Direct observation of the redistribution of sulfur and polysufides in Li-S batteries during first cycle by in situ X-Ray fluorescence microscopy
Abstract
The demands on low cost and high energy density rechargeable batteries for both transportation and large-scale stationary energy storage are stimulating more and more research toward new battery systems. Since sulfur is an earth-abundant material with low cost, research on the high energy density Li–S batteries (2600 W h kg⁻¹) are getting more and more attention. The reactions between sulfur and lithium during charge–discharge cycling are quite complicated, going through multiple electron transfer process associated with chemical and electrochemical equilibrium between long- and short-chain polysulfide Li₂Sx intermediates (1 < x ≤ 8). It is reported that the long-chain polysulfides can be dissolved into electrolyte with aprotic organic solvents and migrated to the Li anode side. This so-called “shuttle effect” is believed to be the main reason for capacity loss and low columbic efficiency of the Li–S batteries. In the past few years, a great deal of efforts have been made on how to overcome the problem of polysulfide dissolution through new sulfur electrode construction and cell designs, as well as the modification of the electrolyte. Although it has been reported by several publications that some Li–S cells can sustain more than a thousand cycles based on the thin film electrodemore »
- Authors:
-
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Pacific Northwest National Laboratory, Joint Center for Energy Storage Research, Richland, WA (United States)
- Dongguk University-Seoul, Department of Energy and Materials Engineering, (Republic of Korea)
- Univ. of Massachusetts at Boston, Dept. of Chemistry, MA (United States)
- Argonne National Laboratory, X-ray Science Division, Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1177848
- Report Number(s):
- BNL-107699-2015-JA
Journal ID: ISSN 1614-6832; R&D Project: MA453MAEA; VT1201000
- Grant/Contract Number:
- SC00112704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 16; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; energy storage; in situ techniques; lithium–sulfur batteries; microspectroscopy; reaction mechanism
Citation Formats
Yu, Xiquian, Pan, Huilin, Zhou, Yongning, Northrup, Paul, Xiao, Jie, Bak, Seongmin, Liu, Mingzhao, Nam, Kyung-Wan, Qu, Deyang, Liu, Jun, Wu, Tianpin, and Yang, Xiao-Qing. Direct observation of the redistribution of sulfur and polysufides in Li-S batteries during first cycle by in situ X-Ray fluorescence microscopy. United States: N. p., 2015.
Web. doi:10.1002/aenm.201500072.
Yu, Xiquian, Pan, Huilin, Zhou, Yongning, Northrup, Paul, Xiao, Jie, Bak, Seongmin, Liu, Mingzhao, Nam, Kyung-Wan, Qu, Deyang, Liu, Jun, Wu, Tianpin, & Yang, Xiao-Qing. Direct observation of the redistribution of sulfur and polysufides in Li-S batteries during first cycle by in situ X-Ray fluorescence microscopy. United States. https://doi.org/10.1002/aenm.201500072
Yu, Xiquian, Pan, Huilin, Zhou, Yongning, Northrup, Paul, Xiao, Jie, Bak, Seongmin, Liu, Mingzhao, Nam, Kyung-Wan, Qu, Deyang, Liu, Jun, Wu, Tianpin, and Yang, Xiao-Qing. Wed .
"Direct observation of the redistribution of sulfur and polysufides in Li-S batteries during first cycle by in situ X-Ray fluorescence microscopy". United States. https://doi.org/10.1002/aenm.201500072. https://www.osti.gov/servlets/purl/1177848.
