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Title: Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries

Abstract

Deviation between thermodynamic and experimental voltages is one of the key issues in Li-ion conversion-type electrode materials; the factor that affects this phenomenon has not been understood well in spite of its importance. In this work, we combine first principles calculations and electrochemical experiments with characterization tools to probe the conversion reaction voltage of transition metal difluorides MF2 (M = Fe, Ni, and Cu). We find that the conversion reaction voltage is heavily dependent on the size of the metal nanoparticles generated. The surface energy of metal nanoparticles appears to penalize the reaction energy, which results in a lower voltage compared to the thermodynamic voltage of a bulk-phase reaction. Furthermore, we develop a reversible CuF2 electrode coated with NiO. Electron energy loss spectroscopy (EELS) elemental maps demonstrate that the lithiation process mostly occurs in the area of high NiO content. This suggests that NiO can be considered a suitable artificial solid electrolyte interphase that prevents direct contact between Cu nanoparticles and the electrolyte. Thus, it alleviates Cu dissolution into the electrolyte and improves the reversibility of CuF2.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division; USDOE Office of Science - Energy Frontier Research Center - NorthEast Center for Chemical Energy Storage (NECCES)
OSTI Identifier:
1459949
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Nano Research; Journal Volume: 10; Journal Issue: 12
Country of Publication:
United States
Language:
English

Citation Formats

Seo, Joon Kyo, Cho, Hyung-Man, Takahara, Katsunori, Chapman, Karena W., Borkiewicz, Olaf J., Sina, Mahsa, and Shirley Meng, Y. Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries. United States: N. p., 2017. Web. doi:10.1007/s12274-016-1365-6.
Seo, Joon Kyo, Cho, Hyung-Man, Takahara, Katsunori, Chapman, Karena W., Borkiewicz, Olaf J., Sina, Mahsa, & Shirley Meng, Y. Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries. United States. doi:10.1007/s12274-016-1365-6.
Seo, Joon Kyo, Cho, Hyung-Man, Takahara, Katsunori, Chapman, Karena W., Borkiewicz, Olaf J., Sina, Mahsa, and Shirley Meng, Y. Mon . "Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries". United States. doi:10.1007/s12274-016-1365-6.
@article{osti_1459949,
title = {Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries},
author = {Seo, Joon Kyo and Cho, Hyung-Man and Takahara, Katsunori and Chapman, Karena W. and Borkiewicz, Olaf J. and Sina, Mahsa and Shirley Meng, Y.},
abstractNote = {Deviation between thermodynamic and experimental voltages is one of the key issues in Li-ion conversion-type electrode materials; the factor that affects this phenomenon has not been understood well in spite of its importance. In this work, we combine first principles calculations and electrochemical experiments with characterization tools to probe the conversion reaction voltage of transition metal difluorides MF2 (M = Fe, Ni, and Cu). We find that the conversion reaction voltage is heavily dependent on the size of the metal nanoparticles generated. The surface energy of metal nanoparticles appears to penalize the reaction energy, which results in a lower voltage compared to the thermodynamic voltage of a bulk-phase reaction. Furthermore, we develop a reversible CuF2 electrode coated with NiO. Electron energy loss spectroscopy (EELS) elemental maps demonstrate that the lithiation process mostly occurs in the area of high NiO content. This suggests that NiO can be considered a suitable artificial solid electrolyte interphase that prevents direct contact between Cu nanoparticles and the electrolyte. Thus, it alleviates Cu dissolution into the electrolyte and improves the reversibility of CuF2.},
doi = {10.1007/s12274-016-1365-6},
journal = {Nano Research},
number = 12,
volume = 10,
place = {United States},
year = {Mon Feb 13 00:00:00 EST 2017},
month = {Mon Feb 13 00:00:00 EST 2017}
}