The kinetics of lithium transport through Li1-δCoO2 by theoretical analysis of current transient

被引:65
作者
Shin, HC [1 ]
Pyun, SI [1 ]
机构
[1] Korea Adv Inst Sci & Technol, Dept Mat Sci & Engn, Taejon 305701, South Korea
关键词
potentiostatic current transient; cell-impedance; lithium cobalt dioxide; phase boundary movement; numerical analysis;
D O I
10.1016/S0013-4686(99)00270-4
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The kinetics of alkali atom transport through intercalation compounds was theoretically considered through numerical simulation of the current transient and concentration profile across the electrode with time. For the theoretical calculation of those two different points of view, the following were considered: that alkali ion diffusion is a rate-controlling step of alkali atom transport through the electrode subjected to 'real potentiostatic' constraint; and that cell-impedance purely governs alkali atom transport. We presented current transient and change in alkali atom content profile across the electrode with time, numerically simulated based upon the two approaches. As an example lithium transport through a carbon-dispersed Li1-deltaCoO2 composite electrode was examined from the two points of view. From the comparison of experimentally obtained current transients with those numerically simulated, it is suggested that lithium transport during intercalation into and deintercalation from the Li1-deltaCoO2 composite electrode in the single alpha phase region are purely governed by cell-impedance. However, the 'cell-impedance-controlled' lithium transport during intercalation into the Li1-deltaCoO2 electrode in the coexistence of two phases alpha and beta is converted into 'diffusion-controlled' lithium transport. This transition in transport mechanism can be accounted for in terms of the input flux at the subsurface toward the electrode between by chemical diffusion and by the quotient of potential drop divided by cell-impedance. (C) 1999 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:489 / 501
页数:13
相关论文
共 23 条
[1]   Electrochemical lithium intercalation into and deintercalation from vanadium oxide electrode by using potentiostatic current transient technique [J].
Bae, JS ;
Pyun, SI .
SOLID STATE IONICS, 1996, 90 (1-4) :251-260
[2]   STRESS-INDUCED DIFFUSION IN HYDROGEN PERMEATION THROUGH PD81PT19 MEMBRANES [J].
BARANOWSKI, B .
JOURNAL OF THE LESS-COMMON METALS, 1989, 154 (02) :329-353
[3]   AN ELECTROCHEMICAL QUARTZ-CRYSTAL MICROBALANCE STUDY OF LITHIUM INSERTION INTO THIN-FILMS OF TUNGSTEN TRIOXIDE .1. MODELING OF THE IONIC INSERTION MECHANISM [J].
BOHNKE, O ;
VUILLEMIN, B ;
GABRIELLI, C ;
KEDDAM, M ;
PERROT, H ;
TAKENOUTI, H ;
TORRESI, R .
ELECTROCHIMICA ACTA, 1995, 40 (17) :2755-2764
[4]  
CARSLAW HS, 1959, CONDUCTION HEAT SOLI, P112
[5]  
CHOI YM, 1995, J POWER SOURCES, V56, P25, DOI 10.1016/0378-7753(95)80004-Z
[6]   Lithium transport through porous Li1-δCoO2 electrode:: analysis of current transient [J].
Choi, YM ;
Pyun, SI ;
Paulsen, JM .
ELECTROCHIMICA ACTA, 1998, 44 (04) :623-632
[7]  
Crank J., 1975, MATH DIFFUSION, P17
[8]   A comparison of the electrochromic properties of WO3 films intercalated with H+, Li+ and Na+ [J].
Dini, D ;
Decker, F ;
Masetti, E .
JOURNAL OF APPLIED ELECTROCHEMISTRY, 1996, 26 (06) :647-653
[9]   SEVERAL ELECTROCHEMICAL METHODS FOR THE SIMULTANEOUS MEASUREMENT OF THERMODYNAMIC ACTIVITY AND EFFECTIVE KINETIC-PROPERTIES OF INSERTED IONS IN SOLID-SOLUTION ELECTRODES [J].
HONDERS, A ;
YOUNG, EWA ;
VANHEEREN, AH ;
DEWIT, JHW ;
BROERS, GHJ .
SOLID STATE IONICS, 1983, 9-10 (DEC) :375-381
[10]   Hydrogen transport through anodic WO3 films [J].
Kim, DJ ;
Pyun, SI .
ELECTROCHIMICA ACTA, 1998, 43 (16-17) :2341-2347