@article{osti_1177848,
title = {Direct observation of the redistribution of sulfur and polysufides in Li-S batteries during first cycle by in situ X-Ray fluorescence microscopy},
author = {Yu, Xiquian and Pan, Huilin and Zhou, Yongning and Northrup, Paul and Xiao, Jie and Bak, Seongmin and Liu, Mingzhao and Nam, Kyung-Wan and Qu, Deyang and Liu, Jun and Wu, Tianpin and Yang, Xiao-Qing},
abstractNote = {The demands on low cost and high energy density rechargeable batteries for both transportation and large-scale stationary energy storage are stimulating more and more research toward new battery systems. Since sulfur is an earth-abundant material with low cost, research on the high energy density Li–S batteries (2600 W h kg⁻¹) are getting more and more attention. The reactions between sulfur and lithium during charge–discharge cycling are quite complicated, going through multiple electron transfer process associated with chemical and electrochemical equilibrium between long- and short-chain polysulfide Li₂Sx intermediates (1 < x ≤ 8). It is reported that the long-chain polysulfides can be dissolved into electrolyte with aprotic organic solvents and migrated to the Li anode side. This so-called “shuttle effect” is believed to be the main reason for capacity loss and low columbic efficiency of the Li–S batteries. In the past few years, a great deal of efforts have been made on how to overcome the problem of polysulfide dissolution through new sulfur electrode construction and cell designs, as well as the modification of the electrolyte. Although it has been reported by several publications that some Li–S cells can sustain more than a thousand cycles based on the thin film electrode configurations, the long-term cycling stability is still one of the major barriers for the real application of Li–S batteries. More in-depth studies on the fundamental understanding of the sulfur reaction mechanism and interactions among the different polysulfide species, the electrolyte and the electrodes are still greatly needed. Various in situ techniques have been developed and applied to study the mechanism of the sulfur chemistry in Li–S batteries during electrochemical cycling, such as transmission X-ray microscopy (TXM), X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), UV–visible spectroscopy, and electron paramagnetic resonance (EPR). The applications of these characterization techniques have demonstrated their power in probing the structure changes, morphology evolutions, and coordination of sulfur and polysulfides with the electrolyte in Li–S cells, providing complementary information to each other thus enhancing the understanding in Li–S battery systems. In this communication, in situ X-ray fluorescence (XRF) microscopy was combined with XAS to directly probe the morphology changes of Li–S batteries during first cycle. The morphology changes of the sulfur electrode and the redistribution of sulfur and polysulfides were monitored in real time through the XRF images, while the changes of the sulfur containing compounds were characterized through the XAS spectra simultaneously. In contrast to other studies using ex situ or single characterization technique as reported in the literatures, the in situ technique used in this work has the unique feature of probing the Li–S cell under operating conditions, as well as the combination of XRF imaging with spectroscopy data. By doing this, the morphology evolution and redistribution of specific sulfur particles during cycling can be tracked and identified at certain locations in a real time. In addition, this technique allows us to select the field-of-view (FOV) area from micrometer to centimeter size, providing the capability to study the Li–S reactions not just at the material level, but also at the electrode level. This is very important for both understanding Li–S chemistry and designing effective strategies for Li–S batteries.},
doi = {10.1002/aenm.201500072},
journal = {Advanced Energy Materials},
number = 16,
volume = 5,
place = {United States},
year = {Wed Mar 25 00:00:00 EDT 2015},
month = {Wed Mar 25 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011
- Dunn, B.; Kamath, H.; Tarascon, J. -M.
- Science, Vol. 334, Issue 6058
Li–O2 and Li–S batteries with high energy storage
journal, January 2012
- Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
- Nature Materials, Vol. 11, Issue 1, p. 19-29
Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid
journal, June 2012
- Liu, Jun; Zhang, Ji-Guang; Yang, Zhenguo
- Advanced Functional Materials, Vol. 23, Issue 8
Room-temperature stationary sodium-ion batteries for large-scale electric energy storage
journal, January 2013
- Pan, Huilin; Hu, Yong-Sheng; Chen, Liquan
- Energy & Environmental Science, Vol. 6, Issue 8
A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries
journal, May 2009
- Ji, Xiulei; Lee, Kyu Tae; Nazar, Linda F.
