An update on the high temperature ageing mechanism in LiMn2O4-based Li-ion cells

被引:47
作者
du Pasquier, A [1 ]
Blyr, A [1 ]
Cressent, A [1 ]
Lenain, C [1 ]
Amatucci, G [1 ]
Tarascon, JM [1 ]
机构
[1] Univ Picardie, F-80039 Amiens, France
关键词
lithium; batteries;
D O I
10.1016/S0378-7753(99)00136-6
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
LiMn2O4-based Li-ion cells suffer from a limited cycle-life and a poor storage performance at 55 degrees C, both in their charged and discharged states. From 3-electrode type electrochemical measurements, the non-stability of LiMn2O4 in electrolytes containing traces of HF was identified as being the source of such a poor performance. To gel some insight in the mechanism by which the high-temperature ageing proceeds, a survey of the chemical stability of high surface area LiMn2O4 in various Li-based electrolytes was performed as a function of temperature. The growth of a protonated lambda-MnO2 phase was identified when LiMn2O4 powders were stored into the electrolyte at 100 degrees C for several hours. Such a protonated phase is partially inactive with respect to lithium intercalation, thereby accounting for same of the irreversible capacity loss experienced at 55 degrees C far LiMn2O4-based Li-ion cells. (C) 1999 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:54 / 59
页数:6
相关论文
共 15 条
[1]   Surface treatments of Li1+xMn2-xO4 spinels for improved elevated temperature performance [J].
Amatucci, GG ;
Blyr, A ;
Sigala, C ;
Alfonse, P ;
Tarascon, JM .
SOLID STATE IONICS, 1997, 104 (1-2) :13-25
[2]   MECHANISM OF PROTON INSERTION AND CHARACTERIZATION OF THE PROTON SITES IN LITHIUM MANGANATE SPINELS [J].
AMMUNDSEN, B ;
JONES, DJ ;
ROZIERE, J ;
BURNS, GR .
CHEMISTRY OF MATERIALS, 1995, 7 (11) :2151-2160
[3]   Proton insertion and lithium-proton exchange in spinel lithium manganates [J].
Ammundsen, B ;
Aitchison, PB ;
Burns, GR ;
Jones, DJ ;
Roziere, J .
SOLID STATE IONICS, 1997, 97 (1-4) :269-276
[4]  
AUBARCH D, 1995, J ELECTROCHEM SOC, V142, P2873
[5]   Origin of Self-discharge Mechanism in LiMn2O4-based Li-ion Cells: A Chemical and Electrochemical Approach [J].
Blyr, A. ;
Du Pasquier, A. ;
Amatucci, G. ;
Tarascon, J. -M. .
IONICS, 1997, 3 (5-6) :321-331
[6]   Self-discharge of LiMn2O4/C Li-ion cells in their discharged state -: Understanding by means of three-electrode measurements [J].
Blyr, A ;
Sigala, C ;
Amatucci, G ;
Guyomard, D ;
Chabre, Y ;
Tarascon, JM .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (01) :194-209
[7]  
DUPASQUIER A, IN PRESS J ELECTROCH
[8]   Extraction of lithium from spinel phases of the system Li1+xMn2-xO4-δ [J].
Endres, P ;
Ott, A ;
Kemmler-Sack, S ;
Jager, A ;
Mayer, HA ;
Praas, HW ;
Brandt, K .
JOURNAL OF POWER SOURCES, 1997, 69 (1-2) :145-156
[9]   PREPARATION OF A NEW CRYSTAL FORM OF MANGANESE-DIOXIDE - LAMBDA-MNO2 [J].
HUNTER, JC .
JOURNAL OF SOLID STATE CHEMISTRY, 1981, 39 (02) :142-147
[10]   Electrolyte effects on spinel dissolution and cathodic capacity losses in 4 v Li/LixMn2O4 rechargeable cells [J].
Jang, DH ;
Oh, SM .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1997, 144 (10) :3342-3348