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Title: Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives

Abstract

In an effort to improve the cycle life and rate capability of olivine LiCoPO4, Cr, Fe, and Si were added to produce nominal Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025. This cathode material has an energy density comparable to LiCoPO4, with markedly improved electrochemical performance. Here, we apply operando X-ray diffraction to gain an understanding of the crystallographic delithiation mechanism of this new substituted electrode material, compared to both LiCo0.75Fe0.25PO4 and LiCo0.75Fe0.25PO4. Throughout charging, the extent of solid-solution domains was significantly increased in Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 and LiCo0.75Fe0.25PO4 compared to LiCoPO4. These domains reduce the mechanical strain during electrode function, providing a clear explanation for the high durability with Co substitution. Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 operated at notably higher average potential than LiCo0.75Fe0.25PO4, which would increase the energy density of the cell. Ex situ measurements reveal the persistence of structural irreversibilities in the substituted phase after the first cycle, identifying avenues for further improvement in durability. Overall, this finding sheds light on the strategies for judicious cation substitution in LiCoPO4 electrodes to maximize the cycle life while preserving high energy density, especially compared to LiFePO4.

Authors:
 [1];  [2];  [2];  [3];  [3]; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
  3. Army Research Lab., Adelphi, MD (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
US Army Research Laboratory (USARL); USDOE Office of Science (SC)
OSTI Identifier:
1660418
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 18; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Lithium-ion battery; crystallography; electrochemistry; lithium cobalt phosphate; operando x-ray diffraction

Citation Formats

Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, and Cabana, Jordi. Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives. United States: N. p., 2020. Web. doi:10.1021/acsami.0c04110.
Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, & Cabana, Jordi. Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives. United States. https://doi.org/10.1021/acsami.0c04110
Lapping, J. G., Borkiewicz, O. J., Wiaderek, K. M., Allen, Jan L., Jow, T. Richard, and Cabana, Jordi. Thu . "Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives". United States. https://doi.org/10.1021/acsami.0c04110. https://www.osti.gov/servlets/purl/1660418.
@article{osti_1660418,
title = {Structural Changes and Reversibility Upon Deintercalation of Li from LiCoPO4 Derivatives},
author = {Lapping, J. G. and Borkiewicz, O. J. and Wiaderek, K. M. and Allen, Jan L. and Jow, T. Richard and Cabana, Jordi},
abstractNote = {In an effort to improve the cycle life and rate capability of olivine LiCoPO4, Cr, Fe, and Si were added to produce nominal Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025. This cathode material has an energy density comparable to LiCoPO4, with markedly improved electrochemical performance. Here, we apply operando X-ray diffraction to gain an understanding of the crystallographic delithiation mechanism of this new substituted electrode material, compared to both LiCo0.75Fe0.25PO4 and LiCo0.75Fe0.25PO4. Throughout charging, the extent of solid-solution domains was significantly increased in Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 and LiCo0.75Fe0.25PO4 compared to LiCoPO4. These domains reduce the mechanical strain during electrode function, providing a clear explanation for the high durability with Co substitution. Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 operated at notably higher average potential than LiCo0.75Fe0.25PO4, which would increase the energy density of the cell. Ex situ measurements reveal the persistence of structural irreversibilities in the substituted phase after the first cycle, identifying avenues for further improvement in durability. Overall, this finding sheds light on the strategies for judicious cation substitution in LiCoPO4 electrodes to maximize the cycle life while preserving high energy density, especially compared to LiFePO4.},
doi = {10.1021/acsami.0c04110},
journal = {ACS Applied Materials and Interfaces},
number = 18,
volume = 12,
place = {United States},
year = {2020},
month = {4}
}

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

Olivine LiFePO 4 : the remaining challenges for future energy storage
journal, January 2015

  • Wang, Jiajun; Sun, Xueliang
  • Energy & Environmental Science, Vol. 8, Issue 4
  • DOI: 10.1039/C4EE04016C

Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries
journal, January 1999

  • Amine, K.
  • Electrochemical and Solid-State Letters, Vol. 3, Issue 4
  • DOI: 10.1149/1.1390994

Improved cycle life of Fe-substituted LiCoPO4
journal, October 2011


Direct Observation of Antisite Defects in LiCoPO 4 Cathode Materials by Annular Dark- and Bright-Field Electron Microscopy
journal, October 2013

  • Truong, Quang Duc; Devaraju, Murukanahally Kempaiah; Tomai, Takaaki
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 20
  • DOI: 10.1021/am403018n

Vanadium Substitution of LiFePO 4 Cathode Materials To Enhance the Capacity of LiFePO 4 -Based Lithium-Ion Batteries
journal, November 2012

  • Chiang, Ching-Yu; Su, Hui-Chia; Wu, Pin-Jiun
  • The Journal of Physical Chemistry C, Vol. 116, Issue 46
  • DOI: 10.1021/jp307047w

Aliovalent Substitutions in Olivine Lithium Iron Phosphate and Impact on Structure and Properties
journal, April 2009

  • Meethong, Nonglak; Kao, Yu-Hua; Speakman, Scott A.
  • Advanced Functional Materials, Vol. 19, Issue 7, p. 1060-1070
  • DOI: 10.1002/adfm.200801617

Why Substitution Enhances the Reactivity of LiFePO 4
journal, December 2012

  • Omenya, Fredrick; Chernova, Natasha A.; Zhang, Ruibo
  • Chemistry of Materials, Vol. 25, Issue 1
  • DOI: 10.1021/cm303259j

Changes in Electronic Structure upon Li Deintercalation from LiCoPO 4 Derivatives
journal, February 2018


Crystal and magnetic structures of electrochemically delithiated Li1−xCoPO4 phases
journal, January 2009


Identifying the Structure of the Intermediate, Li 2/3 CoPO 4 , Formed during Electrochemical Cycling of LiCoPO 4
journal, October 2014

  • Strobridge, Fiona C.; Clément, Raphaële J.; Leskes, Michal
  • Chemistry of Materials, Vol. 26, Issue 21
  • DOI: 10.1021/cm502680w

X-ray Absorption Spectroscopic Study on the Electronic Structure of Li 1 - x CoPO 4 Electrodes as 4.8 V Positive Electrodes for Rechargeable Lithium Ion Batteries
journal, June 2005

  • Nakayama, Masanobu; Goto, Satoshi; Uchimoto, Yoshiharu
  • The Journal of Physical Chemistry B, Vol. 109, Issue 22
  • DOI: 10.1021/jp050569s

Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO 4
journal, February 2007

  • Bramnik, Natalia N.; Nikolowski, Kristian; Baehtz, Carsten
  • Chemistry of Materials, Vol. 19, Issue 4
  • DOI: 10.1021/cm062246u

Unraveling the Complex Delithiation Mechanisms of Olivine-Type Cathode Materials, LiFe x Co 1– x PO 4
journal, May 2016


The AMPIX electrochemical cell: a versatile apparatus for in situ X-ray scattering and spectroscopic measurements
journal, November 2012

  • Borkiewicz, Olaf J.; Shyam, Badri; Wiaderek, Kamila M.
  • Journal of Applied Crystallography, Vol. 45, Issue 6
  • DOI: 10.1107/S0021889812042720

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976