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Title: An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries

Abstract

Abstract With a high theoretical capacity of 1162 mA h g −1 , Li 2 S is a promising cathode that can couple with silicon, tin, or graphite anodes for next‐generation energy storage devices. Unfortunately, Li 2 S is highly insulating, exhibits large charge overpotential, and suffers from active‐material loss as soluble polysulfides during battery cycling. To date, low‐cost, scalable synthesis of an electrochemically active Li 2 S cathode remains a challenge. This work demonstrates that the low conductivity and material loss issues associated with Li 2 S cathodes can be overcome by forming a stable, conductive encapsulation layer at the surface of the Li 2 S bulk particles through in situ surface reactions between Li 2 S and electrolyte additives containing transition‐metal salts. It is identified that the electronic band structure in the valence band region of the thus‐generated encapsulation layers, consisting largely of transition‐metal sulfides, determines the initial charging resistance of Li 2 S. Furthermore, among the transition metals tested, the encapsulation layer formed with an addition of 10 wt% manganese (II) acetylacetonate salt proved to be robust within the cycling window, which is attributed to the chemically generated MnS surface species. This work provides an effective strategymore » to use micrometer‐sized Li 2 S directly as a cathode material and opens up new prospects to tune the surface properties of electrode materials for energy‐storage applications.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Materials Science and Engineering Program and Texas Materials Institute The University of Texas at Austin Austin TX 78712 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401069
Grant/Contract Number:  
DE‐SC0005397
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Name: Advanced Energy Materials Journal Volume: 7 Journal Issue: 20; Journal ID: ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Klein, Michael J., Dolocan, Andrei, Zu, Chenxi, and Manthiram, Arumugam. An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries. Germany: N. p., 2017. Web. doi:10.1002/aenm.201701122.
Klein, Michael J., Dolocan, Andrei, Zu, Chenxi, & Manthiram, Arumugam. An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries. Germany. https://doi.org/10.1002/aenm.201701122
Klein, Michael J., Dolocan, Andrei, Zu, Chenxi, and Manthiram, Arumugam. Fri . "An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries". Germany. https://doi.org/10.1002/aenm.201701122.
@article{osti_1401069,
title = {An Effective Lithium Sulfide Encapsulation Strategy for Stable Lithium–Sulfur Batteries},
author = {Klein, Michael J. and Dolocan, Andrei and Zu, Chenxi and Manthiram, Arumugam},
abstractNote = {Abstract With a high theoretical capacity of 1162 mA h g −1 , Li 2 S is a promising cathode that can couple with silicon, tin, or graphite anodes for next‐generation energy storage devices. Unfortunately, Li 2 S is highly insulating, exhibits large charge overpotential, and suffers from active‐material loss as soluble polysulfides during battery cycling. To date, low‐cost, scalable synthesis of an electrochemically active Li 2 S cathode remains a challenge. This work demonstrates that the low conductivity and material loss issues associated with Li 2 S cathodes can be overcome by forming a stable, conductive encapsulation layer at the surface of the Li 2 S bulk particles through in situ surface reactions between Li 2 S and electrolyte additives containing transition‐metal salts. It is identified that the electronic band structure in the valence band region of the thus‐generated encapsulation layers, consisting largely of transition‐metal sulfides, determines the initial charging resistance of Li 2 S. Furthermore, among the transition metals tested, the encapsulation layer formed with an addition of 10 wt% manganese (II) acetylacetonate salt proved to be robust within the cycling window, which is attributed to the chemically generated MnS surface species. This work provides an effective strategy to use micrometer‐sized Li 2 S directly as a cathode material and opens up new prospects to tune the surface properties of electrode materials for energy‐storage applications.},
doi = {10.1002/aenm.201701122},
journal = {Advanced Energy Materials},
number = 20,
volume = 7,
place = {Germany},
year = {Fri Jul 14 00:00:00 EDT 2017},
month = {Fri Jul 14 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/aenm.201701122

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Cited by: 41 works
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Works referenced in this record:

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

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Progress in Mechanistic Understanding and Characterization Techniques of Li-S Batteries
journal, May 2015


Insight into the role of Li 2 S 2 in Li–S batteries: a first-principles study
journal, January 2015

  • Yang, Guochun; Shi, Shaoqing; Yang, Jinghai
  • Journal of Materials Chemistry A, Vol. 3, Issue 16
  • DOI: 10.1039/C5TA00499C

Mesoporous Titanium Nitride-Enabled Highly Stable Lithium-Sulfur Batteries
journal, May 2016


Photoelectron spectroscopy and atomic force microscopy study of 1,2-dicyano-methanofullerene C60(CN)2 thin film for photovoltaic applications
journal, April 2011

  • Koppolu, Vaishali Rao; Gupta, Mool C.; Scudiero, Louis
  • Solar Energy Materials and Solar Cells, Vol. 95, Issue 4
  • DOI: 10.1016/j.solmat.2010.12.024

Optical properties, phonons and electronic structure of iron pyrite (FeS 2 )
journal, September 1976


Activated Li 2 S as a High-Performance Cathode for Rechargeable Lithium–Sulfur Batteries
journal, November 2014

  • Zu, Chenxi; Klein, Michael; Manthiram, Arumugam
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 22
  • DOI: 10.1021/jz5021108

Conductivities and electronic structures of some phases in the lithium-iron-sulfur system
journal, July 1982


A Hierarchical Particle-Shell Architecture for Long-Term Cycle Stability of Li 2 S Cathodes
journal, August 2015


