Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors
Abstract
Here, we report on a new family of halide-deficient and Li-rich argyrodite fast-ion conductors, Li6+xPS5+x(Cl/Br/I)1–x (0 ≤ x ≤ 0.85). Exploration of the influence of aliovalent anion substitution in Li6PS5X (X = Cl, Br, I)–using a combination of high-resolution powder neutron diffraction and electrochemical impedance spectroscopy–reveals that aliovalent anion substitution induces higher Li-ion concentration and Li site disorder, and creates S2–/I– anion site disorder on the 4a site. In the series Li6+xPS5+xI1–x (0 ≤ x ≤ 0.4), the resulting conductivity for Li6.4PS5.4I0.6 (0.13 mS·cm–1) represents almost a 100-fold increase over that of the parent phase, Li6PS5I (0.0033 mS·cm–1), and establishes one of the first fast-ion conducting argyrodite thiophosphate iodides. For Cl-argyrodites, the ionic conductivity decreases a little with lower halide-content but ionic conductivity for the Br-argyrodites is almost unchanged. Overall, all Cl/Br-argyrodites Li6+xPS5+x(Cl/Br)1–x (0 ≤ x ≤ 0.75) with a low halide content exhibit surprisingly high ionic conductivities > 1 mS·cm–1 despite a very low degree of sulfur/halogen anion site disorder. Our findings highlight the importance of attaining a disordered Li-ion sublattice and sulfur/halogen anion site disorder (anionic charge homogeneity) in argyrodites, where Li ions occupy high energy sites and activate concerted ion migration that drives the ionic conductivity.
- Authors:
-
[1];
[2];
[1]
- Univ. of Waterloo, ON (Canada); Argonne National Lab. (ANL), Lemont, IL (United States). Joint Center for Energy Storage Research (JCESR)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1896963
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 21; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; activation energy; anions; diseases and disorders; ionic conductivity; ions
Citation Formats
Zhou, Laidong, Zhang, Qiang, and Nazar, Linda F. Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors. United States: N. p., 2022.
Web. doi:10.1021/acs.chemmater.2c02343.
Zhou, Laidong, Zhang, Qiang, & Nazar, Linda F. Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors. United States. https://doi.org/10.1021/acs.chemmater.2c02343
Zhou, Laidong, Zhang, Qiang, and Nazar, Linda F. Tue .
"Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors". United States. https://doi.org/10.1021/acs.chemmater.2c02343. https://www.osti.gov/servlets/purl/1896963.
@article{osti_1896963,
title = {Li-Rich and Halide-Deficient Argyrodite Fast Ion Conductors},
author = {Zhou, Laidong and Zhang, Qiang and Nazar, Linda F.},
abstractNote = {Here, we report on a new family of halide-deficient and Li-rich argyrodite fast-ion conductors, Li6+xPS5+x(Cl/Br/I)1–x (0 ≤ x ≤ 0.85). Exploration of the influence of aliovalent anion substitution in Li6PS5X (X = Cl, Br, I)–using a combination of high-resolution powder neutron diffraction and electrochemical impedance spectroscopy–reveals that aliovalent anion substitution induces higher Li-ion concentration and Li site disorder, and creates S2–/I– anion site disorder on the 4a site. In the series Li6+xPS5+xI1–x (0 ≤ x ≤ 0.4), the resulting conductivity for Li6.4PS5.4I0.6 (0.13 mS·cm–1) represents almost a 100-fold increase over that of the parent phase, Li6PS5I (0.0033 mS·cm–1), and establishes one of the first fast-ion conducting argyrodite thiophosphate iodides. For Cl-argyrodites, the ionic conductivity decreases a little with lower halide-content but ionic conductivity for the Br-argyrodites is almost unchanged. Overall, all Cl/Br-argyrodites Li6+xPS5+x(Cl/Br)1–x (0 ≤ x ≤ 0.75) with a low halide content exhibit surprisingly high ionic conductivities > 1 mS·cm–1 despite a very low degree of sulfur/halogen anion site disorder. Our findings highlight the importance of attaining a disordered Li-ion sublattice and sulfur/halogen anion site disorder (anionic charge homogeneity) in argyrodites, where Li ions occupy high energy sites and activate concerted ion migration that drives the ionic conductivity.},
doi = {10.1021/acs.chemmater.2c02343},
journal = {Chemistry of Materials},
number = 21,
volume = 34,
place = {United States},
year = {Tue Oct 25 00:00:00 EDT 2022},
month = {Tue Oct 25 00:00:00 EDT 2022}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Changing the Static and Dynamic Lattice Effects for the Improvement of the Ionic Transport Properties within the Argyrodite Li 6 PS 5– x Se x I
journal, October 2019
- Schlem, Roman; Ghidiu, Michael; Culver, Sean P.
