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

A. D. Robertson; S. H. Lu; W. F. Howard

doi:10.1149/1.1838041

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

Academic Development

Research output: Contribution to journal › Article

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 language	English
Pages (from-to)	3505-3512
Number of pages	8
Journal	Journal of the Electrochemical Society
Volume	144
Issue number	10
DOIs	https://doi.org/10.1149/1.1838041
Publication status	Published - 1 Oct 1997

Keywords

electrochemical cycling
cathode materials
electrochemical performance
spinell
intercalcation

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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.",

keywords = "electrochemical cycling, cathode materials, electrochemical performance, spinell, intercalcation",

author = "Robertson, {A. D.} and Lu, {S. H.} and Howard, {W. F.}",

year = "1997",

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doi = "10.1149/1.1838041",

language = "English",

volume = "144",

pages = "3505--3512",

journal = "Journal of the Electrochemical Society",

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TY - JOUR

T1 - M3+-modified LiMn2O4 spinel intercalation cathodes: 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.

KW - electrochemical cycling

KW - cathode materials

KW - electrochemical performance

KW - spinell

KW - intercalcation

U2 - 10.1149/1.1838041

DO - 10.1149/1.1838041

M3 - Article

VL - 144

SP - 3505

EP - 3512

JO - Journal of the Electrochemical Society

JF - Journal of the Electrochemical Society

SN - 1945-7111

IS - 10

ER -