Tailoring Solution-Processable Li Argyrodites Li6+xP1-xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries
Abstract
Owing to their high Li+ conductivities, mechanical sinterability, and solution processability, sulfide Li argyrodites have attracted much attention as enablers in the development of high-performance all-solid-state batteries with practicability. However, solution-processable Li argyrodites have been developed only for a composition of Li6PS5X (X = Cl, Br, I) with insufficiently high Li+ conductivities (~10–4 S cm–1). In this work, we report the highest Li+ conductivity of 0.54 mS cm–1 at 30 °C (Li6.5P0.5Ge0.5S5I) for solution-processable iodine-based Li argyrodites. Furthermore, a comparative investigation of three iodine-based argyrodites of unsubstituted and Ge- and Sn-substituted solution-processed Li6PS5I with varied heat-treatment temperature elucidates the effect of microstructural evolution on Li+ conductivity. Notably, local nanostructures consisting of argyrodite nanocrystallites in solution-processed Li6.5P0.5Ge0.5S5I have been directly captured by cryogenic transmission electron microscopy, which is a first for sulfide solid electrolyte materials. Specifically, the promising electrochemical performances of all-solid-state batteries at 30 °C employing LiCoO2 electrodes tailored by the infiltration of Li6.5P0.5Ge0.5S5I–ethanol solutions are successfully demonstrated.
- Authors:
-
[5];
[2];
[3];
[1]
- Hanyang Univ., Seoul (Korea, Republic of)
- Dongguk Univ., Seoul (Korea, Republic of)
- Ulsan National Institute of Science and Technology (UNIST), Ulsan (Korea, Republic of)
- UNIST Central Research Facilities (UCRF), Ulsan (Korea, Republic of)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Research Foundation of Korea (NRF); National Research Council of Science & Technology (NST)
- OSTI Identifier:
- 1642414
- Report Number(s):
- BNL-216186-2020-JAAM
Journal ID: ISSN 1530-6984
- Grant/Contract Number:
- SC0012704; NRF-2017M1A2A2044501; NRF-2018R1A2B600499; 2019R1C1C1009324
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nano Letters
- Additional Journal Information:
- Journal Volume: 20; Journal Issue: 6; Journal ID: ISSN 1530-6984
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; Solid-state batteries; solid electrolytes; cryo-TEM; sulfides; solution processes; electrodes; physical and chemical processes; electrical conductivity
Citation Formats
Song, Yong Bae, Kim, Dong Hyeon, Kwak, Hiram, Han, Daseul, Kang, Sujin, Lee, Jong Hoon, Bak, Seong-Min, Nam, Kyung-Wan, Lee, Hyun-Wook, and Jung, Yoon Seok. Tailoring Solution-Processable Li Argyrodites Li6+xP1-xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries. United States: N. p., 2020.
Web. doi:10.1021/acs.nanolett.0c01028.
Song, Yong Bae, Kim, Dong Hyeon, Kwak, Hiram, Han, Daseul, Kang, Sujin, Lee, Jong Hoon, Bak, Seong-Min, Nam, Kyung-Wan, Lee, Hyun-Wook, & Jung, Yoon Seok. Tailoring Solution-Processable Li Argyrodites Li6+xP1-xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries. United States. https://doi.org/10.1021/acs.nanolett.0c01028
Song, Yong Bae, Kim, Dong Hyeon, Kwak, Hiram, Han, Daseul, Kang, Sujin, Lee, Jong Hoon, Bak, Seong-Min, Nam, Kyung-Wan, Lee, Hyun-Wook, and Jung, Yoon Seok. Tue .
"Tailoring Solution-Processable Li Argyrodites Li6+xP1-xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries". United States. https://doi.org/10.1021/acs.nanolett.0c01028. https://www.osti.gov/servlets/purl/1642414.
