Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules
Abstract
The two major barriers of practical lithium–sulfur batteries are the poor reversibility of lithium-metal anode and sluggish kinetics of sulfur cathode. Here, we report a simple yet cogent, molecular tailoring approach for lithium polysulfides, enabling a synergistic enhancement of anode reversibility and cathode kinetics. In this study, we show that SnI4 coordinates with lithium polysulfides to form soluble complexes, resulting in a Li2SnS3-rich anode interphase layer. As Li2SnS3 is stable against parasitic reactions and has a lower ionic resistance over cycling, the Li plating/stripping efficiency is greatly improved. In addition, the formation of soluble complexes between SnI4 and lithium polysulfides play a non-negligible role in suppressing the clustering behavior of lithium polysulfide molecules, resulting in a significant enhancement in sulfur conversion kinetics under lean electrolyte conditions. The synergistic improvement is validated in anode-free, lean-electrolyte pouch cells with a Li2S cathode that displays capacity retention of 78 % after 100 cycles.
- Authors:
-
- University of Texas, Austin, TX (United States)
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE
- OSTI Identifier:
- 2217438
- Alternate Identifier(s):
- OSTI ID: 1882752; OSTI ID: 1976284
- Grant/Contract Number:
- EE0007762
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 61; Journal Issue: 35; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; batteries; anode-free cells; anode solid electrolyte interphase; anode-free batteries; cathode kinetics; electrolyte additive; pouch cells
Citation Formats
Ren, Yuxun, Bhargav, Amruth, Shin, Woochul, Sul, Hyunki, and Manthiram, Arumugam. Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules. United States: N. p., 2022.
Web. doi:10.1002/anie.202207907.
Ren, Yuxun, Bhargav, Amruth, Shin, Woochul, Sul, Hyunki, & Manthiram, Arumugam. Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules. United States. https://doi.org/10.1002/anie.202207907
Ren, Yuxun, Bhargav, Amruth, Shin, Woochul, Sul, Hyunki, and Manthiram, Arumugam. Thu .
"Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules". United States. https://doi.org/10.1002/anie.202207907. https://www.osti.gov/servlets/purl/2217438.
@article{osti_2217438,
title = {Anode–Free Lithium–Sulfur Cells Enabled by Rationally Tuning Lithium Polysulfide Molecules},
author = {Ren, Yuxun and Bhargav, Amruth and Shin, Woochul and Sul, Hyunki and Manthiram, Arumugam},
abstractNote = {The two major barriers of practical lithium–sulfur batteries are the poor reversibility of lithium-metal anode and sluggish kinetics of sulfur cathode. Here, we report a simple yet cogent, molecular tailoring approach for lithium polysulfides, enabling a synergistic enhancement of anode reversibility and cathode kinetics. In this study, we show that SnI4 coordinates with lithium polysulfides to form soluble complexes, resulting in a Li2SnS3-rich anode interphase layer. As Li2SnS3 is stable against parasitic reactions and has a lower ionic resistance over cycling, the Li plating/stripping efficiency is greatly improved. In addition, the formation of soluble complexes between SnI4 and lithium polysulfides play a non-negligible role in suppressing the clustering behavior of lithium polysulfide molecules, resulting in a significant enhancement in sulfur conversion kinetics under lean electrolyte conditions. The synergistic improvement is validated in anode-free, lean-electrolyte pouch cells with a Li2S cathode that displays capacity retention of 78 % after 100 cycles.},
doi = {10.1002/anie.202207907},
journal = {Angewandte Chemie (International Edition)},
number = 35,
volume = 61,
place = {United States},
year = {Thu Jul 07 00:00:00 EDT 2022},
month = {Thu Jul 07 00:00:00 EDT 2022}
}
Works referenced in this record:
Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries
journal, July 2019
- Ren, Y. X.; Zeng, L.; Jiang, H. R.
