Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study

Abstract

In this paper, in situ high-energy synchrotron XRD studies were carried out on commercial 18650 LiFePO4 cells at different cycles to track and investigate the dynamic, chemical, and structural changes in the course of long-term cycling to elucidate the capacity fading mechanism. The results indicate that the crystalline structural deterioration of the LiFePO4 cathode and the graphite anode is unlikely to happen before capacity fades below 80% of the initial capacity. Rather, the loss of the active lithium source is the primary cause for the capacity fade, which leads to the appearance of inactive FePO4 that is proportional to the absence of the lithium source. Our in situ HESXRD studies further show that the lithium-ion insertion and deinsertion behavior of LiFePO4 continuously changed with cycling. For a fresh cell, the LiFePO4 experienced a dual-phase solid-solution behavior, whereas with increasing cycle numbers, the dynamic change, which is characteristic of the continuous decay of solid solution behavior, is obvious. Finally, the unpredicted dynamic change may result from the morphology evolution of LiFePO4 particles and the loss of the lithium source, which may be the cause of the decreased rate capability of LiFePO4 cells after long-term cycling.

Authors:
 [1];  [2];  [1];  [2];  [3];  [3];  [4]; ORCiD logo [5]; ORCiD logo [2]
+ Show Author Affiliations
  1. Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States). Dept. of Mechanical and Energy Engineering. Purdue School of Engineering and Technology; Purdue Univ., West Lafayette, IN (United States). School of Mechanical Engineering
  2. Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States). Dept. of Mechanical and Energy Engineering. Purdue School of Engineering and Technology
  3. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division. Advanced Photon Source
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Science and Engineering Division
  5. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering. School of Engineering and Applied Science
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1461322
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 5; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 18650 cell; capacity fade mechanism; in situ study; LiFePO4; synchrotron XRD

Citation Formats

Liu, Qi, Liu, Yadong, Yang, Fan, He, Hao, Xiao, Xianghui, Ren, Yang, Lu, Wenquan, Stach, Eric, and Xie, Jian. Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study. United States: N. p., 2018. Web. doi:10.1021/acsami.7b13060.
Copy to clipboard
Liu, Qi, Liu, Yadong, Yang, Fan, He, Hao, Xiao, Xianghui, Ren, Yang, Lu, Wenquan, Stach, Eric, & Xie, Jian. Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study. United States. https://doi.org/10.1021/acsami.7b13060
Copy to clipboard
Liu, Qi, Liu, Yadong, Yang, Fan, He, Hao, Xiao, Xianghui, Ren, Yang, Lu, Wenquan, Stach, Eric, and Xie, Jian. Mon . "Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study". United States. https://doi.org/10.1021/acsami.7b13060. https://www.osti.gov/servlets/purl/1461322.
Copy to clipboard
@article{osti_1461322,
title = {Capacity Fading Mechanism of the Commercial 18650 LiFePO4-Based Lithium-Ion Batteries: An in Situ Time-Resolved High-Energy Synchrotron XRD Study},
author = {Liu, Qi and Liu, Yadong and Yang, Fan and He, Hao and Xiao, Xianghui and Ren, Yang and Lu, Wenquan and Stach, Eric and Xie, Jian},
abstractNote = {In this paper, in situ high-energy synchrotron XRD studies were carried out on commercial 18650 LiFePO4 cells at different cycles to track and investigate the dynamic, chemical, and structural changes in the course of long-term cycling to elucidate the capacity fading mechanism. The results indicate that the crystalline structural deterioration of the LiFePO4 cathode and the graphite anode is unlikely to happen before capacity fades below 80% of the initial capacity. Rather, the loss of the active lithium source is the primary cause for the capacity fade, which leads to the appearance of inactive FePO4 that is proportional to the absence of the lithium source. Our in situ HESXRD studies further show that the lithium-ion insertion and deinsertion behavior of LiFePO4 continuously changed with cycling. For a fresh cell, the LiFePO4 experienced a dual-phase solid-solution behavior, whereas with increasing cycle numbers, the dynamic change, which is characteristic of the continuous decay of solid solution behavior, is obvious. Finally, the unpredicted dynamic change may result from the morphology evolution of LiFePO4 particles and the loss of the lithium source, which may be the cause of the decreased rate capability of LiFePO4 cells after long-term cycling.},
doi = {10.1021/acsami.7b13060},
journal = {ACS Applied Materials and Interfaces},
number = 5,
volume = 10,
place = {United States},
year = {Mon Jan 08 00:00:00 EST 2018},
month = {Mon Jan 08 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsami.7b13060
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: (a) Voltage profiles at 1C for the A123 LiFePO4 commercial cell at different cycle numbers; (b) The capacity retention of an A123 18650 cell with cycle numbers under normal charge/discharge conditions at a 1C rate. (c) The capacity retention of an A123 18650 cell with different cycling ratesmore » at the 1st and 2500th cycles. (d) Electrochemical impedance spectroscopy (Nyquist plot) of an A123 18650 cell at the 1st and 2500th cycles.« less
All figures and tables (8 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Introduction:  Batteries and Fuel Cells
journal, October 2004

