skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Changes in Electronic Structure upon Li Deintercalation from LiCoPO4 Derivatives

Abstract

On the path toward the design of Li-ion batteries with increased energy densities, efforts are focused on the development of positive electrodes that can maximize the voltage of the full cell. However, the development of novel materials that operate at high voltage, while also showing high efficiency and meeting strict safety standards, is an ongoing challenge. LiCoPO4 is being explored as a possible candidate, as the Co2+/3+ redox couple operates at 4.8 V versus Li+/Li0. The presence of phosphate groups is typically expected to stabilize the compound against oxygen loss, yet the changes in Co-O bonding upon Li extraction have not been ascertained. In addition, LiCoPO4 is riddled with problems relating to poor transport and strain in the crystal structure of the delithiated phase, which handicap its use as a high-voltage electrode. In this work, substituting ions to generate Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 is found to stabilize both the electronic structure and crystal structure and, therefore, substantially improve the ability to fully utilize the redox capacity of the material. A thorough study by spectroscopic tools, combined with computations of the electronic structure, was used to probe changes in chemical bonding. The measurements revealed the existence of redox gradients between surface and bulk thatmore » are common in other materials that react at high potential. Lastly, the study offers a comprehensive understanding of the fundamental reactions in LiCoPO4-type frameworks, while further demonstrating that ion substitution is an effective tool for improving their performance.« less

Authors:
 [1];  [2];  [2];  [2];  [3];  [4];  [1];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States)
  2. U.S. Army Research Lab., Adelphi, MD (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Naval Research Lab., Washington, D.C. (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
U.S. Army Research Laboratory; US Department of the Navy, Office of Naval Research (ONR); USDOE
OSTI Identifier:
1464630
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 6; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lapping, Jacob G., Delp, Samuel A., Allen, Joshua L., Allen, Jan L., Freeland, John W., Johannes, Michelle D., Hu, Linhua, Tran, Dat T., Jow, T. Richard, and Cabana, Jordi. Changes in Electronic Structure upon Li Deintercalation from LiCoPO4 Derivatives. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.7b04739.
Lapping, Jacob G., Delp, Samuel A., Allen, Joshua L., Allen, Jan L., Freeland, John W., Johannes, Michelle D., Hu, Linhua, Tran, Dat T., Jow, T. Richard, & Cabana, Jordi. Changes in Electronic Structure upon Li Deintercalation from LiCoPO4 Derivatives. United States. https://doi.org/10.1021/acs.chemmater.7b04739
Lapping, Jacob G., Delp, Samuel A., Allen, Joshua L., Allen, Jan L., Freeland, John W., Johannes, Michelle D., Hu, Linhua, Tran, Dat T., Jow, T. Richard, and Cabana, Jordi. Fri . "Changes in Electronic Structure upon Li Deintercalation from LiCoPO4 Derivatives". United States. https://doi.org/10.1021/acs.chemmater.7b04739. https://www.osti.gov/servlets/purl/1464630.
@article{osti_1464630,
title = {Changes in Electronic Structure upon Li Deintercalation from LiCoPO4 Derivatives},
author = {Lapping, Jacob G. and Delp, Samuel A. and Allen, Joshua L. and Allen, Jan L. and Freeland, John W. and Johannes, Michelle D. and Hu, Linhua and Tran, Dat T. and Jow, T. Richard and Cabana, Jordi},
abstractNote = {On the path toward the design of Li-ion batteries with increased energy densities, efforts are focused on the development of positive electrodes that can maximize the voltage of the full cell. However, the development of novel materials that operate at high voltage, while also showing high efficiency and meeting strict safety standards, is an ongoing challenge. LiCoPO4 is being explored as a possible candidate, as the Co2+/3+ redox couple operates at 4.8 V versus Li+/Li0. The presence of phosphate groups is typically expected to stabilize the compound against oxygen loss, yet the changes in Co-O bonding upon Li extraction have not been ascertained. In addition, LiCoPO4 is riddled with problems relating to poor transport and strain in the crystal structure of the delithiated phase, which handicap its use as a high-voltage electrode. In this work, substituting ions to generate Li1.025Co0.84Fe0.10Cr0.05Si0.01(PO4)1.025 is found to stabilize both the electronic structure and crystal structure and, therefore, substantially improve the ability to fully utilize the redox capacity of the material. A thorough study by spectroscopic tools, combined with computations of the electronic structure, was used to probe changes in chemical bonding. The measurements revealed the existence of redox gradients between surface and bulk that are common in other materials that react at high potential. Lastly, the study offers a comprehensive understanding of the fundamental reactions in LiCoPO4-type frameworks, while further demonstrating that ion substitution is an effective tool for improving their performance.},
doi = {10.1021/acs.chemmater.7b04739},
journal = {Chemistry of Materials},
number = 6,
volume = 30,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Galvanostatic charging data for LiCoPO4 (black), Li1.025Co0.084Fe0.10Cr0.05Si0.01(PO4)1.025 (blue) and LiFe0.25Co0.75PO4 (green). All electrodes were cycled at a rate of C/10.

