Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte
Abstract
Sulfide-based solid electrolytes are promising candidates for all solid-state batteries (ASSBs) due to their high ionic conductivity and ease of processability. However, their narrow electrochemical stability window causes undesirable electrolyte decomposition. Existing literature on Li-ion ASSBs report an irreversible nature of such decompositions, while Li–S ASSBs show evidence of some reversibility. Here, we explain these observations by investigating the redox mechanism of argyrodite Li6PS5Cl at various chemical potentials. We found that Li–In | Li6PS5Cl | Li6PS5Cl–C half-cells can be cycled reversibly, delivering capacities of 965 mAh g–1 for the electrolyte itself. During charging, Li6PS5Cl forms oxidized products of sulfur (S) and phosphorus pentasulfide (P2S5), while during discharge, these products are first reduced to a Li3PS4 intermediate before forming lithium sulfide (Li2S) and lithium phosphide (Li3P). Lastly, we quantified the relative contributions of the products toward cell impedance and proposed a strategy to reduce electrolyte decomposition and increase cell Coulombic efficiency.
- Authors:
-
[2];
[1];
[2]
- Univ. of California San Diego, La Jolla, CA (United States). Dept. of NanoEngineering
- Univ. of California San Diego, La Jolla, CA (United States). Dept. of NanoEngineering; Univ. of California San Diego, La Jolla, CA (United States). Sustainable Power & Energy Center (SPEC)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Science Directorate
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1573940
- Report Number(s):
- LLNL-JRNL-786041
Journal ID: ISSN 2380-8195; 981644
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Volume: 4; Journal Issue: 10; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE
Citation Formats
Tan, Darren H. S., Wu, Erik A., Nguyen, Han, Chen, Zheng, Marple, Maxwell A. T., Doux, Jean -Marie, Wang, Xuefeng, Yang, Hedi, Banerjee, Abhik, and Meng, Ying Shirley. Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte. United States: N. p., 2019.
Web. doi:10.1021/acsenergylett.9b01693.
Tan, Darren H. S., Wu, Erik A., Nguyen, Han, Chen, Zheng, Marple, Maxwell A. T., Doux, Jean -Marie, Wang, Xuefeng, Yang, Hedi, Banerjee, Abhik, & Meng, Ying Shirley. Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte. United States. https://doi.org/10.1021/acsenergylett.9b01693
Tan, Darren H. S., Wu, Erik A., Nguyen, Han, Chen, Zheng, Marple, Maxwell A. T., Doux, Jean -Marie, Wang, Xuefeng, Yang, Hedi, Banerjee, Abhik, and Meng, Ying Shirley. Tue .
"Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte". United States. https://doi.org/10.1021/acsenergylett.9b01693. https://www.osti.gov/servlets/purl/1573940.
@article{osti_1573940,
title = {Elucidating Reversible Electrochemical Redox of Li6PS5Cl Solid Electrolyte},
author = {Tan, Darren H. S. and Wu, Erik A. and Nguyen, Han and Chen, Zheng and Marple, Maxwell A. T. and Doux, Jean -Marie and Wang, Xuefeng and Yang, Hedi and Banerjee, Abhik and Meng, Ying Shirley},
abstractNote = {Sulfide-based solid electrolytes are promising candidates for all solid-state batteries (ASSBs) due to their high ionic conductivity and ease of processability. However, their narrow electrochemical stability window causes undesirable electrolyte decomposition. Existing literature on Li-ion ASSBs report an irreversible nature of such decompositions, while Li–S ASSBs show evidence of some reversibility. Here, we explain these observations by investigating the redox mechanism of argyrodite Li6PS5Cl at various chemical potentials. We found that Li–In | Li6PS5Cl | Li6PS5Cl–C half-cells can be cycled reversibly, delivering capacities of 965 mAh g–1 for the electrolyte itself. During charging, Li6PS5Cl forms oxidized products of sulfur (S) and phosphorus pentasulfide (P2S5), while during discharge, these products are first reduced to a Li3PS4 intermediate before forming lithium sulfide (Li2S) and lithium phosphide (Li3P). Lastly, we quantified the relative contributions of the products toward cell impedance and proposed a strategy to reduce electrolyte decomposition and increase cell Coulombic efficiency.},
