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

Title: Anode Overpotential Control via Interfacial Modification: Inhibition of Lithium Plating on Graphite Anodes

Abstract

Lithium-metal deposition on graphite anodes limits the cycle life and negatively impacts safety of the current state of the art Li-ion batteries. Herein, deliberate interfacial modification of graphite electrodes via direct current (DC) magnetron sputtering of nanoscale layers of Cu and Ni is employed to increase the overpotential for Li deposition and suppress Li plating under high rate charge conditions. Due to their nanoscale, the deposited surface films have minimal impact (~0.16% decrease) on cell level theoretical energy density. Interfacial properties of the anodes are thoroughly characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and spatially resolved mapping X-ray absorption near edge structure (XANES) spectroscopy. The spectroscopic measurements indicate that the Cu and Ni coatings form oxide upon exposure to an ambient environment, but they are reduced within the electrochemical cell and remain in a metallic state. Li plating is quantified by X-ray diffraction and associated electrochemistry measurements revealing that the surface treatment effectively reduces the quantity of the plated Li metal by ~50% compared to untreated electrodes. Furthermore, these results establish an effective method using interfacial modification to achieve deliberate control of Li-metal deposition overpotential and reduction of lithium plating on graphite.

Authors:
 [1];  [1]; ORCiD logo [2];  [2];  [3];  [2];  [2];  [2]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [5]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
  4. Stony Brook Univ., NY (United States); Univ. of Pennsylvania, Philadelphia, PA (United States)
  5. Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1593243
Report Number(s):
BNL-213556-2020-JAAM
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
SC0012704; EE0007785; SC0012673
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 50; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium plating; lithium-ion battery; fast charging; interfacial modification; graphite anode

Citation Formats

Tallman, Killian R., Zhang, Bingjie, Wang, Lei, Yan, Shan, Thompson, Katherine, Tong, Xiao, Thieme, Juergen, Kiss, Andrew, Marschilok, Amy C., Takeuchi, Kenneth J., Bock, David C., and Takeuchi, Esther S. Anode Overpotential Control via Interfacial Modification: Inhibition of Lithium Plating on Graphite Anodes. United States: N. p., 2019. Web. doi:10.1021/acsami.9b16794.
Tallman, Killian R., Zhang, Bingjie, Wang, Lei, Yan, Shan, Thompson, Katherine, Tong, Xiao, Thieme, Juergen, Kiss, Andrew, Marschilok, Amy C., Takeuchi, Kenneth J., Bock, David C., & Takeuchi, Esther S. Anode Overpotential Control via Interfacial Modification: Inhibition of Lithium Plating on Graphite Anodes. United States. doi:10.1021/acsami.9b16794.
Tallman, Killian R., Zhang, Bingjie, Wang, Lei, Yan, Shan, Thompson, Katherine, Tong, Xiao, Thieme, Juergen, Kiss, Andrew, Marschilok, Amy C., Takeuchi, Kenneth J., Bock, David C., and Takeuchi, Esther S. Fri . "Anode Overpotential Control via Interfacial Modification: Inhibition of Lithium Plating on Graphite Anodes". United States. doi:10.1021/acsami.9b16794. https://www.osti.gov/servlets/purl/1593243.
@article{osti_1593243,
title = {Anode Overpotential Control via Interfacial Modification: Inhibition of Lithium Plating on Graphite Anodes},
author = {Tallman, Killian R. and Zhang, Bingjie and Wang, Lei and Yan, Shan and Thompson, Katherine and Tong, Xiao and Thieme, Juergen and Kiss, Andrew and Marschilok, Amy C. and Takeuchi, Kenneth J. and Bock, David C. and Takeuchi, Esther S.},
abstractNote = {Lithium-metal deposition on graphite anodes limits the cycle life and negatively impacts safety of the current state of the art Li-ion batteries. Herein, deliberate interfacial modification of graphite electrodes via direct current (DC) magnetron sputtering of nanoscale layers of Cu and Ni is employed to increase the overpotential for Li deposition and suppress Li plating under high rate charge conditions. Due to their nanoscale, the deposited surface films have minimal impact (~0.16% decrease) on cell level theoretical energy density. Interfacial properties of the anodes are thoroughly characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and spatially resolved mapping X-ray absorption near edge structure (XANES) spectroscopy. The spectroscopic measurements indicate that the Cu and Ni coatings form oxide upon exposure to an ambient environment, but they are reduced within the electrochemical cell and remain in a metallic state. Li plating is quantified by X-ray diffraction and associated electrochemistry measurements revealing that the surface treatment effectively reduces the quantity of the plated Li metal by ~50% compared to untreated electrodes. Furthermore, these results establish an effective method using interfacial modification to achieve deliberate control of Li-metal deposition overpotential and reduction of lithium plating on graphite.},
doi = {10.1021/acsami.9b16794},
journal = {ACS Applied Materials and Interfaces},
number = 50,
volume = 11,
place = {United States},
year = {2019},
month = {11}
}