  • Whittingham, M. Stanley; Savinell, Robert F.; Zawodzinski, Thomas
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020705e

Kinetic study on low-temperature synthesis of LiFePO4 via solid-state reaction
journal, July 2006

Electronically conductive phospho-olivines as lithium storage electrodes
journal, September 2002

  • Chung, Sung-Yoon; Bloking, Jason T.; Chiang, Yet-Ming
  • Nature Materials, Vol. 1, Issue 2, p. 123-128
  • DOI: 10.1038/nmat732

Approaching Theoretical Capacity of LiFePO[sub 4] at Room Temperature at High Rates
journal, January 2001

  • Huang, H.; Yin, S. -C.; Nazar, L. F.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 10
  • DOI: 10.1149/1.1396695

In Situ Synthesis and Properties of Carbon-Coated LiFePO[sub 4] as Li-Ion Battery Cathodes
journal, January 2005

  • Mi, C. H.; Zhao, X. B.; Cao, G. S.
  • Journal of The Electrochemical Society, Vol. 152, Issue 3
  • DOI: 10.1149/1.1852438

A High-Rate, Nanocomposite LiFePO4∕Carbon Cathode
journal, July 2005

  • Sides, Charles R.; Croce, Fausto; Young, Vaneica Y.
  • Electrochemical and Solid-State Letters, Vol. 8, Issue 9, A484-A487
  • DOI: 10.1149/1.1999916

LiFePO 4 Nanoparticles Embedded in a Nanoporous Carbon Matrix: Superior Cathode Material for Electrochemical Energy-Storage Devices
journal, May 2009

  • Wu, Xing-Long; Jiang, Ling-Yan; Cao, Fei-Fei
  • Advanced Materials, Vol. 21, Issue 25-26
  • DOI: 10.1002/adma.200802998

Capacity loss in rechargeable lithium cells during cycle life testing: The importance of determining state-of-charge
journal, December 2007

LiFePO4/gel/natural graphite cells for the BATT program
journal, June 2003

The development of low cost LiFePO4-based high power lithium-ion batteries
journal, August 2005

LiFePO4/polymer/natural graphite: low cost Li-ion batteries
journal, November 2004

Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells
journal, January 2003

  • Abraham, D. P.; Twesten, R. D.; Balasubramanian, M.
  • Journal of The Electrochemical Society, Vol. 150, Issue 11
  • DOI: 10.1149/1.1613291

Aging of lithium-ion batteries
journal, March 2004

Cyclable Lithium and Capacity Loss in Li-Ion Cells
journal, January 2005

  • Christensen, John; Newman, John
  • Journal of The Electrochemical Society, Vol. 152, Issue 4
  • DOI: 10.1149/1.1870752

Calendar life performance of pouch lithium-ion cells
journal, March 2005

Degradation Mechanism and Life Prediction of Lithium-Ion Batteries
journal, January 2006

  • Yoshida, Toshihiro; Takahashi, Michio; Morikawa, Satoshi
  • Journal of The Electrochemical Society, Vol. 153, Issue 3
  • DOI: 10.1149/1.2162467

Simulation of capacity loss in carbon electrode for lithium-ion cells during storage
journal, March 2007

Aging of a Commercial Graphite/LiFePO4 Cell
journal, January 2011

  • Safari, M.; Delacourt, C.
  • Journal of The Electrochemical Society, Vol. 158, Issue 10
  • DOI: 10.1149/1.3614529

Aging Mechanisms of LiFePO[sub 4] Batteries Deduced by Electrochemical and Structural Analyses
journal, January 2010

  • Liu, Ping; Wang, John; Hicks-Garner, Jocelyn
  • Journal of The Electrochemical Society, Vol. 157, Issue 4
  • DOI: 10.1149/1.3294790

Aging Mechanisms of LiFePO 4 // Graphite Cells Studied by XPS: Redox Reaction and Electrode/Electrolyte Interfaces
journal, January 2012

  • Castro, L.; Dedryvère, R.; Ledeuil, J. -B.
  • Journal of The Electrochemical Society, Vol. 159, Issue 4
  • DOI: 10.1149/2.024204jes

Effects of temperature on charge/discharge behaviors of LiFePO4 cathode for Li-ion batteries
journal, January 2012

Making Li-metal electrodes rechargeable by controlling the dendrite growth direction
journal, June 2017

