Overcharging manganese oxides: extracting lithium beyond Mn4+

A. R. Armstrong*, A. D. Robertson, P. G. Bruce

*Corresponding author for this work

Research output: Contribution to journalArticle

87 Citations (Scopus)

Abstract

It has been demonstrated previously that Li may be removed electrochemically from Mn containing oxides beyond the maximum oxidation state of 4+ for Mn in an octahedral oxygen environment. Here we present a comparison of such overcharge behavior in a series of different layered lithium manganese oxides including Li2MnO3, Lix[Mn 1 - yLiy]O2, (y ≤ 0.2), and Li[Ni xLi1/3 - 2x/3Mn2/3 - x/3]O2 (0 ≤ x ≤ 0.5). We show that there are two competing mechanisms by which electrochemical extraction of lithium can occur in Mn (4+) systems. In the first Li removal is accompanied by O2- loss (effective removal of Li 2O) whilst the second involves oxidation of the non-aqueous electrolyte thus generating H+ ions which exchange for Li +. At 30 °C the first mechanism is dominant in all examples studied, whilst at 55 °C the proton exchange mechanism becomes more important. At 30 °C H+ exchange is more prevalent in Li 2MnO3 than in the other two cases. The preference for O loss in the Mn/Ni system may be understood in terms of the ease with which MnO2 will lose oxygen.

Original languageEnglish
Pages (from-to)275-280
Number of pages6
JournalJournal of Power Sources
Volume146
Issue number1-2
DOIs
Publication statusPublished - 26 Aug 2005
Externally publishedYes

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Manganese oxide
manganese oxides
Ion exchange
Lithium
lithium
Oxygen
Oxidation
nonaqueous electrolytes
Oxides
Electrolytes
Protons
lithium oxides
oxidation
oxygen
protons
oxides
lithium manganese oxide
ions

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Armstrong, A. R. ; Robertson, A. D. ; Bruce, P. G. / Overcharging manganese oxides : extracting lithium beyond Mn4+. In: Journal of Power Sources. 2005 ; Vol. 146, No. 1-2. pp. 275-280.
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Overcharging manganese oxides : extracting lithium beyond Mn4+. / Armstrong, A. R.; Robertson, A. D.; Bruce, P. G.

In: Journal of Power Sources, Vol. 146, No. 1-2, 26.08.2005, p. 275-280.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Overcharging manganese oxides

T2 - extracting lithium beyond Mn4+

AU - Armstrong, A. R.

AU - Robertson, A. D.

AU - Bruce, P. G.

PY - 2005/8/26

Y1 - 2005/8/26

N2 - It has been demonstrated previously that Li may be removed electrochemically from Mn containing oxides beyond the maximum oxidation state of 4+ for Mn in an octahedral oxygen environment. Here we present a comparison of such overcharge behavior in a series of different layered lithium manganese oxides including Li2MnO3, Lix[Mn 1 - yLiy]O2, (y ≤ 0.2), and Li[Ni xLi1/3 - 2x/3Mn2/3 - x/3]O2 (0 ≤ x ≤ 0.5). We show that there are two competing mechanisms by which electrochemical extraction of lithium can occur in Mn (4+) systems. In the first Li removal is accompanied by O2- loss (effective removal of Li 2O) whilst the second involves oxidation of the non-aqueous electrolyte thus generating H+ ions which exchange for Li +. At 30 °C the first mechanism is dominant in all examples studied, whilst at 55 °C the proton exchange mechanism becomes more important. At 30 °C H+ exchange is more prevalent in Li 2MnO3 than in the other two cases. The preference for O loss in the Mn/Ni system may be understood in terms of the ease with which MnO2 will lose oxygen.

AB - It has been demonstrated previously that Li may be removed electrochemically from Mn containing oxides beyond the maximum oxidation state of 4+ for Mn in an octahedral oxygen environment. Here we present a comparison of such overcharge behavior in a series of different layered lithium manganese oxides including Li2MnO3, Lix[Mn 1 - yLiy]O2, (y ≤ 0.2), and Li[Ni xLi1/3 - 2x/3Mn2/3 - x/3]O2 (0 ≤ x ≤ 0.5). We show that there are two competing mechanisms by which electrochemical extraction of lithium can occur in Mn (4+) systems. In the first Li removal is accompanied by O2- loss (effective removal of Li 2O) whilst the second involves oxidation of the non-aqueous electrolyte thus generating H+ ions which exchange for Li +. At 30 °C the first mechanism is dominant in all examples studied, whilst at 55 °C the proton exchange mechanism becomes more important. At 30 °C H+ exchange is more prevalent in Li 2MnO3 than in the other two cases. The preference for O loss in the Mn/Ni system may be understood in terms of the ease with which MnO2 will lose oxygen.

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DO - 10.1016/j.jpowsour.2005.03.104

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