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

Title: Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes

Abstract

Here, surface coating of cathode materials with Al2O3 has been shown to be a promising method for cathode stabilization and improved cycling performance at high operating voltages. However, a detailed understanding on how coating process and cathode composition changes the chemical composition, morphology and distribution of coating within cathode interface and bulk lattice, is still missing. In this study, we use a wet-chemical method to synthesize a series of Al2O3-coated LiNi0.5Co0.2Mn0.3O2 and LiCoO2 cathodes treated under various annealing temperatures and a combination of structural characterization techniques to understand the composition, homogeneity and morphology of coating layer and the bulk cathode. Nuclear magnetic resonance and electron microscopy results reveal that the nature of the interface is highly depended on the annealing temperature and cathode composition. For Al2O3-coated LiNi0.5Co0.2Mn0.3O2, higher annealing temperature leads to more homogeneous and more closely attached coating on cathode materials, corresponding to better electrochemical performance. Lower Al2O3 coating content is found to be helpful to further improve the initial capacity and cyclability, which can greatly outperform the pristine cathode material. For Al2O3-coated LiCoO2, the incorporation of Al into the cathode lattice is observed after annealing at high temperatures, implying the transformation from “surface coatings” to “dopants”, which ismore » not observed for LiNi0.5Co0.2Mn0.3O2. As a result, Al2O3-coated LiCoO2 annealed at higher temperature shows similar initial capacity but lower retention compared to that annealed at a lower temperature, due to the intercalation of surface alumina into the bulk layered structure forming a solid solution.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1374597
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 17; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; 27Al MAS NMR; Al2O3 coating; coating vs doping; LCO; NMC; TEM

Citation Formats

Han, Binghong, Paulauskas, Tadas, Key, Baris, Peebles, Cameron, Park, Joong Sun, Klie, Robert F., Vaughey, John T., and Dogan, Fulya. Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes. United States: N. p., 2017. Web. doi:10.1021/acsami.7b00595.
Han, Binghong, Paulauskas, Tadas, Key, Baris, Peebles, Cameron, Park, Joong Sun, Klie, Robert F., Vaughey, John T., & Dogan, Fulya. Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes. United States. https://doi.org/10.1021/acsami.7b00595
Han, Binghong, Paulauskas, Tadas, Key, Baris, Peebles, Cameron, Park, Joong Sun, Klie, Robert F., Vaughey, John T., and Dogan, Fulya. Fri . "Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes". United States. https://doi.org/10.1021/acsami.7b00595. https://www.osti.gov/servlets/purl/1374597.
@article{osti_1374597,
title = {Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes},
author = {Han, Binghong and Paulauskas, Tadas and Key, Baris and Peebles, Cameron and Park, Joong Sun and Klie, Robert F. and Vaughey, John T. and Dogan, Fulya},
abstractNote = {Here, surface coating of cathode materials with Al2O3 has been shown to be a promising method for cathode stabilization and improved cycling performance at high operating voltages. However, a detailed understanding on how coating process and cathode composition changes the chemical composition, morphology and distribution of coating within cathode interface and bulk lattice, is still missing. In this study, we use a wet-chemical method to synthesize a series of Al2O3-coated LiNi0.5Co0.2Mn0.3O2 and LiCoO2 cathodes treated under various annealing temperatures and a combination of structural characterization techniques to understand the composition, homogeneity and morphology of coating layer and the bulk cathode. Nuclear magnetic resonance and electron microscopy results reveal that the nature of the interface is highly depended on the annealing temperature and cathode composition. For Al2O3-coated LiNi0.5Co0.2Mn0.3O2, higher annealing temperature leads to more homogeneous and more closely attached coating on cathode materials, corresponding to better electrochemical performance. Lower Al2O3 coating content is found to be helpful to further improve the initial capacity and cyclability, which can greatly outperform the pristine cathode material. For Al2O3-coated LiCoO2, the incorporation of Al into the cathode lattice is observed after annealing at high temperatures, implying the transformation from “surface coatings” to “dopants”, which is not observed for LiNi0.5Co0.2Mn0.3O2. As a result, Al2O3-coated LiCoO2 annealed at higher temperature shows similar initial capacity but lower retention compared to that annealed at a lower temperature, due to the intercalation of surface alumina into the bulk layered structure forming a solid solution.},
doi = {10.1021/acsami.7b00595},
journal = {ACS Applied Materials and Interfaces},
number = 17,
volume = 9,
place = {United States},
year = {Fri Apr 07 00:00:00 EDT 2017},
month = {Fri Apr 07 00:00:00 EDT 2017}
}

