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Title: Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries

Abstract

The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. In this paper, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H2. Although the kinetics of HF dissociation and the concomitant production of LiF and H2 is dependent on the structure and nature of surface atoms, the underlying electrochemistry is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Finally, our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [3];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [2];  [3];  [4]; ORCiD logo [4];  [1];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Univ. of Copenhagen (Denmark). Nano-Science Center. Dept. of Chemistry
  3. Technical Univ. of Munich (Germany). Chair of Technical Electrochemistry. Dept. of Chemistry. Catalysis Research Center
  4. BMW Group, Munich (Germany). Battery Cell Technology
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); BMW Group, Munich (Germany)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); BMW Technology Corporation (Germany)
OSTI Identifier:
1433882
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Catalysis
Additional Journal Information:
Journal Volume: 1; Journal Issue: 4; Journal ID: ISSN 2520-1158
Publisher:
Springer Nature
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; batteries; electrocatalysis; electrochemistry

Citation Formats

Strmcnik, Dusan, Castelli, Ivano E., Connell, Justin G., Haering, Dominik, Zorko, Milena, Martins, Pedro, Lopes, Pietro P., Genorio, Bostjan, Ostergaard, Thomas, Gasteiger, Hubert A., Maglia, Filippo, Antonopoulos, Byron K., Stamenkovic, Vojislav R., Rossmeisl, Jan, and Markovic, Nenad M. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries. United States: N. p., 2018. Web. https://doi.org/10.1038/s41929-018-0047-z.
Strmcnik, Dusan, Castelli, Ivano E., Connell, Justin G., Haering, Dominik, Zorko, Milena, Martins, Pedro, Lopes, Pietro P., Genorio, Bostjan, Ostergaard, Thomas, Gasteiger, Hubert A., Maglia, Filippo, Antonopoulos, Byron K., Stamenkovic, Vojislav R., Rossmeisl, Jan, & Markovic, Nenad M. Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries. United States. https://doi.org/10.1038/s41929-018-0047-z
Strmcnik, Dusan, Castelli, Ivano E., Connell, Justin G., Haering, Dominik, Zorko, Milena, Martins, Pedro, Lopes, Pietro P., Genorio, Bostjan, Ostergaard, Thomas, Gasteiger, Hubert A., Maglia, Filippo, Antonopoulos, Byron K., Stamenkovic, Vojislav R., Rossmeisl, Jan, and Markovic, Nenad M. Mon . "Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries". United States. https://doi.org/10.1038/s41929-018-0047-z. https://www.osti.gov/servlets/purl/1433882.
@article{osti_1433882,
title = {Electrocatalytic transformation of HF impurity to H2 and LiF in lithium-ion batteries},
author = {Strmcnik, Dusan and Castelli, Ivano E. and Connell, Justin G. and Haering, Dominik and Zorko, Milena and Martins, Pedro and Lopes, Pietro P. and Genorio, Bostjan and Ostergaard, Thomas and Gasteiger, Hubert A. and Maglia, Filippo and Antonopoulos, Byron K. and Stamenkovic, Vojislav R. and Rossmeisl, Jan and Markovic, Nenad M.},
abstractNote = {The formation of solid electrolyte interphase on graphite anodes plays a key role in the efficiency of Li-ion batteries. However, to date, fundamental understanding of the formation of LiF as one of the main solid electrolyte interphase components in hexafluorophosphate-based electrolytes remains elusive. In this paper, we present experimental and theoretical evidence that LiF formation is an electrocatalytic process that is controlled by the electrochemical transformation of HF impurity to LiF and H2. Although the kinetics of HF dissociation and the concomitant production of LiF and H2 is dependent on the structure and nature of surface atoms, the underlying electrochemistry is the same. The morphology, and thus the role, of the LiF formed is strongly dependent on the nature of the substrate and HF inventory, leading to either complete or partial passivation of the interface. Finally, our finding is of general importance and may lead to new opportunities for the improvement of existing, and design of new, Li-ion technologies.},
doi = {10.1038/s41929-018-0047-z},
journal = {Nature Catalysis},
number = 4,
volume = 1,
place = {United States},
year = {2018},
month = {4}
}

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