Powering Lithium–Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts
journal, December 2015


Process and characterisation of chemical bath deposited manganese sulphide (MnS) thin films
journal, September 1998


Determination of the escape depth of photoemitted electrons in gold in the energy range 25–75 eV by use of synchrotron radiation
journal, January 1976

  • Lindau, I.; Pianetta, P.; Yu, K. Y.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 8, Issue 5
  • DOI: 10.1016/0368-2048(76)80036-9

Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011

  • Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01598b

Elucidation of the charge-discharge mechanism of lithium/polymer electrolyte/pyrite batteries
journal, December 2001

  • Strauss, E.; Golodnitsky, D.; Peled, E.
  • Journal of Solid State Electrochemistry, Vol. 6, Issue 7
  • DOI: 10.1007/s10008-001-0259-y

Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries
journal, January 2016

  • Klein, Michael J.; Goossens, Karel; Bielawski, Christopher W.
  • Journal of The Electrochemical Society, Vol. 163, Issue 9
  • DOI: 10.1149/2.0051610jes

Lithium-ion batteries. A look into the future
journal, January 2011

  • Scrosati, Bruno; Hassoun, Jusef; Sun, Yang-Kook
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01388b

Revealing the planar chemistry of two-dimensional heterostructures at the atomic level
journal, June 2015

  • Chou, Harry; Ismach, Ariel; Ghosh, Rudresh
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8482

Identification of cathode materials for lithium batteries guided by first-principles calculations
journal, April 1998

  • Ceder, G.; Chiang, Y. -M.; Sadoway, D. R.
  • Nature, Vol. 392, Issue 6677
  • DOI: 10.1038/33647

Nanostructured sulfur cathodes
journal, January 2013

  • Yang, Yuan; Zheng, Guangyuan; Cui, Yi
  • Chemical Society Reviews, Vol. 42, Issue 7, p. 3018-3032
  • DOI: 10.1039/c2cs35256g

High-purity iron pyrite (FeS 2 ) nanowires as high-capacity nanostructured cathodes for lithium-ion batteries
journal, January 2014

  • Li, Linsen; Cabán-Acevedo, Miguel; Girard, Steven N.
  • Nanoscale, Vol. 6, Issue 4
  • DOI: 10.1039/C3NR05851D

New Nanostructured Li2S/Silicon Rechargeable Battery with High Specific Energy
journal, April 2010

  • Yang, Yuan; McDowell, Matthew T.; Jackson, Ariel
  • Nano Letters, Vol. 10, Issue 4, p. 1486-1491
  • DOI: 10.1021/nl100504q

Li/CPE/FeS2 rechargeable battery
journal, April 1998


Electrochemical verification of the redox mechanism of FeS2 in a rechargeable lithium battery
journal, September 2015


Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Advances in Li–S batteries
journal, January 2010

  • Ji, Xiulei; Nazar, Linda F.
  • Journal of Materials Chemistry, Vol. 20, Issue 44, p. 9821-9826
  • DOI: 10.1039/b925751a

Thermodynamic analysis on energy densities of batteries
journal, January 2011

  • Zu, Chen-Xi; Li, Hong
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c0ee00777c

Nanomaterials for Rechargeable Lithium Batteries
journal, April 2008

  • Bruce, Peter G.; Scrosati, Bruno; Tarascon, Jean-Marie
  • Angewandte Chemie International Edition, Vol. 47, Issue 16, p. 2930-2946
  • DOI: 10.1002/anie.200702505

Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth
journal, February 2016

  • Yan, Kai; Lu, Zhenda; Lee, Hyun-Wook
  • Nature Energy, Vol. 1, Issue 3, Article No. 16010
  • DOI: 10.1038/nenergy.2016.10

High-Capacity Micrometer-Sized Li2 S Particles as Cathode Materials for Advanced Rechargeable Lithium-Ion Batteries
journal, September 2012

  • Yang, Yuan; Zheng, Guangyuan; Misra, Sumohan
  • Journal of the American Chemical Society, Vol. 134, Issue 37, p. 15387-15394
  • DOI: 10.1021/ja3052206

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

  • Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500062v

Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries
journal, January 2017

  • Zhou, Guangmin; Tian, Hongzhen; Jin, Yang
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 5
  • DOI: 10.1073/pnas.1615837114

Hollow α-MnS Spheres and Their Hybrids with Reduced Graphene Oxide: Synthesis, Microwave Absorption, and Lithium Storage Properties
journal, June 2013


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
  • DOI: 10.1038/ncomms6017

Breaking Down the Crystallinity: The Path for Advanced Lithium Batteries
journal, December 2015

  • Zu, Chenxi; Dolocan, Andrei; Xiao, Penghao
  • Advanced Energy Materials, Vol. 6, Issue 5
  • DOI: 10.1002/aenm.201501933

Understanding of Electrochemical Oxidation Route of Electrically Isolated Li 2 S Particles
journal, January 2014

  • Koh, Jeong Yoon; Park, Min-Sik; Kim, Eun Hee
  • Journal of The Electrochemical Society, Vol. 161, Issue 14
  • DOI: 10.1149/2.0201414jes

The Use of Redox Mediators for Enhancing Utilization of Li 2 S Cathodes for Advanced Li–S Battery Systems
journal, February 2014

  • Meini, Stefano; Elazari, Ran; Rosenman, Ariel
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 5
  • DOI: 10.1021/jz500222f