- Nature Communications, Vol. 10, Issue 1
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
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
A New Class of Ionically Conducting Fluorinated Ether Electrolytes with High Electrochemical Stability
journal, April 2020
- Amanchukwu, Chibueze V.; Yu, Zhiao; Kong, Xian
- Journal of the American Chemical Society, Vol. 142, Issue 16
Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries
journal, September 2021
- Jin, Cheng‐Bin; Zhang, Xue‐Qiang; Sheng, Ou‐Wei
- Angewandte Chemie International Edition, Vol. 60, Issue 42
Atomic Tungsten on Graphene with Unique Coordination Enabling Kinetically Boosted Lithium–Sulfur Batteries
journal, June 2021
- Wang, Peng; Xi, Baojuan; Zhang, Zhengchunyu
- Angewandte Chemie, Vol. 133, Issue 28
An Organodiselenide Comediator to Facilitate Sulfur Redox Kinetics in Lithium–Sulfur Batteries
journal, February 2021
- Zhao, Meng; Chen, Xiang; Li, Xi‐Yao
- Advanced Materials, Vol. 33, Issue 13
Approaching Ultrastable High‐Rate Li–S Batteries through Hierarchically Porous Titanium Nitride Synthesized by Multiscale Phase Separation
journal, September 2018
- Lim, Won‐Gwang; Jo, Changshin; Cho, Ara
- Advanced Materials, Vol. 31, Issue 3
Phosphorous Pentasulfide as a Novel Additive for High-Performance Lithium-Sulfur Batteries
journal, June 2012
- Lin, Zhan; Liu, Zengcai; Fu, Wujun
- Advanced Functional Materials, Vol. 23, Issue 8
A reflection on lithium-ion battery cathode chemistry
journal, March 2020
- Manthiram, Arumugam
- Nature Communications, Vol. 11, Issue 1
Surface Gelation on Disulfide Electrocatalysts in Lithium–Sulfur Batteries
journal, December 2021
- Li, Xi‐Yao; Feng, Shuai; Zhao, Meng
- Angewandte Chemie International Edition, Vol. 61, Issue 7
Organosulfides: An Emerging Class of Cathode Materials for Rechargeable Lithium Batteries
journal, July 2019
- Wang, Dan-Yang; Guo, Wei; Fu, Yongzhu
- Accounts of Chemical Research, Vol. 52, Issue 8
A safe and efficient lithiated silicon-sulfur battery enabled by a bi-functional composite interlayer
journal, March 2020
- Ren, Y. X.; Zeng, L.; Zhao, C.
- Energy Storage Materials, Vol. 25
Shielding Polysulfide Intermediates by an Organosulfur‐Containing Solid Electrolyte Interphase on the Lithium Anode in Lithium–Sulfur Batteries
journal, August 2020
- Wei, Jun‐Yu; Zhang, Xue‐Qiang; Hou, Li‐Peng
- Advanced Materials, Vol. 32, Issue 37
Lithium-Sulfur Batteries: Attaining the Critical Metrics
journal, February 2020
- Bhargav, Amruth; He, Jiarui; Gupta, Abhay
- Joule, Vol. 4, Issue 2
A Cobalt‐ and Manganese‐Free High‐Nickel Layered Oxide Cathode for Long‐Life, Safer Lithium‐Ion Batteries
journal, October 2021
- Cui, Zehao; Xie, Qiang; Manthiram, Arumugam
- Advanced Energy Materials, Vol. 11, Issue 41
Lithium degradation in lithium–sulfur batteries: insights into inventory depletion and interphasial evolution with cycling
journal, January 2020
- Nanda, Sanjay; Manthiram, Arumugam
- Energy & Environmental Science, Vol. 13, Issue 8
The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries
journal, January 2019
- Steudel, Ralf; Chivers, Tristram
- Chemical Society Reviews, Vol. 48, Issue 12
Modeling of lithium-sulfur batteries incorporating the effect of Li2S precipitation
journal, December 2016
- Ren, Y. X.; Zhao, T. S.; Liu, M.