- Nature Materials, Vol. 8, Issue 6, p. 500-506
Challenges and Prospects of Lithium–Sulfur Batteries
journal, June 2012
- Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng
- Accounts of Chemical Research, Vol. 46, Issue 5
Rechargeable Lithium–Sulfur Batteries
journal, July 2014
- Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
- Chemical Reviews, Vol. 114, Issue 23
Capacity Fading Mechanisms on Cycling a High-Capacity Secondary Sulfur Cathode
journal, January 2004
- Cheon, Sang-Eun; Choi, Soo-Seok; Han, Ji-Seong
- Journal of The Electrochemical Society, Vol. 151, Issue 12
Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions
journal, June 2013
- Zhang, Sheng S.
- Journal of Power Sources, Vol. 231, p. 153-162
Polysulfide Shuttle Study in the Li/S Battery System
journal, January 2004
- Mikhaylik, Yuriy V.; Akridge, James R.
- Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976
Advances in Li–S batteries
journal, January 2010
- Ji, Xiulei; Nazar, Linda F.
- Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826
Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer
journal, January 2012
- Su, Yu-Sheng; Manthiram, Arumugam
- Nature Communications, Vol. 3, Article No. 1166
Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability
journal, July 2011
- Wang, Hailiang; Yang, Yuan; Liang, Yongye
- Nano Letters, Vol. 11, Issue 7, p. 2644-2647
A new class of Solvent-in-Salt electrolyte for high-energy rechargeable metallic lithium batteries
journal, February 2013
- Suo, Liumin; Hu, Yong-Sheng; Li, Hong
- Nature Communications, Vol. 4, Issue 1
Smaller Sulfur Molecules Promise Better Lithium–Sulfur Batteries
journal, October 2012
- Xin, Sen; Gu, Lin; Zhao, Na-Hong
- Journal of the American Chemical Society, Vol. 134, Issue 45
Lithium-Sulfur Batteries: Electrochemistry, Materials, and Prospects
journal, November 2013
- Yin, Ya-Xia; Xin, Sen; Guo, Yu-Guo
- Angewandte Chemie International Edition, Vol. 52, Issue 50
Polysulfide dissolution control: the common ion effect
journal, January 2013
- Shin, Eon Sung; Kim, Keon; Oh, Si Hyoung
- Chem. Commun., Vol. 49, Issue 20
Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries
journal, January 2013
- Wei Seh, Zhi; Li, Weiyang; Cha, Judy J.
- Nature Communications, Vol. 4, Article No. 1331
In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries
journal, March 2012
- Nelson, Johanna; Misra, Sumohan; Yang, Yuan
- Journal of the American Chemical Society, Vol. 134, Issue 14
Understanding dynamics of polysulfide dissolution and re-deposition in working lithium–sulfur battery by in-operando transmission X-ray microscopy
journal, October 2014
- Lin, Chia-Nan; Chen, Wen-Chin; Song, Yen-Fang
- Journal of Power Sources, Vol. 263
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy
journal, September 2013
- Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 19
X-ray Absorption Near-Edge Structure and Nuclear Magnetic Resonance Study of the Lithium-Sulfur Battery and its Components
journal, February 2014
- Patel, Manu U. M.; Arčon, Iztok; Aquilanti, Giuliana
- ChemPhysChem, Vol. 15, Issue 5
Mechanistic insights into operational lithium–sulfur batteries by in situ X-ray diffraction and absorption spectroscopy
journal, January 2014
- Lowe, Michael A.; Gao, Jie; Abruña, Héctor D.
