(De)lithiation mechanism of Li/SeSx (x = 0-7) batteries determined by in situ synchrotron x-ray diffraction and X-ray absorption spectroscopy

Yanjie Cui, Ali Abouimrane, Jun Lu, Trudy Bolin, Yang Ren, Wei Weng, Chengjun Sun, Victor A. Maroni, Steve M. Heald, Khalil Amine

Research output: Contribution to journalArticle

159 Citations (Scopus)

Abstract

Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li 2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

Original languageEnglish
Pages (from-to)8047-8056
Number of pages10
JournalJournal of the American Chemical Society
Volume135
Issue number21
DOIs
Publication statusPublished - 29 May 2013
Externally publishedYes

Fingerprint

X-Ray Absorption Spectroscopy
Synchrotrons
X ray absorption spectroscopy
Electrolytes
Diffraction
X-Rays
X rays
Crystalline materials
Lithium
Ether
Energy storage
Ethers
Dielectric Spectroscopy
Photoelectron Spectroscopy
Carbonates
Phase Transition
X ray absorption
Electrochemical impedance spectroscopy
X-Ray Diffraction
Electrodes

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

(De)lithiation mechanism of Li/SeSx (x = 0-7) batteries determined by in situ synchrotron x-ray diffraction and X-ray absorption spectroscopy. / Cui, Yanjie; Abouimrane, Ali; Lu, Jun; Bolin, Trudy; Ren, Yang; Weng, Wei; Sun, Chengjun; Maroni, Victor A.; Heald, Steve M.; Amine, Khalil.

In: Journal of the American Chemical Society, Vol. 135, No. 21, 29.05.2013, p. 8047-8056.

Research output: Contribution to journalArticle

Cui, Yanjie ; Abouimrane, Ali ; Lu, Jun ; Bolin, Trudy ; Ren, Yang ; Weng, Wei ; Sun, Chengjun ; Maroni, Victor A. ; Heald, Steve M. ; Amine, Khalil. / (De)lithiation mechanism of Li/SeSx (x = 0-7) batteries determined by in situ synchrotron x-ray diffraction and X-ray absorption spectroscopy. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 21. pp. 8047-8056.
@article{163c9dee7e464840a1424d8212092ea8,
title = "(De)lithiation mechanism of Li/SeSx (x = 0-7) batteries determined by in situ synchrotron x-ray diffraction and X-ray absorption spectroscopy",
abstract = "Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li 2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.",
author = "Yanjie Cui and Ali Abouimrane and Jun Lu and Trudy Bolin and Yang Ren and Wei Weng and Chengjun Sun and Maroni, {Victor A.} and Heald, {Steve M.} and Khalil Amine",
year = "2013",
month = "5",
day = "29",
doi = "10.1021/ja402597g",
language = "English",
volume = "135",
pages = "8047--8056",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - (De)lithiation mechanism of Li/SeSx (x = 0-7) batteries determined by in situ synchrotron x-ray diffraction and X-ray absorption spectroscopy

AU - Cui, Yanjie

AU - Abouimrane, Ali

AU - Lu, Jun

AU - Bolin, Trudy

AU - Ren, Yang

AU - Weng, Wei

AU - Sun, Chengjun

AU - Maroni, Victor A.

AU - Heald, Steve M.

AU - Amine, Khalil

PY - 2013/5/29

Y1 - 2013/5/29

N2 - Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li 2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

AB - Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li 2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

UR - http://www.scopus.com/inward/record.url?scp=84878416571&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84878416571&partnerID=8YFLogxK

U2 - 10.1021/ja402597g

DO - 10.1021/ja402597g

M3 - Article

VL - 135

SP - 8047

EP - 8056

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 21

ER -