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

Citation Metrics:
Cited by: 104 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Performance of layered Li(Ni1/3Co1/3Mn1/3)O2 as cathode for Li-ion batteries
journal, November 2002


Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013

  • Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
  • Advanced Energy Materials, Vol. 4, Issue 1
  • DOI: 10.1002/aenm.201300787

Synthesis, Characterization, and Electrochemical Behavior of Improved Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] (0.1≤x≤0.5)
journal, January 2003

  • Jouanneau, S.; Eberman, K. W.; Krause, L. J.
  • Journal of The Electrochemical Society, Vol. 150, Issue 12
  • DOI: 10.1149/1.1622956

Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries
journal, January 2001

  • Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 12
  • DOI: 10.1149/1.1413182

Novel lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for advanced lithium-ion batteries
journal, June 2003


Layered Lithium Insertion Material of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 for Lithium-Ion Batteries
journal, July 2001

  • Ohzuku, Tsutomu; Makimura, Yoshinari
  • Chemistry Letters, Vol. 30, Issue 7
  • DOI: 10.1246/cl.2001.642

Synthesis and characterization of LiNi1−x−yCoxMnyO2 as the cathode materials of secondary lithium batteries
journal, September 1999


Influence of the synthesis route on the electrochemical properties of LiNi0.425Mn0.425Co0.15O2
journal, May 2005


Structural and electrochemical behavior of LiMn0.4Ni0.4Co0.2O2
journal, March 2007


Electrochemical Evaluation and Structural Characterization of Commercial LiCoO[sub 2] Surfaces Modified with MgO for Lithium-Ion Batteries
journal, January 2002

  • Wang, Zhaoxiang; Wu, Chuan; Liu, Lijun
  • Journal of The Electrochemical Society, Vol. 149, Issue 4
  • DOI: 10.1149/1.1456919

A simple mechano-thermal coating process for improved lithium battery cathode materials
journal, May 2004


Electrochemical Performance and Surface Properties of Bare and TiO 2 -Coated Cathode Materials in Lithium-Ion Batteries
journal, November 2004

  • Zhang, Zhongru; Gong, Zhengliang; Yang, Yong
  • The Journal of Physical Chemistry B, Vol. 108, Issue 45
  • DOI: 10.1021/jp046980h

Improvement of Degradation at Elevated Temperature and at High State-of-Charge Storage by ZrO[sub 2] Coating on LiCoO[sub 2]
journal, January 2006

  • Miyashiro, Hajime; Yamanaka, Atsushi; Tabuchi, Mitsuharu
  • Journal of The Electrochemical Society, Vol. 153, Issue 2
  • DOI: 10.1149/1.2149306

Effects of ZnO coating on electrochemical performance and thermal stability of LiCoO2 as cathode material for lithium-ion batteries
journal, January 2010


Novel LiCoO2 Cathode Material with Al2O3 Coating for a Li Ion Cell
journal, December 2000

  • Cho, Jaephil; Kim, Yong Jeong; Park, Byungwoo
  • Chemistry of Materials, Vol. 12, Issue 12, p. 3788-3791
  • DOI: 10.1021/cm000511k

Al2O3-coated LiCoO2 as cathode material for lithium ion batteries
journal, December 2002


High Capacity Surface-Modified LiCoO[sub 2] Cathodes for Lithium-Ion Batteries
journal, January 2003

  • Kannan, A. M.; Rabenberg, L.; Manthiram, A.
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 1
  • DOI: 10.1149/1.1526782

Electrochemical and solid-state NMR studies on LiCoO2 coated with Al2O3 derived from carboxylate-alumoxane
journal, December 2006


Surface-modified concentration-gradient Ni-rich layered oxide cathodes for high-energy lithium-ion batteries
journal, May 2015


Role of Alumina Coating on Li−Ni−Co−Mn−O Particles as Positive Electrode Material for Lithium-Ion Batteries
journal, July 2005

  • Myung, Seung-Taek; Izumi, Kentarou; Komaba, Shinichi
  • Chemistry of Materials, Vol. 17, Issue 14, p. 3695-3704
  • DOI: 10.1021/cm050566s

Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Electrochemical effects of ALD surface modification on combustion synthesized LiNi1/3Mn1/3Co1/3O2 as a layered-cathode material
journal, March 2011