doi = {10.1021/acsenergylett.9b01693},
journal = {ACS Energy Letters},
number = 10,
volume = 4,
place = {United States},
year = {Tue Aug 20 00:00:00 EDT 2019},
month = {Tue Aug 20 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 165 works
Citation information provided by
Web of Science
Web of Science
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:
Issues and Challenges for Bulk-Type All-Solid-State Rechargeable Lithium Batteries using Sulfide Solid Electrolytes
journal, January 2015
- Jung, Yoon Seok; Oh, Dae Yang; Nam, Young Jin
- Israel Journal of Chemistry, Vol. 55, Issue 5
Review—Practical Challenges Hindering the Development of Solid State Li Ion Batteries
journal, January 2017
- Kerman, Kian; Luntz, Alan; Viswanathan, Venkatasubramanian
- Journal of The Electrochemical Society, Vol. 164, Issue 7
Synthesis, structure and electrochemical performance of the argyrodite Li 6 PS 5 Cl solid electrolyte for Li-ion solid state batteries
journal, October 2016
- Yu, Chuang; van Eijck, Lambert; Ganapathy, Swapna
- Electrochimica Acta, Vol. 215
Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li 6 PS 5 Cl Solid-State Electrolyte
journal, September 2018
- Yu, Chuang; Ganapathy, Swapna; Hageman, Jart
- ACS Applied Materials & Interfaces, Vol. 10, Issue 39
Interface Stability of Argyrodite Li 6 PS 5 Cl toward LiCoO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , and LiMn 2 O 4 in Bulk All-Solid-State Batteries
journal, April 2017
- Auvergniot, Jérémie; Cassel, Alice; Ledeuil, Jean-Bernard
- Chemistry of Materials, Vol. 29, Issue 9
High-Conductivity Argyrodite Li 6 PS 5 Cl Solid Electrolytes Prepared via Optimized Sintering Processes for All-Solid-State Lithium–Sulfur Batteries
journal, November 2018
- Wang, Shuo; Zhang, Yibo; Zhang, Xue
- ACS Applied Materials & Interfaces, Vol. 10, Issue 49
Interphase formation and degradation of charge transfer kinetics between a lithium metal anode and highly crystalline Li7P3S11 solid electrolyte
journal, March 2016
- Wenzel, Sebastian; Weber, Dominik A.; Leichtweiss, Thomas
- Solid State Ionics, Vol. 286
Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li 10 GeP 2 S 12 at the Lithium Metal Anode
journal, March 2016
- Wenzel, Sebastian; Randau, Simon; Leichtweiß, Thomas
- Chemistry of Materials, Vol. 28, Issue 7
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 Observation between LiCoO 2 Electrode and Li 2 S−P 2 S 5 Solid Electrolytes of All-Solid-State Lithium Secondary Batteries Using Transmission Electron Microscopy †
journal, February 2010
- Sakuda, Atsushi; Hayashi, Akitoshi; Tatsumisago, Masahiro
- Chemistry of Materials, Vol. 22, Issue 3
Structural and Electronic-State Changes of a Sulfide Solid Electrolyte during the Li Deinsertion–Insertion Processes
journal, May 2017
- Hakari, Takashi; Deguchi, Minako; Mitsuhara, Kei
- Chemistry of Materials, Vol. 29, Issue 11
Electrochemical Redox Behavior of Li Ion Conducting Sulfide Solid Electrolytes
journal, January 2019
- Swamy, Tushar; Chen, Xinwei; Chiang, Yet-Ming
- Chemistry of Materials, Vol. 31, Issue 3
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
journal, October 2015
- Zhu, Yizhou; He, Xingfeng; Mo, Yifei
- ACS Applied Materials & Interfaces, Vol. 7, Issue 42
Interface Stability in Solid-State Batteries
journal, December 2015