In Situ X-ray Near-Edge Absorption Spectroscopy Investigation of the State of Charge of All-Vanadium Redox Flow Batteries
journal, September 2014

  • Jia, Chuankun; Liu, Qi; Sun, Cheng-Jun
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 20
  • DOI: 10.1021/am5046422

Graphene-modified nanostructured vanadium pentoxide hybrids with extraordinary electrochemical performance for Li-ion batteries
journal, January 2015

  • Liu, Qi; Li, Zhe-Fei; Liu, Yadong
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7127

New phases and phase transitions observed in Li1−xCoO2 during charge: in situ synchrotron X-ray diffraction studies
journal, February 2000

Failure Investigation of LiFePO 4 Cells in Over-Discharge Conditions
journal, January 2013

  • He, Hao; Liu, Yadong; Liu, Qi
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.039306jes

Failure Investigation of LiFePO 4 Cells under Overcharge Conditions
journal, January 2012

  • Xu, Fan; He, Hao; Liu, YaDong
  • Journal of The Electrochemical Society, Vol. 159, Issue 5
  • DOI: 10.1149/2.024206jes

Capacity and power fading mechanism identification from a commercial cell evaluation
journal, March 2007

Identify capacity fading mechanism in a commercial LiFePO4 cell
journal, October 2009

Identifying battery aging mechanisms in large format Li ion cells
journal, April 2011

Cycling performance of low-cost lithium ion batteries with natural graphite and LiFePO4
journal, June 2003

Failure Study of Commercial LiFePO 4 Cells in over-Discharge Conditions Using Electrochemical Impedance Spectroscopy
journal, January 2014

  • Liu, Yadong; Liu, Qi; Li, Zhefei
  • Journal of The Electrochemical Society, Vol. 161, Issue 4
  • DOI: 10.1149/2.090404jes

Failure Study of Commercial LiFePO 4 Cells in Overcharge Conditions Using Electrochemical Impedance Spectroscopy
journal, January 2015

  • Liu, Yadong; Xie, Jian
  • Journal of The Electrochemical Society, Vol. 162, Issue 10
  • DOI: 10.1149/2.0911510jes

Kinetic analysis on LiFePO4 thin films by CV, GITT, and EIS
journal, May 2011

Mechanisms for Lithium Insertion in Carbonaceous Materials
journal, October 1995

In Situ Observation of Strains during Lithiation of a Graphite Electrode
journal, January 2010

  • Qi, Yue; Harris, Stephen J.
  • Journal of The Electrochemical Society, Vol. 157, Issue 6, p. A741-A747
  • DOI: 10.1149/1.3377130

Threefold Increase in the Young’s Modulus of Graphite Negative Electrode during Lithium Intercalation
journal, January 2010

  • Qi, Yue; Guo, Haibo; Hector, Louis G.
  • Journal of The Electrochemical Society, Vol. 157, Issue 5
  • DOI: 10.1149/1.3327913

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

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Kinetics of non-equilibrium lithium incorporation in LiFePO4
journal, July 2011

  • Malik, Rahul; Zhou, Fei; Ceder, G.
  • Nature Materials, Vol. 10, Issue 8
  • DOI: 10.1038/nmat3065

Rate-Dependent, Li-Ion Insertion/Deinsertion Behavior of LiFePO 4 Cathodes in Commercial 18650 LiFePO 4 Cells
journal, February 2014

  • Liu, Qi; He, Hao; Li, Zhe-Fei
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 5
  • DOI: 10.1021/am405150c

Direct Evidence of Concurrent Solid-Solution and Two-Phase Reactions and the Nonequilibrium Structural Evolution of LiFePO 4
journal, April 2012

  • Sharma, Neeraj; Guo, Xianwei; Du, Guodong
  • Journal of the American Chemical Society, Vol. 134, Issue 18
  • DOI: 10.1021/ja301187u
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries
    journal, July 2018

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

    SiOC nanolayer wrapped 3D interconnected graphene sponge as a high-performance anode for lithium ion batteries
    journal, January 2018

    • Sang, Zhiyuan; Zhao, Zhihao; Su, Dong
    • Journal of Materials Chemistry A, Vol. 6, Issue 19
    • DOI: 10.1039/c8ta01570h

    Application of Operando X-ray Diffractometry in Various Aspects of the Investigations of Lithium/Sodium-Ion Batteries
    journal, November 2018

    • Zhu, Wen; Wang, Yuesheng; Liu, Dongqiang
    • Energies, Vol. 11, Issue 11
    • DOI: 10.3390/en11112963
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 10)figure
      Figure 2 (p. 11)figure
      Figure 3 (p. 12)figure
      Figure 4 (p. 14)figure
      Figure 5 (p. 16)figure
      Table 1 (p. 17)table
      Figure 6 (p. 18)figure
      Figure 7 (p. 22)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: