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Title: Insights into the Interconnection of the Electrodes and Electrolyte Species in Lithium–Sulfur Batteries Using Spatially Resolved Operando X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping

Abstract

The lithium–sulfur (Li–S) battery chemistry has attracted great interest in the last decade because of its outstanding theoretical gravimetric energy density compared to the state-of-the-art lithium-ion battery technology. However, practically achieved energy density is still far below the theoretical value, even in small laboratory-scale batteries. The problems seen in laboratory-scale batteries will inevitably increase during scale-up to large application-format cells, as the electrolyte to active material (AM) ratio will need to be reduced in these cells to achieve high gravimetric energy density on cell-level basis. Our paper shows the unique possibility of X-ray fluorescence (XRF) mapping to visualize the spatial distribution of the AM inside operating Li–S batteries in all cell components [working electrode (WE), separator, and counter electrode (CE)]. Through a combination of operando XRF mapping and X-ray absorption spectroscopy, we show that unless self-discharge is efficiently prevented, the AM can completely dissolve and distribute throughout the cell stack within a time frame of 2 h, causing poor capacity retention. Finally, using a polysulfide diffusion barrier between the WE and the CE, we successfully suppress these processes and thereby establish a tool for examining the sealed cathode electrode compartment, enabling sophisticated studies for future optimization of the WE processes.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [1];  [3]; ORCiD logo [1]
  1. Technical Univ. of Munich, Garching (Germany). Chair of Technical Electrochemistry. Dept. of Chemistry. Catalysis Research Center
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource
  3. Univ. of Amsterdam (Netherlands). Sustainable Materials Characterization. Van’t Hoff Inst. for Molecular Sciences
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Munich, Garching (Germany); Univ. of Amsterdam (Netherlands)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Federal Ministry for Economic Affairs and Energy (BMWi) (Germany); Netherlands Organisation for Scientific Research (NWO)
OSTI Identifier:
1471518
Grant/Contract Number:  
AC02-76SF00515; 03ET6045D; VIDI 723.014.010
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 10; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Freiberg, Anna T. S., Siebel, Armin, Berger, Anne, Webb, Samuel M., Gorlin, Yelena, Tromp, Moniek, and Gasteiger, Hubert A.. Insights into the Interconnection of the Electrodes and Electrolyte Species in Lithium–Sulfur Batteries Using Spatially Resolved Operando X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jpcc.7b12799.
Freiberg, Anna T. S., Siebel, Armin, Berger, Anne, Webb, Samuel M., Gorlin, Yelena, Tromp, Moniek, & Gasteiger, Hubert A.. Insights into the Interconnection of the Electrodes and Electrolyte Species in Lithium–Sulfur Batteries Using Spatially Resolved Operando X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping. United States. https://doi.org/10.1021/acs.jpcc.7b12799
Freiberg, Anna T. S., Siebel, Armin, Berger, Anne, Webb, Samuel M., Gorlin, Yelena, Tromp, Moniek, and Gasteiger, Hubert A.. Thu . "Insights into the Interconnection of the Electrodes and Electrolyte Species in Lithium–Sulfur Batteries Using Spatially Resolved Operando X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping". United States. https://doi.org/10.1021/acs.jpcc.7b12799. https://www.osti.gov/servlets/purl/1471518.
@article{osti_1471518,
title = {Insights into the Interconnection of the Electrodes and Electrolyte Species in Lithium–Sulfur Batteries Using Spatially Resolved Operando X-ray Absorption Spectroscopy and X-ray Fluorescence Mapping},
author = {Freiberg, Anna T. S. and Siebel, Armin and Berger, Anne and Webb, Samuel M. and Gorlin, Yelena and Tromp, Moniek and Gasteiger, Hubert A.},
abstractNote = {The lithium–sulfur (Li–S) battery chemistry has attracted great interest in the last decade because of its outstanding theoretical gravimetric energy density compared to the state-of-the-art lithium-ion battery technology. However, practically achieved energy density is still far below the theoretical value, even in small laboratory-scale batteries. The problems seen in laboratory-scale batteries will inevitably increase during scale-up to large application-format cells, as the electrolyte to active material (AM) ratio will need to be reduced in these cells to achieve high gravimetric energy density on cell-level basis. Our paper shows the unique possibility of X-ray fluorescence (XRF) mapping to visualize the spatial distribution of the AM inside operating Li–S batteries in all cell components [working electrode (WE), separator, and counter electrode (CE)]. Through a combination of operando XRF mapping and X-ray absorption spectroscopy, we show that unless self-discharge is efficiently prevented, the AM can completely dissolve and distribute throughout the cell stack within a time frame of 2 h, causing poor capacity retention. Finally, using a polysulfide diffusion barrier between the WE and the CE, we successfully suppress these processes and thereby establish a tool for examining the sealed cathode electrode compartment, enabling sophisticated studies for future optimization of the WE processes.},
doi = {10.1021/acs.jpcc.7b12799},
journal = {Journal of Physical Chemistry. C},
number = 10,
volume = 122,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: Scheme of discharging processes of a Li-S battery. Because the optimum discharge process with confinement of the Sa/Soe2-/Li2S species within the sulfur WE is not possible without a preformed pasalvating surface film on the anode, the apparent discharge process leads to AM loss at the anode and tomore » polysulfide shuttling (see upper right figure). The illustrated crosstalk is a main focus of this study. The use of a polysulfide-repelling membrane might be a feasible way to confine the reactants to the WE compartment. This configuration also allows for sophisticated studies on the reactions within the working compartment with respect to electrolyte or catalyst influence.« less