- Richards, William D.; Miara, Lincoln J.; Wang, Yan
- Chemistry of Materials, Vol. 28, Issue 1
The Detrimental Effects of Carbon Additives in Li 10 GeP 2 S 12 -Based Solid-State Batteries
journal, October 2017
- Zhang, Wenbo; Leichtweiß, Thomas; Culver, Sean P.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 41
Capacity Fade in Solid-State Batteries: Interphase Formation and Chemomechanical Processes in Nickel-Rich Layered Oxide Cathodes and Lithium Thiophosphate Solid Electrolytes
journal, June 2017
- Koerver, Raimund; Aygün, Isabel; Leichtweiß, Thomas
- Chemistry of Materials, Vol. 29, Issue 13
Redox activity of argyrodite Li6PS5Cl electrolyte in all-solid-state Li-ion battery: An XPS study
journal, February 2017
- Auvergniot, Jérémie; Cassel, Alice; Foix, Dominique
- Solid State Ionics, Vol. 300
High Cycle Capability of All-Solid-State Lithium–Sulfur Batteries Using Composite Electrodes by Liquid-Phase and Mechanical Mixing
journal, May 2018
- Suzuki, Kota; Mashimo, Naohiro; Ikeda, Yuki
- ACS Applied Energy Materials, Vol. 1, Issue 6
A Battery Made from a Single Material
journal, April 2015
- Han, Fudong; Gao, Tao; Zhu, Yujie
- Advanced Materials, Vol. 27, Issue 23
All Solid-State Lithium–Sulfur Battery Using a Glass-Type P 2 S 5 –Li 2 S Electrolyte: Benefits on Anode Kinetics
journal, January 2015
- Yamada, Takanobu; Ito, Seitaro; Omoda, Ryo
- Journal of The Electrochemical Society, Vol. 162, Issue 4
All solid-state battery with sulfur electrode and thio-LISICON electrolyte
journal, August 2008
- Kobayashi, Takeshi; Imade, Yuki; Shishihara, Daisuke
- Journal of Power Sources, Vol. 182, Issue 2, p. 621-625
All-solid-state lithium battery with sulfur/carbon composites as positive electrode materials
journal, March 2014
- Kinoshita, Shunji; Okuda, Kazuya; Machida, Nobuya
- Solid State Ionics, Vol. 256
Electrochemical properties of sulfur as cathode materials in a solid-state lithium battery with inorganic solid electrolytes
journal, November 2004
- Machida, N.
- Solid State Ionics, Vol. 175, Issue 1-4
High-capacity Li2S–nanocarbon composite electrode for all-solid-state rechargeable lithium batteries
journal, January 2012
- Nagao, Motohiro; Hayashi, Akitoshi; Tatsumisago, Masahiro
- Journal of Materials Chemistry, Vol. 22, Issue 19
Lithium Polysulfidophosphates: A Family of Lithium-Conducting Sulfur-Rich Compounds for Lithium-Sulfur Batteries
journal, June 2013
- Lin, Zhan; Liu, Zengcai; Fu, Wujun
- Angewandte Chemie International Edition, Vol. 52, Issue 29
All-solid-state rechargeable lithium batteries with Li2S as a positive electrode material
journal, August 2008
- Hayashi, Akitoshi; Ohtsubo, Ryoji; Ohtomo, Takamasa
- Journal of Power Sources, Vol. 183, Issue 1, p. 422-426
Rechargeable lithium batteries, using sulfur-based cathode materials and Li2S–P2S5 glass-ceramic electrolytes
journal, November 2004
- Hayashi, Akitoshi; Ohtomo, Takamasa; Mizuno, Fuminori
- Electrochimica Acta, Vol. 50, Issue 2-3
Sulfur–carbon composite electrode for all-solid-state Li/S battery with Li2S–P2S5 solid electrolyte
journal, July 2011
- Nagao, Motohiro; Hayashi, Akitoshi; Tatsumisago, Masahiro
- Electrochimica Acta, Vol. 56, Issue 17, p. 6055-6059
Fabrication of favorable interface between sulfide solid electrolyte and Li metal electrode for bulk-type solid-state Li/S battery
journal, August 2012
- Nagao, Motohiro; Hayashi, Akitoshi; Tatsumisago, Masahiro
- Electrochemistry Communications, Vol. 22
Activation of sulfur active material in an all-solid-state lithium–sulfur battery
journal, October 2014
- Nagata, Hiroshi; Chikusa, Yasuo
- Journal of Power Sources, Vol. 263
Lithium Superionic Sulfide Cathode for All-Solid Lithium–Sulfur Batteries
journal, March 2013
- Lin, Zhan; Liu, Zengcai; Dudney, Nancy J.
