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Title: Mechanistic Insights into Surface Chemical Interactions between Lithium Polysulfides and Transition Metal Oxides

Abstract

The design and development of materials for electrochemical energy storage and conversion devices requires fundamental understanding of chemical interactions at electrode/electrolyte interfaces. For Li–S batteries that hold the promise for outperforming the current generation of Li ion batteries, the interactions of lithium polysulfide (LPS) intermediates with the electrode surface strongly influence the efficiency and cycle life of the sulfur cathode. While metal oxides have been demonstrated to be useful in trapping LPS, the actual binding modes of LPS on 3d transition metal oxides and their dependence on the metal element identity across the periodic table remain poorly understood. Here, we investigate the chemical interactions between LPS and oxides of Mn, Fe, Co, and Cu by combining X-ray photoelectron spectroscopy and density functional theory calculations. We believe that Li–O interactions dominate LPS binding to the oxides (Mn 3O 4, Fe 2O 3, and Co 3O 4), with increasing strength from Mn to Fe to Co. For Co 3O 4, LPS binding also involves metal–sulfur interactions. Moreover, we find that the metal oxides exhibit different binding preferences for different LPS, with Co 3O 4 binding shorter-chain LPS more strongly than Mn 3O 4. In contrast to the other oxides, CuO undergoes intensemore » reduction and dissolution reactions upon interaction with LPS. The reported findings are thus particularly relevant to the design of LPS/oxide interfaces for high-performance Li–S batteries.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480491
Grant/Contract Number:  
FG02-07ER15909
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 26; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Zhong, Yiren, Yang, Ke R., Liu, Wen, He, Peng, Batista, Victor, and Wang, Hailiang. Mechanistic Insights into Surface Chemical Interactions between Lithium Polysulfides and Transition Metal Oxides. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b04170.
Zhong, Yiren, Yang, Ke R., Liu, Wen, He, Peng, Batista, Victor, & Wang, Hailiang. Mechanistic Insights into Surface Chemical Interactions between Lithium Polysulfides and Transition Metal Oxides. United States. doi:10.1021/acs.jpcc.7b04170.
Zhong, Yiren, Yang, Ke R., Liu, Wen, He, Peng, Batista, Victor, and Wang, Hailiang. Thu . "Mechanistic Insights into Surface Chemical Interactions between Lithium Polysulfides and Transition Metal Oxides". United States. doi:10.1021/acs.jpcc.7b04170. https://www.osti.gov/servlets/purl/1480491.
@article{osti_1480491,
title = {Mechanistic Insights into Surface Chemical Interactions between Lithium Polysulfides and Transition Metal Oxides},
author = {Zhong, Yiren and Yang, Ke R. and Liu, Wen and He, Peng and Batista, Victor and Wang, Hailiang},
abstractNote = {The design and development of materials for electrochemical energy storage and conversion devices requires fundamental understanding of chemical interactions at electrode/electrolyte interfaces. For Li–S batteries that hold the promise for outperforming the current generation of Li ion batteries, the interactions of lithium polysulfide (LPS) intermediates with the electrode surface strongly influence the efficiency and cycle life of the sulfur cathode. While metal oxides have been demonstrated to be useful in trapping LPS, the actual binding modes of LPS on 3d transition metal oxides and their dependence on the metal element identity across the periodic table remain poorly understood. Here, we investigate the chemical interactions between LPS and oxides of Mn, Fe, Co, and Cu by combining X-ray photoelectron spectroscopy and density functional theory calculations. We believe that Li–O interactions dominate LPS binding to the oxides (Mn3O4, Fe2O3, and Co3O4), with increasing strength from Mn to Fe to Co. For Co3O4, LPS binding also involves metal–sulfur interactions. Moreover, we find that the metal oxides exhibit different binding preferences for different LPS, with Co3O4 binding shorter-chain LPS more strongly than Mn3O4. In contrast to the other oxides, CuO undergoes intense reduction and dissolution reactions upon interaction with LPS. The reported findings are thus particularly relevant to the design of LPS/oxide interfaces for high-performance Li–S batteries.},
doi = {10.1021/acs.jpcc.7b04170},
journal = {Journal of Physical Chemistry. C},
number = 26,
volume = 121,
place = {United States},
year = {2017},
month = {6}
}

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