Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries

Pengfei Yan, Anmin Nie, Jianming Zheng, Yungang Zhou, Dongping Lu, Xiaofeng Zhang, Rui Xu, Ilias Belharouak, Xiaotao Zu, Jie Xiao, Khalil Amine, Jun Liu, Fei Gao, Reza Shahbazian-Yassar, Ji Guang Zhang, Chong Min Wang

Research output: Contribution to journalArticle

114 Citations (Scopus)

Abstract

Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.

Original languageEnglish
Pages (from-to)514-522
Number of pages9
JournalNano Letters
Volume15
Issue number1
DOIs
Publication statusPublished - 14 Jan 2015

Fingerprint

Surface reconstruction
electric batteries
chemical composition
Cathodes
lithium
cathodes
Manganese
Lithium
Chemical analysis
manganese
Ions
ions
Electrolytes
Anions
fading
Cations
Negative ions
Positive ions
surface layers
electric potential

Keywords

  • ion migration
  • lithium ion battery
  • LMR cathode
  • Ni surface segregation
  • surface reconstruction
  • voltage fading

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Mechanical Engineering

Cite this

Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries. / Yan, Pengfei; Nie, Anmin; Zheng, Jianming; Zhou, Yungang; Lu, Dongping; Zhang, Xiaofeng; Xu, Rui; Belharouak, Ilias; Zu, Xiaotao; Xiao, Jie; Amine, Khalil; Liu, Jun; Gao, Fei; Shahbazian-Yassar, Reza; Zhang, Ji Guang; Wang, Chong Min.

In: Nano Letters, Vol. 15, No. 1, 14.01.2015, p. 514-522.

Research output: Contribution to journalArticle

Yan, P, Nie, A, Zheng, J, Zhou, Y, Lu, D, Zhang, X, Xu, R, Belharouak, I, Zu, X, Xiao, J, Amine, K, Liu, J, Gao, F, Shahbazian-Yassar, R, Zhang, JG & Wang, CM 2015, 'Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries', Nano Letters, vol. 15, no. 1, pp. 514-522. https://doi.org/10.1021/nl5038598
Yan, Pengfei ; Nie, Anmin ; Zheng, Jianming ; Zhou, Yungang ; Lu, Dongping ; Zhang, Xiaofeng ; Xu, Rui ; Belharouak, Ilias ; Zu, Xiaotao ; Xiao, Jie ; Amine, Khalil ; Liu, Jun ; Gao, Fei ; Shahbazian-Yassar, Reza ; Zhang, Ji Guang ; Wang, Chong Min. / Evolution of lattice structure and chemical composition of the surface reconstruction layer in Li1.2Ni0.2Mn0.6O2 cathode material for lithium ion batteries. In: Nano Letters. 2015 ; Vol. 15, No. 1. pp. 514-522.
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abstract = "Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.",
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AU - Yan, Pengfei

AU - Nie, Anmin

AU - Zheng, Jianming

AU - Zhou, Yungang

AU - Lu, Dongping

AU - Zhang, Xiaofeng

AU - Xu, Rui

AU - Belharouak, Ilias

AU - Zu, Xiaotao

AU - Xiao, Jie

AU - Amine, Khalil

AU - Liu, Jun

AU - Gao, Fei

AU - Shahbazian-Yassar, Reza

AU - Zhang, Ji Guang

AU - Wang, Chong Min

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N2 - Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.

AB - Voltage and capacity fading of layer structured lithium and manganese rich (LMR) transition metal oxide is directly related to the structural and composition evolution of the material during the cycling of the battery. However, understanding such evolution at atomic level remains elusive. On the basis of atomic level structural imaging, elemental mapping of the pristine and cycled samples, and density functional theory calculations, it is found that accompanying the hoping of Li ions is the simultaneous migration of Ni ions toward the surface from the bulk lattice, leading to the gradual depletion of Ni in the bulk lattice and thickening of a Ni enriched surface reconstruction layer (SRL). Furthermore, Ni and Mn also exhibit concentration partitions within the thin layer of SRL in the cycled samples where Ni is almost depleted at the very surface of the SRL, indicating the preferential dissolution of Ni ions in the electrolyte. Accompanying the elemental composition evolution, significant structural evolution is also observed and identified as a sequential phase transition of C2/m →I41 → Spinel. For the first time, it is found that the surface facet terminated with pure cation/anion is more stable than that with a mixture of cation and anion. These findings firmly established how the elemental species in the lattice of LMR cathode transfer from the bulk lattice to surface layer and further into the electrolyte, clarifying the long-standing confusion and debate on the structure and chemistry of the surface layer and their correlation with the voltage fading and capacity decaying of LMR cathode. Therefore, this work provides critical insights for design of cathode materials with both high capacity and voltage stability during cycling.

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KW - lithium ion battery

KW - LMR cathode

KW - Ni surface segregation

KW - surface reconstruction

KW - voltage fading

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