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Title: Structural Transformation of LiFePO4 during Ultrafast Delithiation

Abstract

The prolific lithium battery electrode material lithium iron phosphate (LiFePO4) stores and releases lithium ions by undergoing a crystallographic phase change. Nevertheless, it performs unexpectedly well at high rate and exhibits good cycling stability. Here we investigate here the ultrafast charging reaction to resolve the underlying mechanism while avoiding the limitations of prevailing electrochemical methods by using a gaseous oxidant to deintercalate lithium from the LiFePO4 structure. Oxidizing LiFePO4 with nitrogen dioxide gas reveals structural changes through in situ synchrotron X-ray diffraction and electronic changes through in situ UV/vis reflectance spectroscopy. This study clearly shows that ultrahigh rates reaching 100% state of charge in 10 s does not lead to a particle-wide union of the olivine and heterosite structures. An extensive solid solution phase is therefore not a prerequisite for ultrafast charge/discharge.

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [2];  [3];  [1]
  1. Univ. of Quebec, Montreal, QC (Canada). Dept. de chimie
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  3. Johnson Matthey Battery Materials Ltd, Candiac, QC (Canada)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Natural Sciences and Engineering Research Council of Canada (NSERC)
OSTI Identifier:
1425270
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 24; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE; lithium-ion; In-Situ; Uv-vis; XRD; biphasic; electronic structure; reaction mechanism; structural analysis

Citation Formats

Kuss, Christian, Trinh, Ngoc Duc, Andjelic, Stefan, Saulnier, Mathieu, Dufresne, Eric M., Liang, Guoxian, and Schougaard, Steen B.. Structural Transformation of LiFePO4 during Ultrafast Delithiation. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpclett.7b02569.
Kuss, Christian, Trinh, Ngoc Duc, Andjelic, Stefan, Saulnier, Mathieu, Dufresne, Eric M., Liang, Guoxian, & Schougaard, Steen B.. Structural Transformation of LiFePO4 during Ultrafast Delithiation. United States. https://doi.org/10.1021/acs.jpclett.7b02569
Kuss, Christian, Trinh, Ngoc Duc, Andjelic, Stefan, Saulnier, Mathieu, Dufresne, Eric M., Liang, Guoxian, and Schougaard, Steen B.. Tue . "Structural Transformation of LiFePO4 during Ultrafast Delithiation". United States. https://doi.org/10.1021/acs.jpclett.7b02569. https://www.osti.gov/servlets/purl/1425270.
@article{osti_1425270,
title = {Structural Transformation of LiFePO4 during Ultrafast Delithiation},
author = {Kuss, Christian and Trinh, Ngoc Duc and Andjelic, Stefan and Saulnier, Mathieu and Dufresne, Eric M. and Liang, Guoxian and Schougaard, Steen B.},
abstractNote = {The prolific lithium battery electrode material lithium iron phosphate (LiFePO4) stores and releases lithium ions by undergoing a crystallographic phase change. Nevertheless, it performs unexpectedly well at high rate and exhibits good cycling stability. Here we investigate here the ultrafast charging reaction to resolve the underlying mechanism while avoiding the limitations of prevailing electrochemical methods by using a gaseous oxidant to deintercalate lithium from the LiFePO4 structure. Oxidizing LiFePO4 with nitrogen dioxide gas reveals structural changes through in situ synchrotron X-ray diffraction and electronic changes through in situ UV/vis reflectance spectroscopy. This study clearly shows that ultrahigh rates reaching 100% state of charge in 10 s does not lead to a particle-wide union of the olivine and heterosite structures. An extensive solid solution phase is therefore not a prerequisite for ultrafast charge/discharge.},
doi = {10.1021/acs.jpclett.7b02569},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 8,
place = {United States},
year = {2017},
month = {12}
}

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Works referenced in this record:

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

  • Padhi, A. K.
  • Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194
  • DOI: 10.1149/1.1837571

Phase Change in Li[sub x]FePO[sub 4]
journal, January 2005

  • Yamada, Atsuo; Koizumi, Hiroshi; Sonoyama, Noriyuki
  • Electrochemical and Solid-State Letters, Vol. 8, Issue 8
  • DOI: 10.1149/1.1945373

Ultrafast charging of LiFePO4 with gaseous oxidants under ambient conditions
journal, January 2013

  • Kuss, Christian; Lepage, David; Liang, Guoxian
  • Chemical Science, Vol. 4, Issue 11
  • DOI: 10.1039/c3sc51195b

An improved high-power battery with increased thermal operating range: C–LiFePO4//C–Li4Ti5O12
journal, October 2012


Suppression of Phase Separation in LiFePO 4 Nanoparticles During Battery Discharge
journal, November 2011

  • Bai, Peng; Cogswell, Daniel A.; Bazant, Martin Z.
  • Nano Letters, Vol. 11, Issue 11
  • DOI: 10.1021/nl202764f

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014


Comparative Kinetic Study of Olivine Li[sub x]MPO[sub 4] (M=Fe, Mn)
journal, January 2004

  • Yonemura, Masao; Yamada, Atsuo; Takei, Yuki
  • Journal of The Electrochemical Society, Vol. 151, Issue 9
  • DOI: 10.1149/1.1773731

A nanoview of battery operation
journal, August 2016


Nanoscale Measurements of Lithium-Ion-Battery Materials using Scanning Probe Techniques
journal, November 2016

  • Danis, Laurence; Gateman, Samantha M.; Kuss, Christian
  • ChemElectroChem, Vol. 4, Issue 1
  • DOI: 10.1002/celc.201600571

In Situ Observation of Random Solid Solution Zone in LiFePO 4 Electrode
journal, June 2014

  • Niu, Junjie; Kushima, Akihiro; Qian, Xiaofeng
  • Nano Letters, Vol. 14, Issue 7
  • DOI: 10.1021/nl501415b

Electrochromism of Li x FePO 4 Induced by Intervalence Charge Transfer Transition
journal, July 2012

  • Furutsuki, Sho; Chung, Sai-Cheong; Nishimura, Shin-ichi
  • The Journal of Physical Chemistry C, Vol. 116, Issue 29
  • DOI: 10.1021/jp304221z

    Works referencing / citing this record:

    Olivine Positive Electrodes for Li-Ion Batteries: Status and Perspectives
    journal, August 2018