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Title: Operando Studies Reveal Structural Evolution with Electrochemical Cycling in Li–CoS 2

Abstract

The desire for high energy density alternatives to Li-ion batteries has led to great interest in energy storage materials not inherently constrained by the capacity limits of standard intercalation electrode materials currently employed in commercial devices. Among the alternatives under consideration are electrode materials with theoretical capacities many times greater than intercalation electrodes, including those that store charge through so-called conversion reactions. However, the vast structural changes that enable the high theoretical capacity of conversion systems contribute to issues of poor efficiency and short cycle life. To better understand the cycling issues in conversion systems, we study the local structure evolution of the cathode active material in LiCoS 2 cells. Being metallic, and potentially being capable of redox on both the anion and cation, we would expect CoS 2 to be a promising cathode material. Through combined ex situ X-ray absorption near-edge spectroscopy and pair distribution function analysis from operando X-ray total scattering, we describe the reactions that take place over the first 1.5 cycles. In doing so, we identify the irreversible formation of a Co 9S 8-like local structure with significantly limited electrochemical activity as the primary source of capacity fade. The methods employed here and the insights thatmore » emerge inform the rational design of conversion systems for electrochemical energy storage.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [1];  [1];  [3];  [3]; ORCiD logo [3];  [3];  [3]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Univ. of California, Santa Barbara, CA (United States); Fraunhofer IWM, Freiburg (Germany)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division; National Science Foundation (NSF)
OSTI Identifier:
1491740
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 122; Journal Issue: 43; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Butala, Megan M., Doan-Nguyen, Vicky V. T., Lehner, Anna J., Göbel, Claudia, Lumley, Margaret A., Arnon, Shiri, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., Balasubramanian, Mahalingam, and Seshadri, Ram. Operando Studies Reveal Structural Evolution with Electrochemical Cycling in Li–CoS2. United States: N. p., 2018. Web. doi:10.1021/acs.jpcc.8b07828.
Butala, Megan M., Doan-Nguyen, Vicky V. T., Lehner, Anna J., Göbel, Claudia, Lumley, Margaret A., Arnon, Shiri, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., Balasubramanian, Mahalingam, & Seshadri, Ram. Operando Studies Reveal Structural Evolution with Electrochemical Cycling in Li–CoS2. United States. doi:10.1021/acs.jpcc.8b07828.
Butala, Megan M., Doan-Nguyen, Vicky V. T., Lehner, Anna J., Göbel, Claudia, Lumley, Margaret A., Arnon, Shiri, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., Balasubramanian, Mahalingam, and Seshadri, Ram. Wed . "Operando Studies Reveal Structural Evolution with Electrochemical Cycling in Li–CoS2". United States. doi:10.1021/acs.jpcc.8b07828.
@article{osti_1491740,
title = {Operando Studies Reveal Structural Evolution with Electrochemical Cycling in Li–CoS2},
author = {Butala, Megan M. and Doan-Nguyen, Vicky V. T. and Lehner, Anna J. and Göbel, Claudia and Lumley, Margaret A. and Arnon, Shiri and Wiaderek, Kamila M. and Borkiewicz, Olaf J. and Chapman, Karena W. and Chupas, Peter J. and Balasubramanian, Mahalingam and Seshadri, Ram},
abstractNote = {The desire for high energy density alternatives to Li-ion batteries has led to great interest in energy storage materials not inherently constrained by the capacity limits of standard intercalation electrode materials currently employed in commercial devices. Among the alternatives under consideration are electrode materials with theoretical capacities many times greater than intercalation electrodes, including those that store charge through so-called conversion reactions. However, the vast structural changes that enable the high theoretical capacity of conversion systems contribute to issues of poor efficiency and short cycle life. To better understand the cycling issues in conversion systems, we study the local structure evolution of the cathode active material in LiCoS2 cells. Being metallic, and potentially being capable of redox on both the anion and cation, we would expect CoS2 to be a promising cathode material. Through combined ex situ X-ray absorption near-edge spectroscopy and pair distribution function analysis from operando X-ray total scattering, we describe the reactions that take place over the first 1.5 cycles. In doing so, we identify the irreversible formation of a Co9S8-like local structure with significantly limited electrochemical activity as the primary source of capacity fade. The methods employed here and the insights that emerge inform the rational design of conversion systems for electrochemical energy storage.},
doi = {10.1021/acs.jpcc.8b07828},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 43,
volume = 122,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
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