@article{osti_1642414,
title = {Tailoring Solution-Processable Li Argyrodites Li6+xP1-xMxS5I (M = Ge, Sn) and Their Microstructural Evolution Revealed by Cryo-TEM for All-Solid-State Batteries},
author = {Song, Yong Bae and Kim, Dong Hyeon and Kwak, Hiram and Han, Daseul and Kang, Sujin and Lee, Jong Hoon and Bak, Seong-Min and Nam, Kyung-Wan and Lee, Hyun-Wook and Jung, Yoon Seok},
abstractNote = {Owing to their high Li+ conductivities, mechanical sinterability, and solution processability, sulfide Li argyrodites have attracted much attention as enablers in the development of high-performance all-solid-state batteries with practicability. However, solution-processable Li argyrodites have been developed only for a composition of Li6PS5X (X = Cl, Br, I) with insufficiently high Li+ conductivities (~10–4 S cm–1). In this work, we report the highest Li+ conductivity of 0.54 mS cm–1 at 30 °C (Li6.5P0.5Ge0.5S5I) for solution-processable iodine-based Li argyrodites. Furthermore, a comparative investigation of three iodine-based argyrodites of unsubstituted and Ge- and Sn-substituted solution-processed Li6PS5I with varied heat-treatment temperature elucidates the effect of microstructural evolution on Li+ conductivity. Notably, local nanostructures consisting of argyrodite nanocrystallites in solution-processed Li6.5P0.5Ge0.5S5I have been directly captured by cryogenic transmission electron microscopy, which is a first for sulfide solid electrolyte materials. Specifically, the promising electrochemical performances of all-solid-state batteries at 30 °C employing LiCoO2 electrodes tailored by the infiltration of Li6.5P0.5Ge0.5S5I–ethanol solutions are successfully demonstrated.},
doi = {10.1021/acs.nanolett.0c01028},
journal = {Nano Letters},
number = 6,
volume = 20,
place = {United States},
year = {Tue May 05 00:00:00 EDT 2020},
month = {Tue May 05 00:00:00 EDT 2020}
}
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Works referenced in this record:
Challenges for Rechargeable Li Batteries
journal, February 2010
- Goodenough, John B.; Kim, Youngsik
- Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
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
Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017
- Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
- Nature Reviews Materials, Vol. 2, Issue 4
Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All-Solid-State Batteries
journal, April 2018
- Park, Kern Ho; Bai, Qiang; Kim, Dong Hyeon
- Advanced Energy Materials, Vol. 8, Issue 18
New horizons for inorganic solid state ion conductors
journal, January 2018
- Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina
- Energy & Environmental Science, Vol. 11, Issue 8
New Concepts in Electrolytes
journal, February 2020
- Li, Matthew; Wang, Chunsheng; Chen, Zhongwei
- Chemical Reviews
Designing solid-state electrolytes for safe, energy-dense batteries
journal, February 2020
- Zhao, Qing; Stalin, Sanjuna; Zhao, Chen-Zi
- Nature Reviews Materials, Vol. 5, Issue 3
Negating interfacial impedance in garnet-based solid-state Li metal batteries
journal, December 2016
- Han, Xiaogang; Gong, Yunhui; Fu, Kun (Kelvin)
- Nature Materials, Vol. 16, Issue 5
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
Development of the cold sintering process and its application in solid-state lithium batteries
journal, July 2018
- Liu, Yulong; Sun, Qian; Wang, Dawei
- Journal of Power Sources, Vol. 393
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
Variation in structure and Li+-ion migration in argyrodite-type Li6PS5X (X = Cl, Br, I) solid electrolytes
journal, October 2011
- Rayavarapu, Prasada Rao; Sharma, Neeraj; Peterson, Vanessa K.
