Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility
Abstract
Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid–liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid–liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ~100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. We conclude the excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.
- Authors:
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Advanced Research Projects Agency - Energy (ARPA-E); National Aeronautics and Space Administration (NASA)
- OSTI Identifier:
- 1360993
- Alternate Identifier(s):
- OSTI ID: 1406903
- Grant/Contract Number:
- AC02-06CH11357; AR0000389
- Resource Type:
- Journal Article: Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; water-in-salt; rechargeable aqueous battery; aqueous sulfur battery; gel polymer electrolyte; phase separation
Citation Formats
Yang, Chongyin, Suo, Liumin, Borodin, Oleg, Wang, Fei, Sun, Wei, Gao, Tao, Fan, Xiulin, Hou, Singyuk, Ma, Zhaohui, Amine, Khalil, Xu, Kang, and Wang, Chunsheng. Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility. United States: N. p., 2017.
Web. doi:10.1073/pnas.1703937114.
Yang, Chongyin, Suo, Liumin, Borodin, Oleg, Wang, Fei, Sun, Wei, Gao, Tao, Fan, Xiulin, Hou, Singyuk, Ma, Zhaohui, Amine, Khalil, Xu, Kang, & Wang, Chunsheng. Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility. United States. https://doi.org/10.1073/pnas.1703937114
Yang, Chongyin, Suo, Liumin, Borodin, Oleg, Wang, Fei, Sun, Wei, Gao, Tao, Fan, Xiulin, Hou, Singyuk, Ma, Zhaohui, Amine, Khalil, Xu, Kang, and Wang, Chunsheng. 2017.
"Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility". United States. https://doi.org/10.1073/pnas.1703937114.
@article{osti_1360993,
title = {Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility},
author = {Yang, Chongyin and Suo, Liumin and Borodin, Oleg and Wang, Fei and Sun, Wei and Gao, Tao and Fan, Xiulin and Hou, Singyuk and Ma, Zhaohui and Amine, Khalil and Xu, Kang and Wang, Chunsheng},
abstractNote = {Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid–liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid–liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ~100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. We conclude the excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.},
doi = {10.1073/pnas.1703937114},
url = {https://www.osti.gov/biblio/1360993},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = ,
volume = ,
place = {United States},
year = {Wed May 31 00:00:00 EDT 2017},
month = {Wed May 31 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
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
In Situ Raman Spectroscopy of Sulfur Speciation in Lithium–Sulfur Batteries
journal, January 2015
- Wu, Heng-Liang; Huff, Laura A.; Gewirth, Andrew A.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 3
Lithium Batteries and Cathode Materials
journal, October 2004
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Single step transformation of sulphur to Li2S2/Li2S in Li-S batteries
journal, July 2015
- Helen, M.; Reddy, M. Anji; Diemant, Thomas
- Scientific Reports, Vol. 5, Issue 1
A zwitterionic gel electrolyte for efficient solid-state supercapacitors
journal, May 2016
- Peng, Xu; Liu, Huili; Yin, Qin
- Nature Communications, Vol. 7, Issue 1
Hydrate-melt electrolytes for high-energy-density aqueous batteries
journal, August 2016
- Yamada, Yuki; Usui, Kenji; Sodeyama, Keitaro
- Nature Energy, Vol. 1, Issue 10
Systematical electrochemical study on the parasitic shuttle-effect in lithium-sulfur-cells at different temperatures and different rates
journal, August 2014
- Busche, Martin Rolf; Adelhelm, Philipp; Sommer, Heino
- Journal of Power Sources, Vol. 259
Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries
journal, August 2014
- Pang, Quan; Kundu, Dipan; Cuisinier, Marine
- Nature Communications, Vol. 5, Issue 1
Sol–gel encapsulated lithium polysulfide catholyte and its application in lithium–sulfur batteries
journal, January 2016
- Smith, Leland C.; Malati, Peter; Fang, Jonathan
- Materials Horizons, Vol. 3, Issue 2
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
Aqueous Rechargeable Li and Na Ion Batteries
journal, September 2014
- Kim, Haegyeom; Hong, Jihyun; Park, Kyu-Young
- Chemical Reviews, Vol. 114, Issue 23
Aqueous Solubilities, Solubility Products and Standard Oxidation-Reduction Potentials of the Metal Sulfides
journal, January 1988
- Licht, Stuart
- Journal of The Electrochemical Society, Vol. 135, Issue 12
Recent Advances in Electrolytes for Lithium-Sulfur Batteries
journal, April 2015