- ACS Nano, Vol. 7, Issue 3, p. 2829-2833
A lithium–sulfur battery using a solid, glass-type P2S5–Li2S electrolyte
journal, August 2013
- Agostini, Marco; Aihara, Yuichi; Yamada, Takanobu
- Solid State Ionics, Vol. 244
Li2S nanocomposites underlying high-capacity and cycling stability in all-solid-state lithium–sulfur batteries
journal, January 2015
- Nagao, Motohiro; Hayashi, Akitoshi; Tatsumisago, Masahiro
- Journal of Power Sources, Vol. 274
All-solid-state Li–sulfur batteries with mesoporous electrode and thio-LISICON solid electrolyte
journal, January 2013
- Nagao, Miki; Imade, Yuki; Narisawa, Haruto
- Journal of Power Sources, Vol. 222
Performance improvement of all-solid-state Li-S batteries with optimizing morphology and structure of sulfur composite electrode
journal, November 2017
- Choi, Han Ul; Jin, Ju Sung; Park, Jun-Young
- Journal of Alloys and Compounds, Vol. 723
All-solid-state Li/S batteries with highly conductive glass–ceramic electrolytes
journal, August 2003
- Hayashi, Akitoshi; Ohtomo, Takamasa; Mizuno, Fuminori
- Electrochemistry Communications, Vol. 5, Issue 8, p. 701-705
Electrochemical performance of all-solid-state lithium batteries with mechanochemically activated Li2S–Cu composite electrodes
journal, September 2008
- Hayashi, Akitoshi; Ohtsubo, Ryoji; Tatsumisago, Masahiro
- Solid State Ionics, Vol. 179, Issue 27-32
A lithium sulfur battery with high power density
journal, October 2014
- Nagata, Hiroshi; Chikusa, Yasuo
- Journal of Power Sources, Vol. 264
Electrochemical Investigation of All-Solid-State Lithium Batteries with a High Capacity Sulfur-Based Electrode
journal, January 2012
- Trevey, James E.; Gilsdorf, Jeremy R.; Stoldt, Conrad R.