- Journal of Solid State Electrochemistry, Vol. 16, Issue 5
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
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
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
Mechanochemical synthesis of Li-argyrodite Li6PS5X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application
journal, August 2012
- Boulineau, Sylvain; Courty, Matthieu; Tarascon, Jean-Marie
- Solid State Ionics, Vol. 221
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
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
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
Liquid-phase syntheses of sulfide electrolytes for all-solid-state lithium battery
journal, February 2019
- Miura, Akira; Rosero-Navarro, Nataly Carolina; Sakuda, Atsushi
- Nature Reviews Chemistry, Vol. 3, Issue 3
Preparation of high lithium-ion conducting Li6PS5Cl solid electrolyte from ethanol solution for all-solid-state lithium batteries
journal, October 2015
- Yubuchi, So; Teragawa, Shingo; Aso, Keigo
- Journal of Power Sources, Vol. 293
Infiltration of Solution-Processable Solid Electrolytes into Conventional Li-Ion-Battery Electrodes for All-Solid-State Li-Ion Batteries
journal, April 2017
- Kim, Dong Hyeon; Oh, Dae Yang; Park, Kern Ho
- Nano Letters, Vol. 17, Issue 5
Coatable Li 4 SnS 4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries
journal, May 2017
- Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon
- ChemSusChem, Vol. 10, Issue 12
Solution-Processable Glass LiI-Li 4 SnS 4 Superionic Conductors for All-Solid-State Li-Ion Batteries
journal, December 2015
- Park, Kern Ho; Oh, Dae Yang; Choi, Young Eun
- Advanced Materials, Vol. 28, Issue 9
Na 3 SbS 4 : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries
journal, July 2016
- Banerjee, Abhik; Park, Kern Ho; Heo, Jongwook W.
- Angewandte Chemie International Edition, Vol. 55, Issue 33
New Na-Ion Solid Electrolytes Na 4− x Sn 1− x Sb x S 4 (0.02 ≤ x ≤ 0.33) for All-Solid-State Na-Ion Batteries
journal, January 2018
- Heo, Jongwook W.; Banerjee, Abhik; Park, Kern Ho
- Advanced Energy Materials, Vol. 8, Issue 11
Sheet-type Li6PS5Cl-infiltrated Si anodes fabricated by solution process for all-solid-state lithium-ion batteries
journal, June 2019
- Kim, Dong Hyeon; Lee, Han Ah; Song, Yong Bae
- Journal of Power Sources, Vol. 426
Crystallization of closo-borate electrolytes from solution enabling infiltration into slurry-casted porous electrodes for all-solid-state batteries
journal, April 2020
- Duchêne, Léo; Kim, Dong Hyeon; Song, Yong Bae
- Energy Storage Materials, Vol. 26
Thin and Flexible Solid Electrolyte Membranes with Ultrahigh Thermal Stability Derived from Solution-Processable Li Argyrodites for All-Solid-State Li-Ion Batteries
journal, February 2020
- Kim, Dong Hyeon; Lee, Yong-Hyeok; Song, Yong Bae
- ACS Energy Letters, Vol. 5, Issue 3
Anomalous High Ionic Conductivity of Nanoporous β-Li3PS4
journal, January 2013
- Liu, Zengcai; Fu, Wujun; Payzant, E. Andrew
- Journal of the American Chemical Society, Vol. 135, Issue 3, p. 975-978
A synthesis of crystalline Li7P3S11 solid electrolyte from 1,2-dimethoxyethane solvent
journal, December 2014
- Ito, Seitaro; Nakakita, Moeka; Aihara, Yuichi
- Journal of Power Sources, Vol. 271
Suppressing Li Dendrite Formation in Li 2 S-P 2 S 5 Solid Electrolyte by LiI Incorporation
journal, March 2018
- Han, Fudong; Yue, Jie; Zhu, Xiangyang
- Advanced Energy Materials, Vol. 8, Issue 18
Solid Electrolyte Layers by Solution Deposition
journal, January 2018
- Lim, Hee‐Dae; Lim, Hyung‐Kyu; Xing, Xing
- Advanced Materials Interfaces, Vol. 5, Issue 8
Lithium Dendrite Growth Suppression and Ionic Conductivity of Li 2 S-P 2 S 5 -P 2 O 5 Glass Solid Electrolytes Prepared by Mechanical Milling
journal, January 2019
- Cengiz, Mazlum; Oh, Hyukkeun; Lee, Se-Hee
- Journal of The Electrochemical Society, Vol. 166, Issue 16
Taming Active Material-Solid Electrolyte Interfaces with Organic Cathode for All-Solid-State Batteries
journal, May 2019
- Hao, Fang; Chi, Xiaowei; Liang, Yanliang
- Joule, Vol. 3, Issue 5
Lithium ion conductivity in Li 2 S–P 2 S 5 glasses – building units and local structure evolution during the crystallization of superionic conductors Li 3 PS 4 , Li 7 P 3 S 11 and Li 4 P 2 S 7
journal, January 2017
- Dietrich, Christian; Weber, Dominik A.; Sedlmaier, Stefan J.