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

Save / Share:

Works referenced in this record:

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


Understanding undesirable anode lithium plating issues in lithium-ion batteries
journal, January 2016

  • Liu, Qianqian; Du, Chunyu; Shen, Bin
  • RSC Advances, Vol. 6, Issue 91
  • DOI: 10.1039/C6RA19482F

Extreme Fast Charge Challenges for Lithium-Ion Battery: Variability and Positive Electrode Issues
journal, January 2019

  • Tanim, Tanvir R.; Dufek, Eric J.; Evans, Michael
  • Journal of The Electrochemical Society, Vol. 166, Issue 10
  • DOI: 10.1149/2.0731910jes

Electrochemical Interfaces in Electrochemical Energy Storage Systems
journal, January 2015

  • Lucht, Brett L.; Guyomard, Dominique; Edström, Kristina
  • Journal of The Electrochemical Society, Vol. 162, Issue 13
  • DOI: 10.1149/2.0171513jes

Design principles for electrolytes and interfaces for stable lithium-metal batteries
journal, September 2016


Quantification of bottlenecks to fast charging of lithium-ion-insertion cells for electric vehicles
journal, December 2014


Effects of Electrolyte Additives and Solvents on Unwanted Lithium Plating in Lithium-Ion Cells
journal, January 2017

  • Liu, Q. Q.; Petibon, R.; Du, C. Y.
  • Journal of The Electrochemical Society, Vol. 164, Issue 6
  • DOI: 10.1149/2.1081706jes

Low-Temperature Performance Improvement of Graphite Electrode by Allyl Sulfide Additive and Its Film-Forming Mechanism
journal, January 2016

  • Jurng, Sunhyung; Park, Sangjin; Yoon, Taeho
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.0051609jes

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

Nanomaterials for Rechargeable Lithium Batteries
journal, April 2008

  • Bruce, Peter G.; Scrosati, Bruno; Tarascon, Jean-Marie
  • Angewandte Chemie International Edition, Vol. 47, Issue 16, p. 2930-2946
  • DOI: 10.1002/anie.200702505

KOH etched graphite for fast chargeable lithium-ion batteries
journal, June 2015


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

Mathematical Modeling of the Lithium Deposition Overcharge Reaction in Lithium-Ion Batteries Using Carbon-Based Negative Electrodes
journal, January 1999

  • Arora, Pankaj
  • Journal of The Electrochemical Society, Vol. 146, Issue 10
  • DOI: 10.1149/1.1392512

Detection of Li Deposition by Glow Discharge Optical Emission Spectroscopy in Post-Mortem Analysis
journal, January 2015

  • Ghanbari, N.; Waldmann, T.; Kasper, M.
  • ECS Electrochemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1149/2.0041509eel

Inhomogeneous Degradation of Graphite Anodes in Li-Ion Cells: A Postmortem Study Using Glow Discharge Optical Emission Spectroscopy (GD-OES)
journal, September 2016

