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Title: Effective Bipyridine and Pyrazine–Based Polysulfide Dissolution Resistant Complex Framework Material Systems for High Capacity Rechargeable Lithium–Sulfur Batteries

Abstract

Lithium–sulfur (Li–S) batteries with high theoretical capacity (≈1650 mAh g–1) and specific energy density (≈2567 Wh g–1) have not achieved commercialization status due to low cycling stability arising from lithium polysulfide dissolution. Herein, sulfur infiltrated noncarbonized noncarbonate containing metal organic complex framework material (CFM) systems; sulfur–copper–bipyridine–CFM (S–Cu–bpy–CFM) and sulfur–copper–pyrazine–CFM (S–Cu–pyz–CFM) are developed as sulfur cathodes for the first time. The S–Cu–bpy–CFM and S–Cu–pyz–CFM show an initial capacity of 1626 and 1565 mAh g–1 with stable capacities of 1063 and 1025 mAh g–1, respectively, after 150 cycles. An X–ray photoelectron spectroscopy (XPS) analysis after sulfur infiltration reveals the presence of —C—S— bonds arising from the Lewis acid–base interaction of the CFMs with sulfur. The battery separators cycled with the CMF cathodes display complete absence of polysulfides after 150 cycles. These CFM cathodes exhibit an initial fade in capacity during the first ≈25 cycles attributed to the irreversible reaction of nitrogen with sulfur (—N—S—) during cycling. Furthermore, a clear understanding of this chemical interaction between sulfur and nitrogen present in the sulfur–infiltrated CFMs is essential for engineering nitrogen containing hosts for trapping polysulfides effectively. Understanding reported here will lead to new materials for achieving the high specific energy densities characteristic to Li–Smore » batteries.« less

Authors:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Univ. of Pittsburgh, PA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office. Batteries for Advanced Transportation Technologies (BATT) Program; USDOE
OSTI Identifier:
1640024
Alternate Identifier(s):
OSTI ID: 1513059
Grant/Contract Number:  
EE0008199; EE0006825; EE0007797
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Energy Technology
Additional Journal Information:
Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2194-4288
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Lithium-sulfur batteries; noncarbonized sulfate CFM; polysulfide encapsulation

Citation Formats

Shanthi, Pavithra M., Hanumantha, Prashanth J., Kuruba, Ramalinga, Gattu, Bharat, Datta, Moni K., and Kumta, Prashant N. Effective Bipyridine and Pyrazine–Based Polysulfide Dissolution Resistant Complex Framework Material Systems for High Capacity Rechargeable Lithium–Sulfur Batteries. United States: N. p., 2019. Web. doi:10.1002/ente.201900141.
Shanthi, Pavithra M., Hanumantha, Prashanth J., Kuruba, Ramalinga, Gattu, Bharat, Datta, Moni K., & Kumta, Prashant N. Effective Bipyridine and Pyrazine–Based Polysulfide Dissolution Resistant Complex Framework Material Systems for High Capacity Rechargeable Lithium–Sulfur Batteries. United States. https://doi.org/10.1002/ente.201900141
Shanthi, Pavithra M., Hanumantha, Prashanth J., Kuruba, Ramalinga, Gattu, Bharat, Datta, Moni K., and Kumta, Prashant N. 2019. "Effective Bipyridine and Pyrazine–Based Polysulfide Dissolution Resistant Complex Framework Material Systems for High Capacity Rechargeable Lithium–Sulfur Batteries". United States. https://doi.org/10.1002/ente.201900141. https://www.osti.gov/servlets/purl/1640024.
@article{osti_1640024,
title = {Effective Bipyridine and Pyrazine–Based Polysulfide Dissolution Resistant Complex Framework Material Systems for High Capacity Rechargeable Lithium–Sulfur Batteries},
author = {Shanthi, Pavithra M. and Hanumantha, Prashanth J. and Kuruba, Ramalinga and Gattu, Bharat and Datta, Moni K. and Kumta, Prashant N.},
abstractNote = {Lithium–sulfur (Li–S) batteries with high theoretical capacity (≈1650 mAh g–1) and specific energy density (≈2567 Wh g–1) have not achieved commercialization status due to low cycling stability arising from lithium polysulfide dissolution. Herein, sulfur infiltrated noncarbonized noncarbonate containing metal organic complex framework material (CFM) systems; sulfur–copper–bipyridine–CFM (S–Cu–bpy–CFM) and sulfur–copper–pyrazine–CFM (S–Cu–pyz–CFM) are developed as sulfur cathodes for the first time. The S–Cu–bpy–CFM and S–Cu–pyz–CFM show an initial capacity of 1626 and 1565 mAh g–1 with stable capacities of 1063 and 1025 mAh g–1, respectively, after 150 cycles. An X–ray photoelectron spectroscopy (XPS) analysis after sulfur infiltration reveals the presence of —C—S— bonds arising from the Lewis acid–base interaction of the CFMs with sulfur. The battery separators cycled with the CMF cathodes display complete absence of polysulfides after 150 cycles. These CFM cathodes exhibit an initial fade in capacity during the first ≈25 cycles attributed to the irreversible reaction of nitrogen with sulfur (—N—S—) during cycling. Furthermore, a clear understanding of this chemical interaction between sulfur and nitrogen present in the sulfur–infiltrated CFMs is essential for engineering nitrogen containing hosts for trapping polysulfides effectively. Understanding reported here will lead to new materials for achieving the high specific energy densities characteristic to Li–S batteries.},
doi = {10.1002/ente.201900141},
url = {https://www.osti.gov/biblio/1640024}, journal = {Energy Technology},
issn = {2194-4288},
number = 12,
volume = 7,
place = {United States},
year = {Thu Apr 11 00:00:00 EDT 2019},
month = {Thu Apr 11 00:00:00 EDT 2019}
}

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