- Journal of Materials Chemistry A, Vol. 5, Issue 34
Structure of the TRPV1 ion channel determined by electron cryo-microscopy
journal, December 2013
- Liao, Maofu; Cao, Erhu; Julius, David
- Nature, Vol. 504, Issue 7478
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy
journal, October 2017
- Li, Yuzhang; Li, Yanbin; Pei, Allen
- Science, Vol. 358, Issue 6362
Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy
journal, July 2019
- Wang, Jiangyan; Huang, William; Pei, Allen
- Nature Energy, Vol. 4, Issue 8
Cryogenic Electron Microscopy for Characterizing and Diagnosing Batteries
journal, November 2018
- Wang, Xuefeng; Li, Yejing; Meng, Ying Shirley
- Joule, Vol. 2, Issue 11
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007
- Ferrari, Andrea C.
- Solid State Communications, Vol. 143, Issue 1-2, p. 47-57
Raman Spectroscopy of nanomaterials: How spectra relate to disorder, particle size and mechanical properties
journal, March 2007
- Gouadec, Gwénaël; Colomban, Philippe
- Progress in Crystal Growth and Characterization of Materials, Vol. 53, Issue 1
Mechanochemical Synthesis: A Tool to Tune Cation Site Disorder and Ionic Transport Properties of Li 3 MCl 6 (M = Y, Er) Superionic Conductors
journal, December 2019
- Schlem, Roman; Muy, Sokseiha; Prinz, Nils
- Advanced Energy Materials, Vol. 10, Issue 6
Lithium-Ion-Conducting Argyrodite-Type Li 6 PS 5 X (X = Cl, Br, I) Solid Electrolytes Prepared by a Liquid-Phase Technique Using Ethanol as a Solvent
journal, July 2018
- Yubuchi, So; Uematsu, Miwa; Deguchi, Minako
- ACS Applied Energy Materials, Vol. 1, Issue 8
Comparison of Si and Ge low-loss spectra to interpret the Ge contrast in EFTEM images of Si1−x Gex nanostructures
journal, October 2006
- Pantel, R.; Cheynet, M. C.; Tichelaar, F. D.
- Micron, Vol. 37, Issue 7
Implanting Germanium into Graphene
journal, April 2018
- Tripathi, Mukesh; Markevich, Alexander; Böttger, Roman
- ACS Nano, Vol. 12, Issue 5
Li 3 BO 3 –Li 2 CO 3 : Rationally Designed Buffering Phase for Sulfide All-Solid-State Li-Ion Batteries
journal, October 2018
- Jung, Sung Hoo; Oh, Kyungbae; Nam, Young Jin
- Chemistry of Materials, Vol. 30, Issue 22
Ni‐Rich Layered Cathode Materials with Electrochemo‐Mechanically Compliant Microstructures for All‐Solid‐State Li Batteries
journal, December 2019
- Jung, Sung Hoo; Kim, Un‐Hyuck; Kim, Jae‐Hyung
- Advanced Energy Materials, Vol. 10, Issue 6