  • Ghanbari, Niloofar; Waldmann, Thomas; Kasper, Michael
  • The Journal of Physical Chemistry C, Vol. 120, Issue 39
  • DOI: 10.1021/acs.jpcc.6b07117

Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal
journal, January 2017


Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite-Free Lithium Metal Anodes
journal, May 2017

  • Zhang, Rui; Chen, Xiao-Ru; Chen, Xiang
  • Angewandte Chemie International Edition, Vol. 56, Issue 27
  • DOI: 10.1002/anie.201702099

Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth
journal, February 2016

  • Yan, Kai; Lu, Zhenda; Lee, Hyun-Wook
  • Nature Energy, Vol. 1, Issue 3, Article No. 16010
  • DOI: 10.1038/nenergy.2016.10

Neutron powder-diffraction studies of lithium, sodium, and potassium metal
journal, December 1989


Lattice-site location of ion-implanted impurities in copper and other fcc metals
journal, February 1976


Precision Measurements of the Lattice Constants of Twelve Common Metals
journal, June 1925


Electrical conductivity of conductive carbon blacks: influence of surface chemistry and topology
journal, July 2003


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


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Lithium intercalation and interfacial kinetics of composite anodes formed by oxidized graphite and copper
journal, May 2009


Li Mass Transfer Through a Metallic Copper Film on a Carbon Fiber during the Electrochemical Insertion/Extraction Reaction
journal, January 2001

  • Suzuki, Junji; Yoshida, Masaomi; Nakahara, Chieko
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 1
  • DOI: 10.1149/1.1344170

Interfacial Properties of Copper-coated Graphite Electrodes: Coating Thickness Dependence
journal, June 2009


Lithiation of multilayer Ni/NiO electrodes: criticality of nickel layer thicknesses on conversion reaction kinetics
journal, January 2017

  • Evmenenko, Guennadi; Fister, Timothy T.; Buchholz, D. Bruce
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 30
  • DOI: 10.1039/C7CP02448G

Exploring Chemical, Mechanical, and Electrical Functionalities of Binders for Advanced Energy-Storage Devices
journal, August 2018


Advanced analysis of copper X-ray photoelectron spectra: Advanced analysis of copper X-ray photoelectron spectra
journal, May 2017

  • Biesinger, Mark C.
  • Surface and Interface Analysis, Vol. 49, Issue 13
  • DOI: 10.1002/sia.6239

Quantitative Analysis of Copper Oxide Nanoparticle Composition and Structure by X-ray Photoelectron Spectroscopy
journal, December 2006

  • Wu, Chun-Kwei; Yin, Ming; O'Brien, Stephen
  • Chemistry of Materials, Vol. 18, Issue 25
  • DOI: 10.1021/cm061596d

X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems
journal, April 2009

  • Biesinger, Mark C.; Payne, Brad P.; Lau, Leo W. M.
  • Surface and Interface Analysis, Vol. 41, Issue 4
  • DOI: 10.1002/sia.3026

New interpretations of XPS spectra of nickel metal and oxides
journal, May 2006

  • Grosvenor, Andrew P.; Biesinger, Mark C.; Smart, Roger St. C.
  • Surface Science, Vol. 600, Issue 9
  • DOI: 10.1016/j.susc.2006.01.041

Faceted Cu 2 O structures with enhanced Li-ion battery anode performances
journal, January 2015

  • Chen, Kunfeng; Song, Shuyan; Xue, Dongfeng
  • CrystEngComm, Vol. 17, Issue 10
  • DOI: 10.1039/C4CE02340D

Synthesis of Porous NiO Nanorods as High-Performance Anode Materials for Lithium-Ion Batteries
journal, June 2016

  • Li, Qian; Huang, Gang; Yin, Dongming
  • Particle & Particle Systems Characterization, Vol. 33, Issue 10
  • DOI: 10.1002/ppsc.201600084