Save / Share:

Works referenced in this record:

Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr5003003

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

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


Reasons for capacity fading of LiCoPO4 cathodes in LiPF6 containing electrolyte solutions
journal, February 2012


Revealing Electrochemically Induced Antisite Defects in LiCoPO 4 : Evolution upon Cycling
journal, January 2015

  • Boulineau, Adrien; Gutel, Thibaut
  • Chemistry of Materials, Vol. 27, Issue 3
  • DOI: 10.1021/cm503716p

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

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

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

Unit-cell refinement from powder diffraction scans
journal, December 1981


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Projector augmented-wave method
journal, December 1994


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

Formation of Small Hole Polarons in Olivine Phosphate Cathode Materials
journal, May 2012

  • Johannes, Michelle D.; Hoang, Khang; Allen, Jan L.
  • ECS Transactions, Vol. 41, Issue 29
  • DOI: 10.1149/1.3696682

Transport properties of LiCoPO4 and Fe-substituted LiCoPO4
journal, May 2014


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

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

Chemistry and electrochemistry of composite LiFePO4 materials for secondary lithium batteries
journal, May 2006

  • Franger, S.; Benoit, C.; Bourbon, C.
  • Journal of Physics and Chemistry of Solids, Vol. 67, Issue 5-6
  • DOI: 10.1016/j.jpcs.2006.01.066

Probing depth of soft x-ray absorption spectroscopy measured in total-electron-yield mode
journal, January 1992

  • Abbate, M.; Goedkoop, J. B.; de Groot, F. M. F.
  • Surface and Interface Analysis, Vol. 18, Issue 1
  • DOI: 10.1002/sia.740180111

Influence of crystal structure, ligand environment and morphology on Co L -edge XAS spectral characteristics in cobalt compounds
journal, October 2015


Determination of absorption coefficients for concentrated samples by fluorescence detection
journal, June 1993


Electronic structure and spin-state transition of LaCoO 3
journal, June 1993


Phase Transformation and Lithiation Effect on Electronic Structure of Li x FePO 4 : An In-Depth Study by Soft X-ray and Simulations
journal, August 2012

  • Liu, Xiaosong; Liu, Jun; Qiao, Ruimin
  • Journal of the American Chemical Society, Vol. 134, Issue 33
  • DOI: 10.1021/ja303225e

Electronic structure of phospho-olivines LixFePO4 (x=0,1) from soft-x-ray-absorption and -emission spectroscopies
journal, November 2005

  • Augustsson, A.; Zhuang, G. V.; Butorin, S. M.
  • The Journal of Chemical Physics, Vol. 123, Issue 18
  • DOI: 10.1063/1.2107387

    Works referencing / citing this record:

    Improving the Rate Capability of LiFePO 4 Electrode by Controlling Particle Size Distribution
    journal, January 2019

    • Zhang, Yin; Alarco, Jose A.; Nerkar, Jawahar Y.
    • Journal of The Electrochemical Society, Vol. 166, Issue 16
    • DOI: 10.1149/2.0621916jes

    Understanding and development of olivine LiCoPO 4 cathode materials for lithium-ion batteries
    journal, January 2018

    • Zhang, Min; Garcia-Araez, Nuria; Hector, Andrew L.
    • Journal of Materials Chemistry A, Vol. 6, Issue 30
    • DOI: 10.1039/c8ta04063j