- Zhang, Shiguo; Ueno, Kazuhide; Dokko, Kaoru
- Advanced Energy Materials, Vol. 5, Issue 16
Improvement of cycle performance of lithium ion cell LiMn2O4/LixV2O5 with aqueous solution electrolyte by polypyrrole coating on anode
journal, April 2007
- Wang, Haibo; Zeng, Yuqun; Huang, Kelong
- Electrochimica Acta, Vol. 52, Issue 15
Two-dimensional vanadyl phosphate ultrathin nanosheets for high energy density and flexible pseudocapacitors
journal, September 2013
- Wu, Changzheng; Lu, Xiuli; Peng, Lele
- Nature Communications, Vol. 4, Issue 1
High-voltage Zn/LiMn0.8Fe0.2PO4 aqueous rechargeable battery by virtue of “water-in-salt” electrolyte
journal, August 2016
- Zhao, Jingwen; Li, Yuqi; Peng, Xuan
- Electrochemistry Communications, Vol. 69
A High Energy Lithium-Sulfur Battery with Ultrahigh-Loading Lithium Polysulfide Cathode and its Failure Mechanism
journal, February 2016
- Qie, Long; Zu, Chenxi; Manthiram, Arumugam
- Advanced Energy Materials, Vol. 6, Issue 7
Solvent Effect of Room Temperature Ionic Liquids on Electrochemical Reactions in Lithium–Sulfur Batteries
journal, February 2013
- Park, Jun-Woo; Yamauchi, Kento; Takashima, Eriko
- The Journal of Physical Chemistry C, Vol. 117, Issue 9
Advanced High-Voltage Aqueous Lithium-Ion Battery Enabled by “Water-in-Bisalt” Electrolyte
journal, April 2016
- Suo, Liumin; Borodin, Oleg; Sun, Wei
- Angewandte Chemie International Edition, Vol. 55, Issue 25
Exploiting XPS for the identification of sulfides and polysulfides
journal, January 2015
- Fantauzzi, Marzia; Elsener, Bernhard; Atzei, Davide
- RSC Advances, Vol. 5, Issue 93
Lithium Sulfur Battery: Oxidation/Reduction Mechanisms of Polysulfides in THF Solutions
journal, January 1988
- Yamin, H.; Gorenshtein, A.; Penciner, J.
- Journal of The Electrochemical Society, Vol. 135, Issue 5, p. 1045-1048
Advances in Li–S batteries
journal, January 2010
- Ji, Xiulei; Nazar, Linda F.
- Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826
Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries
journal, January 2014
- Cuisinier, M.; Cabelguen, P. -E.; Adams, B. D.
- Energy Environ. Sci., Vol. 7, Issue 8
Porous Hollow Carbon@Sulfur Composites for High-Power Lithium-Sulfur Batteries
journal, May 2011
- Jayaprakash, N.; Shen, J.; Moganty, Surya S.
- Angewandte Chemie International Edition, Vol. 50, Issue 26, p. 5904-5908
Electrochemical properties of TiP2O7 and LiTi2(PO4)3 as anode material for lithium ion battery with aqueous solution electrolyte
journal, February 2007
- Wang, Haibo; Huang, Kelong; Zeng, Yuqun
- Electrochimica Acta, Vol. 52, Issue 9
"Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries
journal, November 2015
- Suo, L.; Borodin, O.; Gao, T.
- Science, Vol. 350, Issue 6263
Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014
- Larcher, D.; Tarascon, J-M.
- Nature Chemistry, Vol. 7, Issue 1
An aqueous dissolved polysulfide cathode for lithium–sulfur batteries
journal, January 2014
- Li, Na; Weng, Zhe; Wang, Yarong
- Energy Environ. Sci., Vol. 7, Issue 10
Raman Spectroscopic and X-ray Diffraction Studies of Sulfur Composite Electrodes during Discharge and Charge
journal, January 2012
- Yeon, Jin-Tak; Jang, Jun-Young; Han, Jung-Gu
- Journal of The Electrochemical Society, Vol. 159, Issue 8
Recent Progress in Aqueous Lithium-Ion Batteries
journal, June 2012
- Wang, Yonggang; Yi, Jin; Xia, Yongyao
- Advanced Energy Materials, Vol. 2, Issue 7
Raman studies of sulfur-containing anions in inorganic polysulfides. Potassium polysulfides
journal, August 1976
- Janz, G. J.; Coutts, J. W.; Downey, J. R.
- Inorganic Chemistry, Vol. 15, Issue 8
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
A strategic approach to recharging lithium-sulphur batteries for long cycle life
journal, December 2013
- Su, Yu-Sheng; Fu, Yongzhu; Cochell, Thomas
- Nature Communications, Vol. 4, Issue 1
Rechargeable Lithium Batteries with Aqueous Electrolytes
journal, May 1994
- Li, W.; Dahn, J. R.; Wainwright, D. S.
- Science, Vol. 264, Issue 5162, p. 1115-1118
Two-dimensional layered transition metal disulphides for effective encapsulation of high-capacity lithium sulphide cathodes
journal, September 2014
- Seh, Zhi Wei; Yu, Jung Ho; Li, Weiyang
- Nature Communications, Vol. 5, Issue 1
Methods to obtain excellent capacity retention in LiCoO2 cycled to 4.5 V
journal, March 2004
- Chen, Zhaohui; Dahn, J. R.
- Electrochimica Acta, Vol. 49, Issue 7
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
Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte
journal, August 2010
- Luo, Jia-Yan; Cui, Wang-Jun; He, Ping
- Nature Chemistry, Vol. 2, Issue 9