- ACS Applied Energy Materials, Vol. 3, Issue 1
Local Charge Inhomogeneity and Lithium Distribution in the Superionic Argyrodites Li 6 PS 5 X (X = Cl, Br, I)
journal, July 2020
- Minafra, Nicolò; Kraft, Marvin A.; Bernges, Tim
- Inorganic Chemistry, Vol. 59, Issue 15
Tunable Lithium-Ion Transport in Mixed-Halide Argyrodites Li 6– x PS 5– x ClBr x : An Unusual Compositional Space
journal, February 2021
- Patel, Sawankumar V.; Banerjee, Swastika; Liu, Haoyu
- Chemistry of Materials, Vol. 33, Issue 4
Boosting Solid-State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution
journal, May 2019
- Adeli, Parvin; Bazak, J. David; Park, Kern Ho
- Angewandte Chemie International Edition, Vol. 58, Issue 26
An argyrodite sulfide-based superionic conductor synthesized by a liquid-phase technique with tetrahydrofuran and ethanol
journal, January 2019
- Yubuchi, So; Uematsu, Miwa; Hotehama, Chie
- Journal of Materials Chemistry A, Vol. 7, Issue 2
New horizons for inorganic solid state ion conductors
journal, January 2018
- Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina
- Energy & Environmental Science, Vol. 11, Issue 8
A review of structural properties and synthesis methods of solid electrolyte materials in the Li2S − P2S5 binary system
journal, December 2018
- Kudu, Ömer Ulaş; Famprikis, Theodosios; Fleutot, Benoit
- Journal of Power Sources, Vol. 407
Innovative Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State Lithium Batteries
journal, May 2021
- Zhou, Laidong; Minafra, Nicolò; Zeier, Wolfgang G.
- Accounts of Chemical Research, Vol. 54, Issue 12
Lithium Argyrodites with Phosphorus and Arsenic: Order and Disorder of Lithium Atoms, Crystal Chemistry, and Phase Transitions
journal, February 2010
- Kong, Shiao-Tong; Deiseroth, Hans-Jörg; Reiner, Christof
- Chemistry - A European Journal, Vol. 16, Issue 7
Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes
journal, September 2021
- Tan, Darren H. S.; Chen, Yu-Ting; Yang, Hedi
- Science, Vol. 373, Issue 6562
A solid future for battery development
journal, September 2016
- Janek, Jürgen; Zeier, Wolfgang G.
- Nature Energy, Vol. 1, Issue 9
Correlated Migration Invokes Higher Na + ‐Ion Conductivity in NaSICON‐Type Solid Electrolytes
journal, October 2019
- Zhang, Zhizhen; Zou, Zheyi; Kaup, Kavish
- Advanced Energy Materials, Vol. 9, Issue 42
Rethinking the Design of Ionic Conductors Using Meyer–Neldel–Conductivity Plot
journal, February 2021
- Gao, Yirong; Li, Nana; Wu, Yifan
- Advanced Energy Materials, Vol. 11, Issue 13
GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013
- Toby, Brian H.; Von Dreele, Robert B.
