID:1863636

Related Subjects

25 ENERGY STORAGE
cluster-ion substitution
solid electrolyte
solid-state battery
superionic conductor

Enhanced ionic conductivity and lack of paddle-wheel effect in pseudohalogen-substituted Li argyrodites

Citation Formats

References (48)

Similar Records

Related Subjects