Ion Diffusivity through the Solid Electrolyte Interphase in Lithium-Ion Batteries
journal, January 2017

  • Benitez, Laura; Seminario, Jorge M.
  • Journal of The Electrochemical Society, Vol. 164, Issue 11
  • DOI: 10.1149/2.0181711jes

Template Free and Binderless NiO Nanowire Foam for Li-ion Battery Anodes with Long Cycle Life and Ultrahigh Rate Capability
journal, July 2016

  • Liu, Chueh; Li, Changling; Ahmed, Kazi
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep29183

Nanostructured NiO electrode for high rate Li-ion batteries
journal, January 2011

  • Wang, Xinghui; Li, Xiuwan; Sun, Xiaolei
  • Journal of Materials Chemistry, Vol. 21, Issue 11
  • DOI: 10.1039/c0jm04356g

Synthesis of different CuO nanostructures from Cu(OH) 2 nanorods through changing drying medium for lithium-ion battery anodes
journal, January 2015

  • Shi, Lin; Fan, Chenyao; Sun, Chunxiao
  • RSC Advances, Vol. 5, Issue 36
  • DOI: 10.1039/C4RA16778C

Review—SEI: Past, Present and Future
journal, January 2017

  • Peled, E.; Menkin, S.
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.1441707jes

A consideration of the morphology of electrochemically deposited lithium in an organic electrolyte
journal, August 1998


High-Precision Coulometry Studies of the Impact of Temperature and Time on SEI Formation in Li-Ion Cells
journal, January 2018

  • Ellis, L. D.; Allen, J. P.; Hill, I. G.
  • Journal of The Electrochemical Society, Vol. 165, Issue 7
  • DOI: 10.1149/2.1091807jes

On the correlation between surface chemistry and performance of graphite negative electrodes for Li ion batteries
journal, September 1999


Experimental determination of the inelastic mean free path of electrons in solids
journal, December 1989


Calculations of electron inelastic mean free paths. IX. Data for 41 elemental solids over the 50 eV to 30 keV range
journal, February 2011

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 43, Issue 3
  • DOI: 10.1002/sia.3522

Calculations of electorn inelastic mean free paths. II. Data for 27 elements over the 50-2000 eV range
journal, December 1991

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 17, Issue 13
  • DOI: 10.1002/sia.740171304

Surface film formation on electrodes in a LiCoO2/graphite cell: A step by step XPS study
journal, December 2007


Surface film formation on a graphite electrode in Li-ion batteries: AFM and XPS study
journal, January 2005

  • Leroy, S.; Blanchard, F.; Dedryvère, R.
  • Surface and Interface Analysis, Vol. 37, Issue 10
  • DOI: 10.1002/sia.2072

Interface Investigations of a Commercial Lithium Ion Battery Graphite Anode Material by Sputter Depth Profile X-ray Photoelectron Spectroscopy
journal, April 2013

  • Niehoff, Philip; Passerini, Stefano; Winter, Martin
  • Langmuir, Vol. 29, Issue 19
  • DOI: 10.1021/la400764r

Kinetics of rapid electrode reactions
journal, January 1947


Increased cycling efficiency and rate capability of copper-coated silicon anodes in lithium-ion batteries
journal, January 2011


Ni-Composite Microencapsulated Graphite as the Negative Electrode in Lithium-Ion Batteries II: Electrochemical Impedance and Self-Discharge Studies
journal, January 2000

  • Yu, P.; Ritter, J. A.; White, R. E.
  • Journal of The Electrochemical Society, Vol. 147, Issue 6, p. 2081-2085
  • DOI: 10.1149/1.1393489

Quantitative X-Ray Diffraction Analysis
journal, February 1958

  • Copeland, L. E.; Bragg, R. H.
  • Analytical Chemistry, Vol. 30, Issue 2
  • DOI: 10.1021/ac60134a011

Physical Orphaning versus Chemical Instability: Is Dendritic Electrodeposition of Li Fatal?
journal, May 2019