- Journal of Power Sources, Vol. 336
Highly Solvating Electrolytes for Lithium–Sulfur Batteries
journal, December 2018
- Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam
- Advanced Energy Materials, Vol. 9, Issue 6
Reclaiming Inactive Lithium with a Triiodide/Iodide Redox Couple for Practical Lithium Metal Batteries
journal, September 2021
- Jin, Cheng‐Bin; Zhang, Xue‐Qiang; Sheng, Ou‐Wei
- Angewandte Chemie, Vol. 133, Issue 42
Rechargeable Lithium–Sulfur Batteries
journal, July 2014
- Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
- Chemical Reviews, Vol. 114, Issue 23
Photoluminescence of antimony(III) and bismuth(III) chloride complexes in solution
journal, November 1991
- Nikol, Hans; Vogler, Arnd
- Journal of the American Chemical Society, Vol. 113, Issue 23
Dual‐Solvent Li‐Ion Solvation Enables High‐Performance Li‐Metal Batteries
journal, May 2021
- Wang, Hansen; Yu, Zhiao; Kong, Xian
- Advanced Materials, Vol. 33, Issue 25
Atomic Tungsten on Graphene with Unique Coordination Enabling Kinetically Boosted Lithium–Sulfur Batteries
journal, June 2021
- Wang, Peng; Xi, Baojuan; Zhang, Zhengchunyu
- Angewandte Chemie International Edition, Vol. 60, Issue 28
Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction
journal, May 2017
- Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita
- Nature Energy, Vol. 2, Issue 6
Tailoring Lithium Polysulfide Coordination and Clustering Behavior through Cationic Electrostatic Competition
journal, April 2021
- Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam
- Chemistry of Materials, Vol. 33, Issue 9
Sulfide‐Based Solid‐State Electrolytes: Synthesis, Stability, and Potential for All‐Solid‐State Batteries
journal, August 2019
- Zhang, Qing; Cao, Daxian; Ma, Yi
- Advanced Materials, Vol. 31, Issue 44
Delineating the Lithium–Electrolyte Interfacial Chemistry and the Dynamics of Lithium Deposition in Lithium–Sulfur Batteries
journal, January 2021
- Nanda, Sanjay; Manthiram, Arumugam
- Advanced Energy Materials, Vol. 11, Issue 11
Insights into the Electrochemical Stability and Lithium Conductivity of Li 4 MS 4 (M = Si, Ge, and Sn)
journal, April 2021
- Chen, Fengjiao; Cheng, Songqi; Liu, Jian-Bo
- ACS Applied Materials & Interfaces, Vol. 13, Issue 19
Amorphous Lithium Sulfide as Lithium‐Sulfur Battery Cathode with Low Activation Barrier
journal, March 2019
- Lodovico, Lucas; Milad Hosseini, Seyed; Varzi, Alberto
- Energy Technology, Vol. 7, Issue 12
Organosulfur Compounds Enable Uniform Lithium Plating and Long-Term Battery Cycling Stability
journal, March 2020
- Boateng, Bismark; Han, Yupei; Zhen, Cheng
- Nano Letters, Vol. 20, Issue 4
Evoking High-Donor-Number-Assisted and Organosulfur-Mediated Conversion in Lithium–Sulfur Batteries
journal, December 2020
- Gupta, Abhay; Bhargav, Amruth; Manthiram, Arumugam
- ACS Energy Letters, Vol. 6, Issue 1
High-Performance Anode-Free Li–S Batteries with an Integrated Li 2 S–Electrocatalyst Cathode
journal, January 2022
- He, Jiarui; Bhargav, Amruth; Manthiram, Arumugam
- ACS Energy Letters, Vol. 7, Issue 2
Anode-free, Lean-Electrolyte Lithium-Sulfur Batteries Enabled by Tellurium-Stabilized Lithium Deposition
journal, May 2020
- Nanda, Sanjay; Bhargav, Amruth; Manthiram, Arumugam
- Joule, Vol. 4, Issue 5
Artificial dual solid-electrolyte interfaces based on in situ organothiol transformation in lithium sulfur battery
journal, May 2021
- Guo, Wei; Zhang, Wanying; Si, Yubing
- Nature Communications, Vol. 12, 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
Degradation mechanism of hybrid tin-based perovskite solar cells and the critical role of tin (IV) iodide
journal, May 2021
- Lanzetta, Luis; Webb, Thomas; Zibouche, Nourdine
- Nature Communications, Vol. 12, Issue 1
Unifying the clustering kinetics of lithium polysulfides with the nucleation behavior of Li 2 S in lithium–sulfur batteries
journal, January 2021
- Gupta, Abhay; Manthiram, Arumugam
- Journal of Materials Chemistry A, Vol. 9, Issue 22
Li2S-based anode-free full batteries with modified Cu current collector
journal, September 2020
- Chen, Jie; Xiang, Jingwei; Chen, Xin
- Energy Storage Materials, Vol. 30
Surface Gelation on Disulfide Electrocatalysts in Lithium–Sulfur Batteries
journal, December 2021
- Li, Xi‐Yao; Feng, Shuai; Zhao, Meng
- Angewandte Chemie, Vol. 134, Issue 7
Achieving three-dimensional lithium sulfide growth in lithium-sulfur batteries using high-donor-number anions
journal, January 2019
- Chu, Hyunwon; Noh, Hyungjun; Kim, Yun-Jung
- Nature Communications, Vol. 10, Issue 1
Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries
journal, September 2021
- Nagarajan, Sudhan; Hwang, Sooyeon; Balasubramanian, Mahalingam
- Journal of the American Chemical Society, Vol. 143, Issue 38