- Journal of Applied Crystallography, Vol. 46, Issue 2
A lithium superionic conductor
journal, July 2011
- Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
- Nature Materials, Vol. 10, Issue 9, p. 682-686
Engineering the Site‐Disorder and Lithium Distribution in the Lithium Superionic Argyrodite Li 6 PS 5 Br
journal, December 2020
- Gautam, Ajay; Sadowski, Marcel; Ghidiu, Michael
- Advanced Energy Materials, Vol. 11, Issue 5
Charging sustainable batteries
journal, March 2022
- Bauer, Christian; Burkhardt, Simon; Dasgupta, Neil P.
- Nature Sustainability, Vol. 5, Issue 3
Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes
journal, January 2020
- Schwietert, Tammo K.; Arszelewska, Violetta A.; Wang, Chao
- Nature Materials, Vol. 19, Issue 4
Fast Ion Conduction and Its Origin in Li 6– x PS 5– x Br 1+ x
journal, April 2020
- Wang, Pengbo; Liu, Haoyu; Patel, Sawankumar
- Chemistry of Materials, Vol. 32, Issue 9
Bond softness sensitive bond-valence parameters for crystal structure plausibility tests
journal, August 2017
- Chen, Haomin; Adams, Stefan
- IUCrJ, Vol. 4, Issue 5
High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016
- Kato, Yuki; Hori, Satoshi; Saito, Toshiya
- Nature Energy, Vol. 1, Issue 4
Interfacial reactivity and interphase growth of argyrodite solid electrolytes at lithium metal electrodes
journal, May 2018
- Wenzel, Sebastian; Sedlmaier, Stefan J.; Dietrich, Christian
- Solid State Ionics, Vol. 318
Bond Valence Pathway Analyzer—An Automatic Rapid Screening Tool for Fast Ion Conductors within softBV
journal, January 2021
- Wong, Lee Loong; Phuah, Kia Chai; Dai, Ruoyu
- Chemistry of Materials, Vol. 33, Issue 2
Elucidating Reversible Electrochemical Redox of Li 6 PS 5 Cl Solid Electrolyte
journal, August 2019
- Tan, Darren H. S.; Wu, Erik A.; Nguyen, Han
- ACS Energy Letters, Vol. 4, Issue 10
Concerted Migration Mechanism in the Li Ion Dynamics of Garnet-Type Li 7 La 3 Zr 2 O 12
journal, January 2013
- Jalem, Randy; Yamamoto, Yoshihiro; Shiiba, Hiromasa
- Chemistry of Materials, Vol. 25, Issue 3
Interfaces and Interphases in All-Solid-State Batteries with Inorganic Solid Electrolytes
journal, June 2020
- Banerjee, Abhik; Wang, Xuefeng; Fang, Chengcheng
- Chemical Reviews, Vol. 120, Issue 14
Superionic Halogen-Rich Li-Argyrodites Using In Situ Nanocrystal Nucleation and Rapid Crystal Growth
journal, March 2020
- Jung, Wo Dum; Kim, Ji-Su; Choi, Sungjun
- Nano Letters, Vol. 20, Issue 4
Mechanistic Origin of Superionic Lithium Diffusion in Anion-Disordered Li 6 PS 5 X Argyrodites
journal, March 2021
- Morgan, Benjamin J.
