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Title: Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon cells with a new electrolyte composition: Potentiostatic studies and application to practical cells

Abstract

To improve the high temperature performance of Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon rocking-chair secondary batteries the authors searched for and identified a new electrolyte composition whose range of stability extends up to 4.9 V vs Li at room temperature and 4.8 V vs Li at 55 C for the Li[sub x]Mn[sub 2]O[sub 4] material. The behavior of the M = LiMn[sub 2]O[sub 4] composite new electrolyte interface at high voltage (4.2 to 5.1 V vs Li) shows the superposition of two phenomena: (i) an irreversible behavior due to a very slow electrolyte oxidation caused by the large surface area of carbon black (mixed with the Li[sub x]Mn[sub 2]O[sub 4] active material to improve the conductivity) and (ii) two reversible Li deintercalation-intercalation processes in the Li[sub x]Mn[sub 2]O[sub 4] spinel structure. In order to evaluate the kinetics of the high voltage phenomena, the behavior of the LiMn[sub 2]O[sub 4]/new electrolyte interface was investigated as a function of time and temperature. The electrolyte oxidative degradation is a well-stabilized reaction with nontime evolving kinetics, and with an activation energy close to 8 kcal/mol. The self-discharge mechanism a local redox process involving electrolyte oxidation at the electrode surface and reversible intercalation of Li in themore » Li[sub x]Mn[sub 2]O[sub 4] spinel structure. The effective stability of this new electrolyte against oxidation allows for better performance of the rocking-chair cells, in terms of cycle-life and self-discharge, over a wider temperature range ([minus]20 to 55 C.)« less

Authors:
;  [1]
  1. Bellcore, Red Bank, NJ (United States)
Publication Date:
OSTI Identifier:
5496225
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society; (United States)
Additional Journal Information:
Journal Volume: 140:11; Journal ID: ISSN 0013-4651
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ELECTRIC BATTERIES; ELECTROLYTES; CHEMICAL COMPOSITION; LITHIUM COMPOUNDS; ELECTROCHEMISTRY; MANGANATES; CHLORATES; COKE; PETROLEUM PRODUCTS; PHOSPHORUS FLUORIDES; REDOX REACTIONS; ALKALI METAL COMPOUNDS; CHEMICAL REACTIONS; CHEMISTRY; CHLORINE COMPOUNDS; ELECTROCHEMICAL CELLS; FLUORIDES; FLUORINE COMPOUNDS; HALIDES; HALOGEN COMPOUNDS; MANGANESE COMPOUNDS; OXYGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; 250903* - Energy Storage- Batteries- Materials, Components, & Auxiliaries; 400400 - Electrochemistry

Citation Formats

Guyomard, D, and Tarascon, J M. Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon cells with a new electrolyte composition: Potentiostatic studies and application to practical cells. United States: N. p., 1993. Web. doi:10.1149/1.2220987.
Guyomard, D, & Tarascon, J M. Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon cells with a new electrolyte composition: Potentiostatic studies and application to practical cells. United States. https://doi.org/10.1149/1.2220987
Guyomard, D, and Tarascon, J M. 1993. "Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon cells with a new electrolyte composition: Potentiostatic studies and application to practical cells". United States. https://doi.org/10.1149/1.2220987.
@article{osti_5496225,
title = {Rechargeable Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon cells with a new electrolyte composition: Potentiostatic studies and application to practical cells},
author = {Guyomard, D and Tarascon, J M},
abstractNote = {To improve the high temperature performance of Li[sub 1+x]Mn[sub 2]O[sub 4]/carbon rocking-chair secondary batteries the authors searched for and identified a new electrolyte composition whose range of stability extends up to 4.9 V vs Li at room temperature and 4.8 V vs Li at 55 C for the Li[sub x]Mn[sub 2]O[sub 4] material. The behavior of the M = LiMn[sub 2]O[sub 4] composite new electrolyte interface at high voltage (4.2 to 5.1 V vs Li) shows the superposition of two phenomena: (i) an irreversible behavior due to a very slow electrolyte oxidation caused by the large surface area of carbon black (mixed with the Li[sub x]Mn[sub 2]O[sub 4] active material to improve the conductivity) and (ii) two reversible Li deintercalation-intercalation processes in the Li[sub x]Mn[sub 2]O[sub 4] spinel structure. In order to evaluate the kinetics of the high voltage phenomena, the behavior of the LiMn[sub 2]O[sub 4]/new electrolyte interface was investigated as a function of time and temperature. The electrolyte oxidative degradation is a well-stabilized reaction with nontime evolving kinetics, and with an activation energy close to 8 kcal/mol. The self-discharge mechanism a local redox process involving electrolyte oxidation at the electrode surface and reversible intercalation of Li in the Li[sub x]Mn[sub 2]O[sub 4] spinel structure. The effective stability of this new electrolyte against oxidation allows for better performance of the rocking-chair cells, in terms of cycle-life and self-discharge, over a wider temperature range ([minus]20 to 55 C.)},
doi = {10.1149/1.2220987},
url = {https://www.osti.gov/biblio/5496225}, journal = {Journal of the Electrochemical Society; (United States)},
issn = {0013-4651},
number = ,
volume = 140:11,
place = {United States},
year = {1993},
month = {11}
}