M3+-modified LiMn2O4 spinel intercalation cathodes: II. Electrochemical stabilization by Cr3+

A. D. Robertson*, S. H. Lu, W. F. Howard

*Corresponding author for this work

Research output: Contribution to journalArticle

115 Citations (Scopus)

Abstract

The 4 V rechargeable capacity of the spinel LiMn2O4 was stabilized by substituting less than 1 mole percent (m/o) Mn3+ with Cr3+. The optimum composition was determined as LiCr0.012Mn1.988O4, which had a discharge capacity exceeding 110 mAh/g even after 100 cycles, although improved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr3+ substitution). The effects of varying electrolyte salt, temperature, and current density were also investigated. Capacity losses in 4 V LiMn2O4-based spinel systems were attributed to Mn dissolution into the electrolyte causing structural degradation of the cathode and an increase in cell polarization from deposited Mn interfering with Li+ transport through the anodic solid-electrolyte interphase. Substitution of even a small amount of Mn3+ by trivalent Cr3+ minimized this dissolution and resulted in enhanced cathodic electrochemical stability.

Original languageEnglish
Pages (from-to)3505-3512
Number of pages8
JournalJournal of the Electrochemical Society
Volume144
Issue number10
DOIs
Publication statusPublished - 1 Oct 1997
Externally publishedYes

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Intercalation
Electrolytes
Dissolution
Cathodes
Substitution reactions
Stabilization
Solid electrolytes
Chemical analysis
Current density
Salts
Polarization
Degradation
Temperature
lithium manganese oxide
spinell

Cite this

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title = "M3+-modified LiMn2O4 spinel intercalation cathodes: II. Electrochemical stabilization by Cr3+",
abstract = "The 4 V rechargeable capacity of the spinel LiMn2O4 was stabilized by substituting less than 1 mole percent (m/o) Mn3+ with Cr3+. The optimum composition was determined as LiCr0.012Mn1.988O4, which had a discharge capacity exceeding 110 mAh/g even after 100 cycles, although improved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr3+ substitution). The effects of varying electrolyte salt, temperature, and current density were also investigated. Capacity losses in 4 V LiMn2O4-based spinel systems were attributed to Mn dissolution into the electrolyte causing structural degradation of the cathode and an increase in cell polarization from deposited Mn interfering with Li+ transport through the anodic solid-electrolyte interphase. Substitution of even a small amount of Mn3+ by trivalent Cr3+ minimized this dissolution and resulted in enhanced cathodic electrochemical stability.",
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M3+-modified LiMn2O4 spinel intercalation cathodes : II. Electrochemical stabilization by Cr3+. / Robertson, A. D.; Lu, S. H.; Howard, W. F.

In: Journal of the Electrochemical Society, Vol. 144, No. 10, 01.10.1997, p. 3505-3512.

Research output: Contribution to journalArticle

TY - JOUR

T1 - M3+-modified LiMn2O4 spinel intercalation cathodes

T2 - II. Electrochemical stabilization by Cr3+

AU - Robertson, A. D.

AU - Lu, S. H.

AU - Howard, W. F.

PY - 1997/10/1

Y1 - 1997/10/1

N2 - The 4 V rechargeable capacity of the spinel LiMn2O4 was stabilized by substituting less than 1 mole percent (m/o) Mn3+ with Cr3+. The optimum composition was determined as LiCr0.012Mn1.988O4, which had a discharge capacity exceeding 110 mAh/g even after 100 cycles, although improved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr3+ substitution). The effects of varying electrolyte salt, temperature, and current density were also investigated. Capacity losses in 4 V LiMn2O4-based spinel systems were attributed to Mn dissolution into the electrolyte causing structural degradation of the cathode and an increase in cell polarization from deposited Mn interfering with Li+ transport through the anodic solid-electrolyte interphase. Substitution of even a small amount of Mn3+ by trivalent Cr3+ minimized this dissolution and resulted in enhanced cathodic electrochemical stability.

AB - The 4 V rechargeable capacity of the spinel LiMn2O4 was stabilized by substituting less than 1 mole percent (m/o) Mn3+ with Cr3+. The optimum composition was determined as LiCr0.012Mn1.988O4, which had a discharge capacity exceeding 110 mAh/g even after 100 cycles, although improved stabilities were attained for all Cr-modified compositions studied (0.1 to 7.0 m/o Cr3+ substitution). The effects of varying electrolyte salt, temperature, and current density were also investigated. Capacity losses in 4 V LiMn2O4-based spinel systems were attributed to Mn dissolution into the electrolyte causing structural degradation of the cathode and an increase in cell polarization from deposited Mn interfering with Li+ transport through the anodic solid-electrolyte interphase. Substitution of even a small amount of Mn3+ by trivalent Cr3+ minimized this dissolution and resulted in enhanced cathodic electrochemical stability.

U2 - 10.1149/1.1838041

DO - 10.1149/1.1838041

M3 - Article

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JO - Journal of the Electrochemical Society

JF - Journal of the Electrochemical Society

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