- RSC Advances, Vol. 4, Issue 35
New insight into the working mechanism of lithium–sulfur batteries: in situ and operando X-ray diffraction characterization
journal, January 2013
- Waluś, Sylwia; Barchasz, Céline; Colin, Jean-François
- Chemical Communications, Vol. 49, Issue 72
Application of In Operando UV/Vis Spectroscopy in Lithium-Sulfur Batteries
journal, July 2014
- Patel, Manu U. M.; Dominko, Robert
- ChemSusChem, Vol. 7, Issue 8
Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries
journal, December 2014
- Wang, Qiang; Zheng, Jianming; Walter, Eric
- Journal of The Electrochemical Society, Vol. 162, Issue 3
Handbook of Nuclear Chemistry
book, January 2011
- Vertes, Attila; Nagy, Sandor; klencsar, Zoltan
- Springer New York, NY
Fast, Reversible Lithium Storage with a Sulfur/Long-Chain-Polysulfide Redox Couple
journal, May 2013
- Su, Yu-Sheng; Fu, Yongzhu; Guo, Bingkun
- Chemistry - A European Journal, Vol. 19, Issue 26
Controlled Nucleation and Growth Process of Li2S2/Li2S in Lithium-Sulfur Batteries
journal, January 2013
- Zheng, Jianming; Gu, Meng; Wang, Chongmin
- Journal of The Electrochemical Society, Vol. 160, Issue 11, p. A1992-A1996
High rate delithiation behaviour of LiFePO4 studied by quick X-ray absorption spectroscopy
journal, January 2012
- Yu, Xiqian; Wang, Qi; Zhou, Yongning
- Chemical Communications, Vol. 48, Issue 94
X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles
journal, April 2014
- Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
High Energy Density Lithium-Sulfur Batteries: Challenges of Thick Sulfur Cathodes
journal, March 2015
- Lv, Dongping; Zheng, Jianming; Li, Qiuyan
- Advanced Energy Materials, Vol. 5, Issue 16, Article No. 1402290
Manipulating surface reactions in lithium–sulphur batteries using hybrid anode structures
journal, January 2014
- Huang, Cheng; Xiao, Jie; Shao, Yuyan
- Nature Communications, Vol. 5, Issue 1, Article No. 3015
A High-Performance Polymer Tin Sulfur Lithium Ion Battery
journal, February 2010
- Hassoun, Jusef; Scrosati, Bruno
- Angewandte Chemie International Edition, Vol. 49, Issue 13, p. 2371-2374
Carbon-Based Anodes for Lithium Sulfur Full Cells with High Cycle Stability
journal, August 2013
- Brückner, Jan; Thieme, Sören; Böttger-Hiller, Falko
- Advanced Functional Materials, Vol. 24, Issue 9
A Lithium-Sulfur Battery with a High Areal Energy Density
journal, June 2014
- Kim, Joo-Seong; Hwang, Tae Hoon; Kim, Byung Gon
- Advanced Functional Materials, Vol. 24, Issue 34
In Situ Formation of Protective Coatings on Sulfur Cathodes in Lithium Batteries with LiFSI-Based Organic Electrolytes
journal, December 2014
- Kim, Hyea; Wu, Feixiang; Lee, Jung Tae
- Advanced Energy Materials, Vol. 5, Issue 6
Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 Cathode Materials
journal, December 2013
- Yu, Xiqian; Lyu, Yingchun; Gu, Lin
- Advanced Energy Materials, Vol. 4, Issue 5
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
A High-Performance Polymer Tin Sulfur Lithium Ion Battery
journal, February 2010
- Hassoun, Jusef; Scrosati, Bruno
- Angewandte Chemie, Vol. 122, Issue 13
Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium-Sulfur-Battery Cathode Material with High Capacity and Cycling Stability
text, January 2011
- Wang, Hailiang; Yang, Yuan; Liang, Yongye
- arXiv
Works referencing / citing this record:
Advanced Characterization Techniques in Promoting Mechanism Understanding for Lithium-Sulfur Batteries
