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Title: Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery

Abstract

Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS 2, can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description ofmore » the reaction mechanism.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [3];  [3];  [3];  [3];  [2];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1413919
Report Number(s):
BNL-114411-2017-JA
Journal ID: ISSN 2045-2322
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Sun, Ke, Zhao, Chonghang, Lin, Cheng-Hung, Stavitski, Eli, Williams, Garth J., Bai, Jianming, Dooryhee, Eric, Attenkofer, Klaus, Thieme, Juergen, Chen-Wiegart, Yu-chen Karen, and Gan, Hong. Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery. United States: N. p., 2017. Web. doi:10.1038/s41598-017-12738-0.
Sun, Ke, Zhao, Chonghang, Lin, Cheng-Hung, Stavitski, Eli, Williams, Garth J., Bai, Jianming, Dooryhee, Eric, Attenkofer, Klaus, Thieme, Juergen, Chen-Wiegart, Yu-chen Karen, & Gan, Hong. Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery. United States. doi:10.1038/s41598-017-12738-0.
Sun, Ke, Zhao, Chonghang, Lin, Cheng-Hung, Stavitski, Eli, Williams, Garth J., Bai, Jianming, Dooryhee, Eric, Attenkofer, Klaus, Thieme, Juergen, Chen-Wiegart, Yu-chen Karen, and Gan, Hong. Wed . "Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery". United States. doi:10.1038/s41598-017-12738-0. https://www.osti.gov/servlets/purl/1413919.
@article{osti_1413919,
title = {Operando Multi-modal Synchrotron Investigation for Structural and Chemical Evolution of Cupric Sulfide (CuS) Additive in Li-S battery},
author = {Sun, Ke and Zhao, Chonghang and Lin, Cheng-Hung and Stavitski, Eli and Williams, Garth J. and Bai, Jianming and Dooryhee, Eric and Attenkofer, Klaus and Thieme, Juergen and Chen-Wiegart, Yu-chen Karen and Gan, Hong},
abstractNote = {Conductive metal sulfides are promising multi-functional additives for future lithium-sulfur (Li-S) batteries. These can increase the sulfur cathode’s electrical conductivity to improve the battery’s power capability, as well as contribute to the overall cell-discharge capacity. This multi-functional electrode design showed initial promise; however, complicated interactions at the system level are accompanied by some detrimental side effects. The metal sulfide additives with a chemical conversion as the reaction mechanism, e.g., CuS and FeS2, can increase the theoretical capacity of the Li-S system. However, these additives may cause undesired parasitic reactions, such as the dissolution of the additive in the electrolyte. Studying such complex reactions presents a challenge because it requires experimental methods that can track the chemical and structural evolution of the system during an electrochemical process. To address the fundamental mechanisms in these systems, we employed an operando multimodal x-ray characterization approach to study the structural and chemical evolution of the metal sulfide—utilizing powder diffraction and fluorescence imaging to resolve the former and absorption spectroscopy the latter—during lithiation and de-lithiation of a Li-S battery with CuS as the multi-functional cathode additive. The resulting elucidation of the structural and chemical evolution of the system leads to a new description of the reaction mechanism.},
doi = {10.1038/s41598-017-12738-0},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {2017},
month = {10}
}

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Works referenced in this record:

Copper sulfides for rechargeable lithium batteries: Linking cycling stability to electrolyte composition
journal, February 2014


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


A multifunctional 3.5 V iron-based phosphate cathode for rechargeable batteries
journal, September 2007

  • Ellis, B. L.; Makahnouk, W. R. M.; Makimura, Y.
  • Nature Materials, Vol. 6, Issue 10
  • DOI: 10.1038/nmat2007

The structure of amorphous copper sulfide precipitates: An X-ray absorption study
journal, May 1997

  • Pattrick, R. A. D.; Mosselmans, J. F. W.; Charnock, J. M.
  • Geochimica et Cosmochimica Acta, Vol. 61, Issue 10
  • DOI: 10.1016/S0016-7037(97)00061-6

Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability
journal, July 2011

  • Wang, Hailiang; Yang, Yuan; Liang, Yongye
  • Nano Letters, Vol. 11, Issue 7, p. 2644-2647
  • DOI: 10.1021/nl200658a

Role of LiNO3 in rechargeable lithium/sulfur battery
journal, May 2012


In Operando X-ray Diffraction and Transmission X-ray Microscopy of Lithium Sulfur Batteries
journal, March 2012

  • Nelson, Johanna; Misra, Sumohan; Yang, Yuan
  • Journal of the American Chemical Society, Vol. 134, Issue 14
  • DOI: 10.1021/ja2121926

Sulfur-Impregnated Activated Carbon Fiber Cloth as a Binder-Free Cathode for Rechargeable Li-S Batteries
journal, November 2011

  • Elazari, Ran; Salitra, Gregory; Garsuch, Arnd
  • Advanced Materials, Vol. 23, Issue 47, p. 5641-5644
  • DOI: 10.1002/adma.201103274

A Multifunctional Load-Bearing Solid-State Supercapacitor
journal, May 2014

  • Westover, Andrew S.; Tian, John W.; Bernath, Shivaprem
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl500531r

Copper-Stabilized Sulfur-Microporous Carbon Cathodes for Li-S Batteries
journal, March 2014

  • Zheng, Shiyou; Yi, Feng; Li, Zhipeng
  • Advanced Functional Materials, Vol. 24, Issue 26
  • DOI: 10.1002/adfm.201304156

A Sulfur Cathode with Pomegranate-Like Cluster Structure
journal, May 2015

  • Li, Weiyang; Liang, Zheng; Lu, Zhenda
  • Advanced Energy Materials, Vol. 5, Issue 16
  • DOI: 10.1002/aenm.201500211

Performance calculations of the X-ray powder diffraction beamline at NSLS-II
journal, January 2013

  • Shi, Xianbo; Ghose, Sanjit; Dooryhee, Eric
  • Journal of Synchrotron Radiation, Vol. 20, Issue 2
  • DOI: 10.1107/S0909049512049175

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


Towards an Understanding of Li 2 O 2 Evolution in Li-O 2 Batteries: An In Operando Synchrotron X-ray Diffraction Study
journal, March 2017


Sulfur-Impregnated Disordered Carbon Nanotubes Cathode for Lithium–Sulfur Batteries
journal, October 2011

  • Guo, Juchen; Xu, Yunhua; Wang, Chunsheng
  • Nano Letters, Vol. 11, Issue 10, p. 4288-4294
  • DOI: 10.1021/nl202297p

Elemental Sulfur and Molybdenum Disulfide Composites for Li–S Batteries with Long Cycle Life and High-Rate Capability
journal, May 2016

  • Dirlam, Philip T.; Park, Jungjin; Simmonds, Adam G.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 21
  • DOI: 10.1021/acsami.6b03200

In-situ X-ray diffraction studies of lithium–sulfur batteries
journal, March 2013


Reactivity of transition metal (Co, Ni, Cu) sulphides versus lithium: The intriguing case of the copper sulphide
journal, June 2006


Multifunctional 3D nanoarchitectures for energy storage and conversion
journal, January 2009

  • Rolison, Debra R.; Long, Jeffrey W.; Lytle, Justin C.
  • Chemical Society Reviews, Vol. 38, Issue 1, p. 226-252
  • DOI: 10.1039/B801151F

New In-Situ and Operando Facilities for Catalysis Science at NSLS-II: The Deployment of Real-Time, Chemical, and Structure-Sensitive X-ray Probes
journal, March 2017


Pyrite FeS 2 as an efficient adsorbent of lithium polysulphide for improved lithium–sulphur batteries
journal, January 2016

  • Zhang, Sheng S.; Tran, Dat T.
  • Journal of Materials Chemistry A, Vol. 4, Issue 12
  • DOI: 10.1039/C6TA01214K