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Works referenced in this record:

Review on Li-Sulfur Battery Systems: an Integral Perspective
journal, May 2015

  • Rosenman, Ariel; Markevich, Elena; Salitra, Gregory
  • Advanced Energy Materials, Vol. 5, Issue 16
  • DOI: 10.1002/aenm.201500212

Review—Electromobility: Batteries or Fuel Cells?
journal, January 2015

  • Gröger, Oliver; Gasteiger, Hubert A.; Suchsland, Jens-Peter
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0211514jes

Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery
journal, January 2015

  • Eroglu, Damla; Zavadil, Kevin R.; Gallagher, Kevin G.
  • Journal of The Electrochemical Society, Vol. 162, Issue 6
  • DOI: 10.1149/2.0611506jes

Sulfur-Impregnated Core-Shell Hierarchical Porous Carbon for Lithium-Sulfur Batteries
journal, October 2014

  • Zhang, Fei-Fei; Huang, Gang; Wang, Xu-Xu
  • Chemistry - A European Journal, Vol. 20, Issue 52
  • DOI: 10.1002/chem.201404439

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
  • DOI: 10.1149/1.1806394

Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries
journal, February 2013

  • Zheng, Guangyuan; Zhang, Qianfan; Cha, Judy J.
  • Nano Letters, Vol. 13, Issue 3, p. 1265-1270
  • DOI: 10.1021/nl304795g

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
  • DOI: 10.1038/nmat2460

Mixed Conduction Membranes Suppress the Polysulfide Shuttle in Lithium-Sulfur Batteries
journal, January 2017

  • Moy, Derek; Narayanan, S. R.
  • Journal of The Electrochemical Society, Vol. 164, Issue 4
  • DOI: 10.1149/2.0181704jes

Sparingly Solvating Electrolytes for High Energy Density Lithium–Sulfur Batteries
journal, August 2016


A highly efficient polysulfide mediator for lithium–sulfur batteries
journal, January 2015

  • Liang, Xiao; Hart, Connor; Pang, Quan
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6682

Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries
journal, March 2017

  • Sun, Zhenhua; Zhang, Jingqi; Yin, Lichang
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14627

Surface Modification of Sulfur Cathodes with PEDOT:PSS Conducting Polymer in Lithium-Sulfur Batteries
journal, January 2015

  • Lee, Jeongyeon; Choi, Wonchang
  • Journal of The Electrochemical Society, Vol. 162, Issue 6
  • DOI: 10.1149/2.0651506jes

Nafion coated sulfur–carbon electrode for high performance lithium–sulfur batteries
journal, January 2014


On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries
journal, January 2009

  • Aurbach, Doron; Pollak, Elad; Elazari, Ran
  • Journal of The Electrochemical Society, Vol. 156, Issue 8, p. A694-A702
  • DOI: 10.1149/1.3148721

High Energy Rechargeable Li-S Cells for EV Application: Status, Remaining Problems and Solutions
conference, January 2010

  • Mikhaylik, Yuriy V.; Kovalev, Igor; Schock, Riley
  • 216th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3414001

Probing the Lithium–Sulfur Redox Reactions: A Rotating-Ring Disk Electrode Study
journal, March 2014

  • Lu, Yi-Chun; He, Qi; Gasteiger, Hubert A.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 11
  • DOI: 10.1021/jp500382s

Operando Characterization of Intermediates Produced in a Lithium-Sulfur Battery
journal, January 2015

  • Gorlin, Yelena; Siebel, Armin; Piana, Michele
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.0081507jes

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy
journal, January 2016

  • Gorlin, Yelena; Patel, Manu U. M.; Freiberg, Anna
  • Journal of The Electrochemical Society, Vol. 163, Issue 6
  • DOI: 10.1149/2.0631606jes

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
  • DOI: 10.1021/jz401763d

Operando Spectromicroscopy of Sulfur Species in Lithium-Sulfur Batteries
journal, June 2017

  • Miller, Elizabeth C.; Kasse, Robert M.; Heath, Khloe N.
  • Journal of The Electrochemical Society, Vol. 165, Issue 1
  • DOI: 10.1149/2.0091801jes

Improving Lithium–Sulfur Battery Performance under Lean Electrolyte through Nanoscale Confinement in Soft Swellable Gels
journal, April 2017


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
  • DOI: 10.1021/jz500260s

    Works referencing / citing this record:

    The Importance of Chemical Reactions in the Charging Process of Lithium-Sulfur Batteries
    journal, January 2018

    • Berger, Anne; Freiberg, Anna T. S.; Siebel, Armin
    • Journal of The Electrochemical Society, Vol. 165, Issue 7
    • DOI: 10.1149/2.0181807jes

    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
    • DOI: 10.1002/aenm.201900148

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.