DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells

Abstract

Fast charging of lithium-ion cells increases voltage polarization of the electrodes and creates conditions that are favorable for Li-deposition at the graphite anode. Repeated fast charging induces changes in the capacity-voltage profiles and increases the probability of lithium-plating on the electrode. This higher probability results from structural, morphological and chemical modifications that are revealed by multi-length scale characterization of graphite anodes extracted from discharged lithium-ion cells, previously charged at rates up to 6 C. The distinct differences between anodes with lithium-plating and as-prepared electrodes are clearly seen in analytical electron microscopy data. Scanning electrode microscopy (SEM) images show that the fast-charged anode is significantly thicker, apparently because of the electrolyte reduction/hydrolysis products that accumulate in electrode pores. High resolution electron microscopy (HREM) images reveal wavy graphite fringes near the particle edges. Analysis of scanning electron nanodiffraction (SEND) data reveal higher d-spacings and greater lattice rotations, indicating disorder in the graphite near the particle edges that extend about 20 nm into the bulk. The extent of this disorder is greater near larger internal pores, highlighting nanoscale heterogeneities within particles. As graphite lithiation occurs primarily through edge planes, this permanent disorder would hinder Li+ intercalation kinetics and favor Li0 plating during repeatedmore » cycling.« less

Authors:
ORCiD logo; ORCiD logo; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS)
OSTI Identifier:
1825158
Alternate Identifier(s):
OSTI ID: 1822495; OSTI ID: 1840052
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 168 Journal Issue: 10; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Energy Dispersive Spectroscopy; High Rate Charging; High Resolution Electron Microscopy; Scanning Electron Nanodiffraction; Solid Electrolyte Interphase; X-ray diffraction

Citation Formats

Pidaparthy, Saran, Rodrigues, Marco-Tulio F., Zuo, Jian-Min, and Abraham, Daniel P. Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells. United States: N. p., 2021. Web. doi:10.1149/1945-7111/ac2a7f.
Pidaparthy, Saran, Rodrigues, Marco-Tulio F., Zuo, Jian-Min, & Abraham, Daniel P. Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells. United States. https://doi.org/10.1149/1945-7111/ac2a7f
Pidaparthy, Saran, Rodrigues, Marco-Tulio F., Zuo, Jian-Min, and Abraham, Daniel P. Fri . "Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells". United States. https://doi.org/10.1149/1945-7111/ac2a7f.
@article{osti_1825158,
title = {Increased Disorder at Graphite Particle Edges Revealed by Multi-length Scale Characterization of Anodes from Fast-Charged Lithium-Ion Cells},
author = {Pidaparthy, Saran and Rodrigues, Marco-Tulio F. and Zuo, Jian-Min and Abraham, Daniel P.},
abstractNote = {Fast charging of lithium-ion cells increases voltage polarization of the electrodes and creates conditions that are favorable for Li-deposition at the graphite anode. Repeated fast charging induces changes in the capacity-voltage profiles and increases the probability of lithium-plating on the electrode. This higher probability results from structural, morphological and chemical modifications that are revealed by multi-length scale characterization of graphite anodes extracted from discharged lithium-ion cells, previously charged at rates up to 6 C. The distinct differences between anodes with lithium-plating and as-prepared electrodes are clearly seen in analytical electron microscopy data. Scanning electrode microscopy (SEM) images show that the fast-charged anode is significantly thicker, apparently because of the electrolyte reduction/hydrolysis products that accumulate in electrode pores. High resolution electron microscopy (HREM) images reveal wavy graphite fringes near the particle edges. Analysis of scanning electron nanodiffraction (SEND) data reveal higher d-spacings and greater lattice rotations, indicating disorder in the graphite near the particle edges that extend about 20 nm into the bulk. The extent of this disorder is greater near larger internal pores, highlighting nanoscale heterogeneities within particles. As graphite lithiation occurs primarily through edge planes, this permanent disorder would hinder Li+ intercalation kinetics and favor Li0 plating during repeated cycling.},
doi = {10.1149/1945-7111/ac2a7f},
journal = {Journal of the Electrochemical Society},
number = 10,
volume = 168,
place = {United States},
year = {Fri Oct 08 00:00:00 EDT 2021},
month = {Fri Oct 08 00:00:00 EDT 2021}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1149/1945-7111/ac2a7f

Save / Share:

Works referenced in this record:

Volume Changes of Graphite Anodes Revisited: A Combined Operando X-ray Diffraction and In Situ Pressure Analysis Study
journal, April 2018

  • Schweidler, Simon; de Biasi, Lea; Schiele, Alexander
  • The Journal of Physical Chemistry C, Vol. 122, Issue 16
  • DOI: 10.1021/acs.jpcc.8b01873

In Situ Neutron Diffraction Study of Lithiation Gradients in Graphite Anodes during Discharge and Relaxation
journal, January 2018

  • Wilhelm, Jörn; Seidlmayer, Stefan; Erhard, Simon
  • Journal of The Electrochemical Society, Vol. 165, Issue 9
  • DOI: 10.1149/2.1231809jes

