Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries

Meng Gu, Ilias Belharouak, Jianming Zheng, Huiming Wu, Jie Xiao, Arda Genc, Khalil Amine, Suntharampillai Thevuthasan, Donald R. Baer, Ji Guang Zhang, Nigel D. Browning, Jun Liu, Chongmin Wang

Research output: Contribution to journalArticle

461 Citations (Scopus)

Abstract

Pristine Li-rich layered cathodes, such as Li1.2Ni 0.2Mn0.6O2 and Li1.2Ni 0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2R3̄m and Li 2MO3C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2R3̄m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF3-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.

Original languageEnglish
Pages (from-to)760-767
Number of pages8
JournalACS Nano
Volume7
Issue number1
DOIs
Publication statusPublished - 22 Jan 2013
Externally publishedYes

Fingerprint

spinel
electric batteries
Cathodes
cathodes
Coatings
composite materials
Composite materials
Crystal lattices
Vacancies
Transition metals
Metal ions
Condensation
ions
Lithium
Nanoparticles
Cracks
Ions
cycles
breakdown
coatings

Keywords

  • layered structure
  • lithium ion battery
  • phase transformation
  • spinel formation

ASJC Scopus subject areas

  • Engineering(all)
  • Materials Science(all)
  • Physics and Astronomy(all)

Cite this

Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries. / Gu, Meng; Belharouak, Ilias; Zheng, Jianming; Wu, Huiming; Xiao, Jie; Genc, Arda; Amine, Khalil; Thevuthasan, Suntharampillai; Baer, Donald R.; Zhang, Ji Guang; Browning, Nigel D.; Liu, Jun; Wang, Chongmin.

In: ACS Nano, Vol. 7, No. 1, 22.01.2013, p. 760-767.

Research output: Contribution to journalArticle

Gu, M, Belharouak, I, Zheng, J, Wu, H, Xiao, J, Genc, A, Amine, K, Thevuthasan, S, Baer, DR, Zhang, JG, Browning, ND, Liu, J & Wang, C 2013, 'Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries', ACS Nano, vol. 7, no. 1, pp. 760-767. https://doi.org/10.1021/nn305065u
Gu, Meng ; Belharouak, Ilias ; Zheng, Jianming ; Wu, Huiming ; Xiao, Jie ; Genc, Arda ; Amine, Khalil ; Thevuthasan, Suntharampillai ; Baer, Donald R. ; Zhang, Ji Guang ; Browning, Nigel D. ; Liu, Jun ; Wang, Chongmin. / Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries. In: ACS Nano. 2013 ; Vol. 7, No. 1. pp. 760-767.
@article{0f50c0a7849d4cc69d82d026893916dd,
title = "Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries",
abstract = "Pristine Li-rich layered cathodes, such as Li1.2Ni 0.2Mn0.6O2 and Li1.2Ni 0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2R3̄m and Li 2MO3C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2R3̄m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF3-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.",
keywords = "layered structure, lithium ion battery, phase transformation, spinel formation",
author = "Meng Gu and Ilias Belharouak and Jianming Zheng and Huiming Wu and Jie Xiao and Arda Genc and Khalil Amine and Suntharampillai Thevuthasan and Baer, {Donald R.} and Zhang, {Ji Guang} and Browning, {Nigel D.} and Jun Liu and Chongmin Wang",
year = "2013",
month = "1",
day = "22",
doi = "10.1021/nn305065u",
language = "English",
volume = "7",
pages = "760--767",
journal = "ACS Nano",
issn = "1936-0851",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Formation of the spinel phase in the layered composite cathode used in Li-Ion batteries

AU - Gu, Meng

AU - Belharouak, Ilias

AU - Zheng, Jianming

AU - Wu, Huiming

AU - Xiao, Jie

AU - Genc, Arda

AU - Amine, Khalil

AU - Thevuthasan, Suntharampillai

AU - Baer, Donald R.

AU - Zhang, Ji Guang

AU - Browning, Nigel D.

AU - Liu, Jun

AU - Wang, Chongmin

PY - 2013/1/22

Y1 - 2013/1/22

N2 - Pristine Li-rich layered cathodes, such as Li1.2Ni 0.2Mn0.6O2 and Li1.2Ni 0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2R3̄m and Li 2MO3C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2R3̄m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF3-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.

AB - Pristine Li-rich layered cathodes, such as Li1.2Ni 0.2Mn0.6O2 and Li1.2Ni 0.1Mn0.525Co0.175O2, were identified to exist in two different structures: LiMO2R3̄m and Li 2MO3C2/m phases. Upon 300 cycles of charge/discharge, both phases gradually transform to the spinel structure. The transition from LiMO2R3̄m to spinel is accomplished through the migration of transition metal ions to the Li site without breaking down the lattice, leading to the formation of mosaic structured spinel grains within the parent particle. In contrast, transition from Li2MO3C2/m to spinel involves removal of Li+ and O2-, which produces large lattice strain and leads to the breakdown of the parent lattice. The newly formed spinel grains show random orientation within the same particle. Cracks and pores were also noticed within some layered nanoparticles after cycling, which is believed to be the consequence of the lattice breakdown and vacancy condensation upon removal of lithium ions. The AlF3-coating can partially relieve the spinel formation in the layered structure during cycling, resulting in a slower capacity decay. However, the AlF3-coating on the layered structure cannot ultimately stop the spinel formation. The observation of structure transition characteristics discussed in this paper provides direct explanation for the observed gradual capacity loss and poor rate performance of the layered composite. It also provides clues about how to improve the materials structure in order to improve electrochemical performance.

KW - layered structure

KW - lithium ion battery

KW - phase transformation

KW - spinel formation

UR - http://www.scopus.com/inward/record.url?scp=84872831090&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84872831090&partnerID=8YFLogxK

U2 - 10.1021/nn305065u

DO - 10.1021/nn305065u

M3 - Article

VL - 7

SP - 760

EP - 767

JO - ACS Nano

JF - ACS Nano

SN - 1936-0851

IS - 1

ER -