- Chemistry of Materials, Vol. 33, Issue 6
Origin of fast ion diffusion in super-ionic conductors
journal, June 2017
- He, Xingfeng; Zhu, Yizhou; Mo, Yifei
- Nature Communications, Vol. 8, Issue 1
On the Lithium Distribution in Halide Superionic Argyrodites by Halide Incorporation in Li7–xPS6–xClx
journal, July 2021
- Gautam, Ajay; Ghidiu, Michael; Suard, Emmanuelle
- ACS Applied Energy Materials, Vol. 4, Issue 7
Superionic Si-Substituted Lithium Argyrodite Sulfide Electrolyte Li 6+ x Sb 1– x Si x S 5 I for All-Solid-State Batteries
journal, December 2020
- Lee, Yongheum; Jeong, Jiwon; Lim, Hee-Dae
- ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 1
Lithium Argyrodite as Solid Electrolyte and Cathode Precursor for Solid‐State Batteries with Long Cycle Life
journal, July 2021
- Wang, Shuo; Tang, Mingxue; Zhang, Qinghua
- Advanced Energy Materials, Vol. 11, Issue 31
Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li 6 PS 5 X (X = Cl, Br, I)
journal, July 2017
- Kraft, Marvin A.; Culver, Sean P.; Calderon, Mario
- Journal of the American Chemical Society, Vol. 139, Issue 31
SoftBV – a software tool for screening the materials genome of inorganic fast ion conductors
journal, January 2019
- Chen, Haomin; Wong, Lee Loong; Adams, Stefan
- Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 75, Issue 1
Further Evidence for Energy Landscape Flattening in the Superionic Argyrodites Li 6+ x P 1– x M x S 5 I (M = Si, Ge, Sn)
journal, June 2019
- Ohno, Saneyuki; Helm, Bianca; Fuchs, Till
- Chemistry of Materials, Vol. 31, Issue 13
A profile refinement method for nuclear and magnetic structures
journal, June 1969
- Rietveld, H. M.
- Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71
New Family of Argyrodite Thioantimonate Lithium Superionic Conductors
journal, October 2019
- Zhou, Laidong; Assoud, Abdeljalil; Zhang, Qiang
- Journal of the American Chemical Society, Vol. 141, Issue 48
Solvent-Engineered Design of Argyrodite Li 6 PS 5 X (X = Cl, Br, I) Solid Electrolytes with High Ionic Conductivity
journal, November 2018
- Zhou, Laidong; Park, Kern-Ho; Sun, Xiaoqi
- ACS Energy Letters, Vol. 4, Issue 1
Li6PS5X: A Class of Crystalline Li-Rich Solids With an Unusually High Li+ Mobility
journal, January 2008
- Deiseroth, Hans-Jörg; Kong, Shiao-Tong; Eckert, Hellmut
- Angewandte Chemie International Edition, Vol. 47, Issue 4
Lithium Argyrodite Sulfide Electrolytes with High Ionic Conductivity and Air Stability for All-Solid-State Li-Ion Batteries
journal, December 2021
- Lee, Yongheum; Jeong, Jiwon; Lee, Ho Jun
- ACS Energy Letters, Vol. 7, Issue 1
Emerging Halide Superionic Conductors for All-Solid-State Batteries: Design, Synthesis, and Practical Applications
journal, April 2022
- Kwak, Hiram; Wang, Shuo; Park, Juhyoun
- ACS Energy Letters, Vol. 7, Issue 5
Correlated Li-ion migration in the superionic conductor Li10GeP2S12
journal, January 2021
- Yajima, Takeshi; Hinuma, Yoyo; Hori, Satoshi
- Journal of Materials Chemistry A
Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017
- Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
- Nature Reviews Materials, Vol. 2, Issue 4
Inducing High Ionic Conductivity in the Lithium Superionic Argyrodites Li 6+ x P 1– x Ge x S 5 I for All-Solid-State Batteries
journal, October 2018
- Kraft, Marvin A.; Ohno, Saneyuki; Zinkevich, Tatiana
- Journal of the American Chemical Society, Vol. 140, Issue 47
Opening Diffusion Pathways through Site Disorder: The Interplay of Local Structure and Ion Dynamics in the Solid Electrolyte Li6+xP1–xGexS5I as Probed by Neutron Diffraction and NMR
journal, January 2022
- Hogrefe, Katharina; Minafra, Nicolò; Hanghofer, Isabel
- Journal of the American Chemical Society, Vol. 144, Issue 4
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
journal, October 2016
- de Klerk, Niek J. J.; Rosłoń, Irek; Wagemaker, Marnix
- Chemistry of Materials, Vol. 28, Issue 21
Mechanochemical synthesis and ion transport properties of Na3OX (X = Cl, Br, I and BH4) antiperovskite solid electrolytes
journal, September 2020
- Ahiavi, Ernest; Dawson, James A.; Kudu, Ulas
- Journal of Power Sources, Vol. 471