The structure of graphitic carbons
journal, May 1951


Enlarging the d-spacing of graphite and polarizing its surface charge for driving lithium ions fast
journal, January 2014

  • Kim, Tae-Hee; Jeon, Eun Kyung; Ko, Younghoon
  • J. Mater. Chem. A, Vol. 2, Issue 20
  • DOI: 10.1039/C3TA15360F

Assessing Reaction Mechanisms of Graphite Negative Electrodes Based on Operando Synchrotron Radiation Diffraction Data
journal, April 2021

  • Fujimoto, Hiroyuki; Kiuchi, Hisao; Takagi, Shigeharu
  • Journal of The Electrochemical Society, Vol. 168, Issue 4
  • DOI: 10.1149/1945-7111/abf181

Multi-scale investigation of thickness changes in a commercial pouch type lithium-ion battery
journal, May 2016


Hydrolysis of LiPF 6 in Carbonate-Based Electrolytes for Lithium-Ion Batteries and in Aqueous Media
journal, April 2018

  • Stich, Michael; Göttlinger, Mara; Kurniawan, Mario
  • The Journal of Physical Chemistry C, Vol. 122, Issue 16
  • DOI: 10.1021/acs.jpcc.8b02080

Dynamic study of Li intercalation into graphite by in situ high energy synchrotron XRD
journal, March 2013


Fast Charging of Li-Ion Cells: Part I. Using Li/Cu Reference Electrodes to Probe Individual Electrode Potentials
journal, January 2019

  • Rodrigues, Marco-Tulio F.; Kalaga, Kaushik; Trask, Stephen E.
  • Journal of The Electrochemical Society, Vol. 166, Issue 6
  • DOI: 10.1149/2.0401906jes

In situ X-ray spatial profiling reveals uneven compression of electrode assemblies and steep lateral gradients in lithium-ion coin cells
journal, January 2020

  • Okasinski, John S.; Shkrob, Ilya A.; Chuang, Andrew
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 38
  • DOI: 10.1039/D0CP04436A

Rechargeable Alkali-Ion Battery Materials: Theory and Computation
journal, February 2020


Spatially-resolved lithiation dynamics from operando X-ray diffraction and electrochemical modeling of lithium-ion cells
journal, February 2021


Fast Charge-Driven Li Plating on Anode and Structural Degradation of Cathode
journal, October 2020

  • Son, Seoung-Bum; Robertson, David; Yang, Zhenzhen
  • Journal of The Electrochemical Society, Vol. 167, Issue 14
  • DOI: 10.1149/1945-7111/abc031

Quantifying lithium concentration gradients in the graphite electrode of Li-ion cells using operando energy dispersive X-ray diffraction
journal, January 2019

  • Yao, Koffi P. C.; Okasinski, John S.; Kalaga, Kaushik
  • Energy & Environmental Science, Vol. 12, Issue 2
  • DOI: 10.1039/C8EE02373E

Apparent Increasing Lithium Diffusion Coefficient with Applied Current in Graphite
journal, August 2020

  • Dees, Dennis W.; Rodrigues, Marco-Tulio F.; Kalaga, Kaushik
  • Journal of The Electrochemical Society, Vol. 167, Issue 12
  • DOI: 10.1149/1945-7111/abaf9f

Lithium-ion battery fast charging: A review
journal, August 2019


Lithium Acetylide: A Spectroscopic Marker for Lithium Deposition During Fast Charging of Li-Ion Cells
journal, December 2018

  • Fonseca Rodrigues, Marco-Tulio; Maroni, Victor A.; Gosztola, David J.
  • ACS Applied Energy Materials, Vol. 2, Issue 1
  • DOI: 10.1021/acsaem.8b01975

Suppression of staging in lithium-intercalated carbon by disorder in the host
journal, October 1990


Deformation and stress in electrode materials for Li-ion batteries
journal, June 2014


Rapid Lithium Diffusion in Order@Disorder Pathways for Fast‐Charging Graphite Anodes
journal, September 2020


How Fast Can a Li-Ion Battery Be Charged? Determination of Limiting Fast Charging Conditions
journal, January 2021

  • F. Rodrigues, Marco T.; Son, Seoung-Bum; Colclasure, Andrew M.
  • ACS Applied Energy Materials, Vol. 4, Issue 2
  • DOI: 10.1021/acsaem.0c03114

Enabling 6C Fast Charging of Li‐Ion Batteries with Graphite/Hard Carbon Hybrid Anodes
journal, December 2020

  • Chen, Kuan‐Hung; Goel, Vishwas; Namkoong, Min Ji
  • Advanced Energy Materials, Vol. 11, Issue 5
  • DOI: 10.1002/aenm.202003336

Graphite structure and lithium intercalation
journal, October 1997


Li intercalation in graphite: A van der Waals density-functional study
journal, October 2014


A Review of Existing and Emerging Methods for Lithium Detection and Characterization in Li‐Ion and Li‐Metal Batteries
journal, March 2021

  • Paul, Partha P.; McShane, Eric J.; Colclasure, Andrew M.
  • Advanced Energy Materials, Vol. 11, Issue 17
  • DOI: 10.1002/aenm.202100372

Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy
journal, May 2013

  • Miller, Dean J.; Proff, Christian; Wen, J. G.
  • Advanced Energy Materials, Vol. 3, Issue 8
  • DOI: 10.1002/aenm.201300015

Edge-Exfoliated Graphites for Facile Kinetics of Delithiation
journal, November 2012

  • Park, Jeong-Seok; Lee, Myeong-Hee; Jeon, In-Yup
  • ACS Nano, Vol. 6, Issue 12
  • DOI: 10.1021/nn3050227

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010


Rate-Dependent Aging Resulting from Fast Charging of Li-Ion Cells
journal, August 2020

  • Raj, Abhi; Rodrigues, Marco-Tulio F.; Abraham, Daniel P.
  • Journal of The Electrochemical Society, Vol. 167, Issue 12
  • DOI: 10.1149/1945-7111/abace9

Dependence of the electrochemical intercalation of lithium in carbons on the crystal structure of the carbon
journal, June 1993


Enabling fast charging – A battery technology gap assessment
journal, November 2017


Asymmetric Temperature Modulation for Extreme Fast Charging of Lithium-Ion Batteries
journal, December 2019


Reversible and irreversible dilation of lithium-ion battery electrodes investigated by in-situ dilatometry
journal, February 2017


Electrochemical Dilatometry of Si-Bearing Electrodes: Dimensional Changes and Experiment Design
journal, December 2020

  • Prado, Andressa Y. R.; Rodrigues, Marco-Tulio F.; Trask, Stephen E.
  • Journal of The Electrochemical Society, Vol. 167, Issue 16
  • DOI: 10.1149/1945-7111/abd465

Fast Charging of Li-Ion Cells: Part IV. Temperature Effects and “Safe Lines” to Avoid Lithium Plating
journal, September 2020

  • Rodrigues, Marco-Tulio F.; Shkrob, Ilya A.; Colclasure, Andrew M.
  • Journal of The Electrochemical Society, Vol. 167, Issue 13
  • DOI: 10.1149/1945-7111/abb70d

Expanded graphite as superior anode for sodium-ion batteries
journal, June 2014

  • Wen, Yang; He, Kai; Zhu, Yujie
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5033

Impact of Selected LiPF 6 Hydrolysis Products on the High Voltage Stability of Lithium-Ion Battery Cells
journal, November 2016

  • Wagner, Ralf; Korth, Martin; Streipert, Benjamin
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 45
  • DOI: 10.1021/acsami.6b09164

Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries
journal, July 2016

  • Billaud, Juliette; Bouville, Florian; Magrini, Tommaso
  • Nature Energy, Vol. 1, Issue 8
  • DOI: 10.1038/nenergy.2016.97

Fast Charging of Li-Ion Cells: Part II. Nonlinear Contributions to Cell and Electrode Polarization
journal, January 2019

  • Shkrob, Ilya A.; Rodrigues, Marco-Tulio Fonseca; Dees, Dennis W.
  • Journal of The Electrochemical Society, Vol. 166, Issue 14
  • DOI: 10.1149/2.0561914jes

Quantitative relationship between electron transfer rate and surface microstructure of laser-modified graphite electrodes
journal, August 1989

  • Rice, Ronald J.; McCreery, Richard L.
  • Analytical Chemistry, Vol. 61, Issue 15
  • DOI: 10.1021/ac00190a010

Opportunities and Challenges of Lithium Ion Batteries in Automotive Applications
journal, January 2021


The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study
journal, December 2016


Li plating as unwanted side reaction in commercial Li-ion cells – A review
journal, April 2018


Electrode scale and electrolyte transport effects on extreme fast charging of lithium-ion cells
journal, March 2020


Quantifying Inhomogeneity of Lithium Ion Battery Electrodes and Its Influence on Electrochemical Performance
journal, January 2018

  • Müller, Simon; Eller, Jens; Ebner, Martin
  • Journal of The Electrochemical Society, Vol. 165, Issue 2
  • DOI: 10.1149/2.0311802jes

Surface structural disordering in graphite upon lithium intercalation/deintercalation
journal, June 2010


Chemical Composition and Morphology of the Elevated Temperature SEI on Graphite
journal, January 2001

  • Andersson, A. M.; Edström, K.
  • Journal of The Electrochemical Society, Vol. 148, Issue 10
  • DOI: 10.1149/1.1397771

Lithium Diffusion in Graphitic Carbon
journal, March 2010

  • Persson, Kristin; Sethuraman, Vijay A.; Hardwick, Laurence J.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 8
  • DOI: 10.1021/jz100188d

The Effects of Defects on Localized Plating in Lithium-Ion Batteries
journal, January 2015

  • Cannarella, John; Arnold, Craig B.
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.1051507jes