Ultrathin Coatings on Nano-LiCoO2 for Li-Ion Vehicular Applications
journal, February 2011

  • Scott, Isaac D.; Jung, Yoon Seok; Cavanagh, Andrew S.
  • Nano Letters, Vol. 11, Issue 2, p. 414-418
  • DOI: 10.1021/nl1030198

Ultrathin Direct Atomic Layer Deposition on Composite Electrodes for Highly Durable and Safe Li-Ion Batteries
journal, April 2010

  • Jung, Yoon Seok; Cavanagh, Andrew S.; Riley, Leah A.
  • Advanced Materials, Vol. 22, Issue 19
  • DOI: 10.1002/adma.200903951

Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1– yz Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy
journal, June 2016

  • Dogan, Fulya; Vaughey, John T.; Iddir, Hakim
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 26
  • DOI: 10.1021/acsami.6b04516

Characterization of interphases appearing on LiNi0.5Mn0.5O2 using 7Li MAS NMR
journal, April 2009


Detection of surface layers using 7Li MAS NMR
journal, January 2008

  • Dupré, Nicolas; Martin, Jean-Frédéric; Guyomard, Dominique
  • Journal of Materials Chemistry, Vol. 18, Issue 36
  • DOI: 10.1039/b807778a

Cobalt(III) Effect on 27 Al NMR Chemical Shifts in LiAl x Co 1 - x O 2
journal, August 2001

  • Gaudin, E.; Taulelle, F.; Stoyanova, R.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 34
  • DOI: 10.1021/jp0105948

How Do Li Atoms Pass through the Al 2 O 3 Coating Layer during Lithiation in Li-ion Batteries?
journal, July 2013

  • Jung, Sung Chul; Han, Young-Kyu
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 16
  • DOI: 10.1021/jz401231e

Works referencing / citing this record:

Editors' Choice—Coating-Dependent Electrode-Electrolyte Interface for Ni-Rich Positive Electrodes in Li-Ion Batteries
journal, January 2019

  • Karayaylali, Pinar; Tatara, Ryoichi; Zhang, Yirui
  • Journal of The Electrochemical Society, Vol. 166, Issue 6
  • DOI: 10.1149/2.0461906jes

Development of Electrolytes for Single Crystal NMC532/Artificial Graphite Cells with Long Lifetime
journal, January 2018

  • Li, Jing; Li, Hongyang; Stone, Will
  • Journal of The Electrochemical Society, Vol. 165, Issue 3
  • DOI: 10.1149/2.0971803jes

Horizons for Li-Ion Batteries Relevant to Electro-Mobility: High-Specific-Energy Cathodes and Chemically Active Separators
journal, July 2018

  • Susai, Francis Amalraj; Sclar, Hadar; Shilina, Yuliya
  • Advanced Materials, Vol. 30, Issue 41
  • DOI: 10.1002/adma.201801348

Ni–Al–Cr superalloy as high temperature cathode current collector for advanced thin film Li batteries
journal, January 2018

  • Filippin, Alejandro N.; Lin, Tzu-Ying; Rawlence, Michael
  • RSC Advances, Vol. 8, Issue 36
  • DOI: 10.1039/c8ra02461h

Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches
journal, April 2019

  • Sharifi‐Asl, Soroosh; Lu, Jun; Amine, Khalil
  • Advanced Energy Materials, Vol. 9, Issue 22
  • DOI: 10.1002/aenm.201900551

Controllable Cathode–Electrolyte Interface of Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 for Lithium Ion Batteries: A Review
journal, August 2019

  • Maleki Kheimeh Sari, Hirbod; Li, Xifei
  • Advanced Energy Materials, Vol. 9, Issue 39
  • DOI: 10.1002/aenm.201901597

Influence of Coating Protocols on Alumina-Coated Cathode Material: Atomic Layer Deposition versus Wet-Chemical Coating
journal, January 2019

  • Han, Binghong; Key, Baris; Lipton, Andrew S.
  • Journal of The Electrochemical Society, Vol. 166, Issue 15
  • DOI: 10.1149/2.0681915jes

Tailoring Alumina Based Interphases on Lithium Ion Cathodes
journal, January 2018

  • Han, Binghong; Dunlop, Alison R.; Trask, Stephen E.
  • Journal of The Electrochemical Society, Vol. 165, Issue 14
  • DOI: 10.1149/2.0211814jes

Ni-Al-Cr superalloy as high temperature cathode current collector for advanced thin film Li batteries
text, January 2018