- Journal of The Electrochemical Society, Vol. 159, Issue 7
High-performance all-solid-state lithium–sulfur batteries with sulfur/carbon nano-hybrids in a composite cathode
journal, January 2018
- Zhang, Yibo; Liu, Ting; Zhang, Qinghua
- Journal of Materials Chemistry A, Vol. 6, Issue 46
In Situ Generated Li 2 S–C Nanocomposite for High-Capacity and Long-Life All-Solid-State Lithium Sulfur Batteries with Ultrahigh Areal Mass Loading
journal, March 2019
- Yan, Hefeng; Wang, Hongchun; Wang, Donghao
- Nano Letters, Vol. 19, Issue 5
Cathode-Supported All-Solid-State Lithium–Sulfur Batteries with High Cell-Level Energy Density
journal, April 2019
- Xu, Ruochen; Yue, Jie; Liu, Sufu
- ACS Energy Letters, Vol. 4, Issue 5
High-Performance All-Solid-State Lithium–Sulfur Battery Enabled by a Mixed-Conductive Li 2 S Nanocomposite
journal, June 2016
- Han, Fudong; Yue, Jie; Fan, Xiulin
- Nano Letters, Vol. 16, Issue 7
All-Solid-State Lithium Secondary Battery with Li[sub 2]S–C Composite Positive Electrode Prepared by Spark-Plasma-Sintering Process
journal, January 2010
- Takeuchi, Tomonari; Kageyama, Hiroyuki; Nakanishi, Koji
- Journal of The Electrochemical Society, Vol. 157, Issue 11
All-solid-state lithium batteries with Li3PS4 glass as active material
journal, October 2015
- Hakari, Takashi; Nagao, Motohiro; Hayashi, Akitoshi
- Journal of Power Sources, Vol. 293
Fast Rotational Dynamics in Argyrodite-Type Li 6 PS 5 X (X: Cl, Br, I) as Seen by 31 P Nuclear Magnetic Relaxation—On Cation–Anion Coupled Transport in Thiophosphates
journal, May 2019
- Hanghofer, Isabel; Gadermaier, Bernhard; Wilkening, H. Martin R.
- Chemistry of Materials, Vol. 31, Issue 12
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
Structural Evolution and Li Dynamics in Nanophase Li 3 PS 4 by Solid-State and Pulsed-Field Gradient NMR
journal, May 2014
- Gobet, Mallory; Greenbaum, Steve; Sahu, Gayatri
- Chemistry of Materials, Vol. 26, Issue 11
Structural transformation of non-oxide chalcogenide glasses. The short-range order of lithium sulfide (Li2S)-phosphorus pentasulfide (P2S5) glasses studied by quantitative phosphorus-31, lithium-6, and lithium-7 high-resolution solid-state NMR
journal, May 1990
- Eckert, Hellmut; Zhang, Zhengming; Kennedy, John H.
- Chemistry of Materials, Vol. 2, Issue 3
Amorphous versus Crystalline Li 3 PS 4 : Local Structural Changes during Synthesis and Li Ion Mobility
journal, April 2019
- Stöffler, Heike; Zinkevich, Tatiana; Yavuz, Murat
- The Journal of Physical Chemistry C, Vol. 123, Issue 16
Analysis of the structure and degree of crystallisation of 70Li 2 S–30P 2 S 5 glass ceramic
journal, January 2015
- Seino, Yoshikatsu; Nakagawa, Masaru; Senga, Minoru
- Journal of Materials Chemistry A, Vol. 3, Issue 6
Identification of lithium–sulfur battery discharge products through 6Li and 33S solid-state MAS and 7Li solution NMR spectroscopy
journal, January 2015
- Huff, Laura A.; Rapp, Jennifer L.; Baughman, Jessi A.
- Surface Science, Vol. 631
Preparation, structure and ionic conductivity of lithium phosphide
journal, April 1989
- Nazri, G.
- Solid State Ionics, Vol. 34, Issue 1-2
Electrochemical Impedance Spectroscopy Study of a Lithium/Sulfur Battery: Modeling and Analysis of Capacity Fading
journal, January 2013
- Deng, Zhaofeng; Zhang, Zhian; Lai, Yanqing
- Journal of The Electrochemical Society, Vol. 160, Issue 4
Works referencing / citing this record:
Stack Pressure Considerations for Room‐Temperature All‐Solid‐State Lithium Metal Batteries
journal, November 2019
- Doux, Jean‐Marie; Nguyen, Han; Tan, Darren H. S.
- Advanced Energy Materials, Vol. 10, Issue 1
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
Design Principles of the Anode–Electrolyte Interface for All Solid‐State Lithium Metal Batteries
journal, October 2019
- Shen, Zeyu; Zhang, Weidong; Zhu, Guannan
- Small Methods, Vol. 4, Issue 1
Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte
journal, October 2015
- Kang, Joonhee; Chung, Habin; Doh, Chilhoon
- Journal of Power Sources, Vol. 293