Quantitative X-ray absorption and emission spectroscopies: electronic structure elucidation of Cu2S and CuS
journal, January 2013

  • Kumar, Prashant; Nagarajan, Rajamani; Sarangi, Ritimukta
  • Journal of Materials Chemistry C, Vol. 1, Issue 13
  • DOI: 10.1039/c3tc00639e

Exploring 3D microstructural evolution in Li-Sulfur battery electrodes using in-situ X-ray tomography
journal, October 2016

  • Yermukhambetova, Assiya; Tan, Chun; Daemi, Sohrab R.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep35291

Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions
journal, June 2013


In Situ X-ray Diffraction Studies of (De)lithiation Mechanism in Silicon Nanowire Anodes
journal, May 2012

  • Misra, Sumohan; Liu, Nian; Nelson, Johanna
  • ACS Nano, Vol. 6, Issue 6
  • DOI: 10.1021/nn301339g

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

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

Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge
journal, September 2016

  • Zheng, Dong; Liu, Dan; Harris, Joshua B.
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 5
  • DOI: 10.1021/acsami.6b08904

Interaction of CuS and Sulfur in Li-S Battery System
journal, January 2015

  • Sun, Ke; Su, Dong; Zhang, Qing
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.1021514jes

Lithium/Sulfur Batteries Upon Cycling: Structural Modifications and Species Quantification by In Situ and Operando X-Ray Diffraction Spectroscopy
journal, May 2015

  • Waluś, Sylwia; Barchasz, Céline; Bouchet, Renaud
  • Advanced Energy Materials, Vol. 5, Issue 16
  • DOI: 10.1002/aenm.201500165

High-Performance Lithium-Sulfur Batteries with a Self-Supported, 3D Li 2 S-Doped Graphene Aerogel Cathodes
journal, November 2015

  • Zhou, Guangmin; Paek, Eunsu; Hwang, Gyeong S.
  • Advanced Energy Materials, Vol. 6, Issue 2
  • DOI: 10.1002/aenm.201501355

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

Djurleite (Cu1.94S) and Low Chalcocite (Cu2S): New Crystal Structure Studies
journal, January 1979


Multifunctional TiO 2 –C/MnO 2 Core–Double-Shell Nanowire Arrays as High-Performance 3D Electrodes for Lithium Ion Batteries
journal, October 2013

  • Liao, Jin-Yun; Higgins, Drew; Lui, Gregory
  • Nano Letters, Vol. 13, Issue 11
  • DOI: 10.1021/nl4030159

Fluorine-Free Pt Nanocomposites for Three-Phase Interfaces in Fuel Cell Electrodes
journal, September 2016


Investigation of Copper Speciation in Pig Slurry by a Multitechnique Approach
journal, September 2010

  • Legros, Samuel; Chaurand, Perrine; Rose, Jérôme
  • Environmental Science & Technology, Vol. 44, Issue 18
  • DOI: 10.1021/es101651w

Direct Observation of Sulfur Radicals as Reaction Media in Lithium Sulfur Batteries
journal, December 2014

  • Wang, Qiang; Zheng, Jianming; Walter, Eric
  • Journal of The Electrochemical Society, Vol. 162, Issue 3
  • DOI: 10.1149/2.0851503jes

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

Interaction of FeS 2 and Sulfur in Li-S Battery System
journal, September 2016

  • Sun, Ke; Cama, Christina A.; DeMayo, Rachel A.
  • Journal of The Electrochemical Society, Vol. 164, Issue 1
  • DOI: 10.1149/2.0041701jes

Sulfur/lithium-insertion compound composite cathodes for Li–S batteries
journal, December 2014


    Works referencing / citing this record:

    Recent Progress in Liquid Electrolyte-Based Li–S Batteries: Shuttle Problem and Solutions
    journal, November 2018


    Recent Progress in Liquid Electrolyte-Based Li–S Batteries: Shuttle Problem and Solutions
    journal, November 2018