journal, March 2018
- Zhao, Enyue; Nie, Kaihui; Yu, Xiqian
- Advanced Functional Materials, Vol. 28, Issue 38
A Comprehensive Understanding of Lithium–Sulfur Battery Technology
journal, June 2019
- Li, Tao; Bai, Xue; Gulzar, Umair
- Advanced Functional Materials, Vol. 29, Issue 32
Structure-Property Relationships of Organic Electrolytes and Their Effects on Li/S Battery Performance
journal, June 2017
- Kaiser, Mohammad Rejaul; Chou, Shulei; Liu, Hua-Kun
- Advanced Materials, Vol. 29, Issue 48
Revisiting the Role of Polysulfides in Lithium-Sulfur Batteries
journal, March 2018
- Li, Gaoran; Wang, Shun; Zhang, Yining
- Advanced Materials, Vol. 30, Issue 22
Review on High-Loading and High-Energy Lithium-Sulfur Batteries
journal, May 2017
- Peng, Hong-Jie; Huang, Jia-Qi; Cheng, Xin-Bing
- Advanced Energy Materials, Vol. 7, Issue 24
Deciphering the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando Synchrotron‐Based Characterization Techniques
journal, March 2019
- Yan, Yingying; Cheng, Chen; Zhang, Liang
- Advanced Energy Materials, Vol. 9, Issue 18
Activating Inert Metallic Compounds for High‐Rate Lithium–Sulfur Batteries Through In Situ Etching of Extrinsic Metal
journal, March 2019
- Zhao, Meng; Peng, Hong‐Jie; Zhang, Ze‐Wen
- Angewandte Chemie International Edition, Vol. 58, Issue 12
A Toolbox for Lithium-Sulfur Battery Research: Methods and Protocols
journal, June 2017
- Zhang, Ge; Zhang, Ze-Wen; Peng, Hong-Jie
- Small Methods, Vol. 1, Issue 7
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries
journal, May 2019
- Zhu, He; Huang, Yalan; Zhu, Hekang
- Small Methods
High-performance Li–S battery cathode with catalyst-like carbon nanotube-MoP promoting polysulfide redox
journal, June 2017
- Mi, Yingying; Liu, Wen; Li, Xiaolin
- Nano Research, Vol. 10, Issue 11
Understanding the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando X-ray Absorption Spectroscopy
journal, March 2019
- Zhang, Liang; Guo, Jinghua
- Arabian Journal for Science and Engineering, Vol. 44, Issue 7
Toward Better Lithium–Sulfur Batteries: Functional Non-aqueous Liquid Electrolytes
journal, August 2018
- Xiong, Shizhao; Regula, Michael; Wang, Donghai
- Electrochemical Energy Reviews, Vol. 1, Issue 3
Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials
journal, January 2020
- Hwang, Sooyeon; Stach, Eric A.
- Journal of Physics D: Applied Physics, Vol. 53, Issue 11
Review—Solid Electrolytes for Safe and High Energy Density Lithium-Sulfur Batteries: Promises and Challenges
journal, June 2017
- Judez, Xabier; Zhang, Heng; Li, Chunmei
- Journal of The Electrochemical Society, Vol. 165, Issue 1
Activating Inert Metallic Compounds for High‐Rate Lithium–Sulfur Batteries Through In Situ Etching of Extrinsic Metal
journal, January 2019
- Zhao, Meng; Peng, Hong‐Jie; Zhang, Ze‐Wen
- Angewandte Chemie, Vol. 131, Issue 12
Review : Solid Electrolytes for Safe and High Energy Density Lithium-Sulfur Batteries : Promises and Challenges
text, January 2018
- Judez, Xabier; Zhang, Heng; Li, Chunmei
- RWTH Aachen University
Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries
journal, May 2017
- Lee, Chang-Wook; Pang, Quan; Ha, Seungbum
- ACS Central Science, Vol. 3, Issue 6
High sulfur-containing carbon polysulfide polymer as a novel cathode material for lithium-sulfur battery
journal, September 2017
- Zhang, Yiyong; Peng, Yueying; Wang, Yunhui
- Scientific Reports, Vol. 7, Issue 1