Nonstoichiometric layered LixMnyO2 intercalation electrodes: a multiple dopant strategy

Alastair D. Robertson*, A. Robert Armstrong, Allan J. Paterson, Morven J. Duncan, Peter G. Bruce

*Corresponding author for this work

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Layered LixMnyO2 materials with the O3 (α-NaFeO2) structure have been synthesised by a low temperature ion exchange route from the corresponding sodium compounds. Previous studies have concentrated upon the undoped and singly doped families of O3 layered lithium manganese oxides. This is the first report of multiply doped analogues. The effects on electrochemical performance (ability to store reversibly large quantities of lithium and hence charge) and crystal chemistry of partially substituting some of the Mn ions with two dopants have been investigated. A range of structural (X-ray and neutron diffraction) and electrochemical (galvanostatic cycling and a.c. impedance) techniques as well as chemical analyses were utilised. The new materials, LixMn y-2zMzM′zO2 (M, M′ = Li, Cu, Mg, Ni, Zn, Al and Co), offer high capacities in excess of 200 mA h g -1 at a rate of 50 mA g-1 (C/4) with the highest values being for the z = 0.025 series. The main advantage of the multiply doped materials over the previously reported undoped and singly doped O3 layered lithium manganese oxides is their far superior rate capability. All the compounds in this study irreversibly transform to spinel-like materials on extended cycling. This is not, however, detrimental to their electrochemical performance and is analogous to the behaviour of other lightly doped O3 layered lithium manganese oxides.

Original languageEnglish
Pages (from-to)2367-2373
Number of pages7
JournalJournal of Materials Chemistry
Volume13
Issue number9
DOIs
Publication statusPublished - 1 Sep 2003
Externally publishedYes

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Intercalation
Manganese oxide
Lithium
Doping (additives)
Electrodes
Sodium Compounds
Sodium compounds
Crystal chemistry
Neutron diffraction
Ion exchange
Ions
X ray diffraction
lithium manganese oxide
Temperature

Cite this

Robertson, Alastair D. ; Armstrong, A. Robert ; Paterson, Allan J. ; Duncan, Morven J. ; Bruce, Peter G. / Nonstoichiometric layered LixMnyO2 intercalation electrodes : a multiple dopant strategy. In: Journal of Materials Chemistry. 2003 ; Vol. 13, No. 9. pp. 2367-2373.
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Nonstoichiometric layered LixMnyO2 intercalation electrodes : a multiple dopant strategy. / Robertson, Alastair D.; Armstrong, A. Robert; Paterson, Allan J.; Duncan, Morven J.; Bruce, Peter G.

In: Journal of Materials Chemistry, Vol. 13, No. 9, 01.09.2003, p. 2367-2373.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nonstoichiometric layered LixMnyO2 intercalation electrodes

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AU - Robertson, Alastair D.

AU - Armstrong, A. Robert

AU - Paterson, Allan J.

AU - Duncan, Morven J.

AU - Bruce, Peter G.

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N2 - Layered LixMnyO2 materials with the O3 (α-NaFeO2) structure have been synthesised by a low temperature ion exchange route from the corresponding sodium compounds. Previous studies have concentrated upon the undoped and singly doped families of O3 layered lithium manganese oxides. This is the first report of multiply doped analogues. The effects on electrochemical performance (ability to store reversibly large quantities of lithium and hence charge) and crystal chemistry of partially substituting some of the Mn ions with two dopants have been investigated. A range of structural (X-ray and neutron diffraction) and electrochemical (galvanostatic cycling and a.c. impedance) techniques as well as chemical analyses were utilised. The new materials, LixMn y-2zMzM′zO2 (M, M′ = Li, Cu, Mg, Ni, Zn, Al and Co), offer high capacities in excess of 200 mA h g -1 at a rate of 50 mA g-1 (C/4) with the highest values being for the z = 0.025 series. The main advantage of the multiply doped materials over the previously reported undoped and singly doped O3 layered lithium manganese oxides is their far superior rate capability. All the compounds in this study irreversibly transform to spinel-like materials on extended cycling. This is not, however, detrimental to their electrochemical performance and is analogous to the behaviour of other lightly doped O3 layered lithium manganese oxides.

AB - Layered LixMnyO2 materials with the O3 (α-NaFeO2) structure have been synthesised by a low temperature ion exchange route from the corresponding sodium compounds. Previous studies have concentrated upon the undoped and singly doped families of O3 layered lithium manganese oxides. This is the first report of multiply doped analogues. The effects on electrochemical performance (ability to store reversibly large quantities of lithium and hence charge) and crystal chemistry of partially substituting some of the Mn ions with two dopants have been investigated. A range of structural (X-ray and neutron diffraction) and electrochemical (galvanostatic cycling and a.c. impedance) techniques as well as chemical analyses were utilised. The new materials, LixMn y-2zMzM′zO2 (M, M′ = Li, Cu, Mg, Ni, Zn, Al and Co), offer high capacities in excess of 200 mA h g -1 at a rate of 50 mA g-1 (C/4) with the highest values being for the z = 0.025 series. The main advantage of the multiply doped materials over the previously reported undoped and singly doped O3 layered lithium manganese oxides is their far superior rate capability. All the compounds in this study irreversibly transform to spinel-like materials on extended cycling. This is not, however, detrimental to their electrochemical performance and is analogous to the behaviour of other lightly doped O3 layered lithium manganese oxides.

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