Electrochemical impedance study of Li-ion insertion into mesocarbon microbead single particle electrode Part 1. Graphitized carbon

被引:188
作者
Umeda, M
Dokko, K
Fujita, Y
Mohamedi, M
Uchida, I
Selman, JR
机构
[1] Tohoku Univ, Dept Appl Chem, Grad Sch Engn, Aoba Ku, Sendai, Miyagi 9808579, Japan
[2] IIT, Ctr Electrochem Sci & Engn, Dept Environm Chem & Engn, Chicago, IL 60616 USA
基金
日本学术振兴会;
关键词
single particle; microelectrode; graphitized carbon; lithium batteries; solid electrolyte interphase;
D O I
10.1016/S0013-4686(01)00799-X
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Li-ion insertion and extraction were investigated by electrochemical impedance spectroscopy (EIS) on a single particle mesocarbon microbead (MCMB) (heat-treated at 2800 degreesC) of 30 mum diameter in I M LiClO4/propylene carbonate + ethylene carbonate solution, The impedance spectra were modeled using an equivalent circuit comprising: (i) Li-ion conduction in the solid electrolyte interphase (SEI) Film, (ii) Two charge transfer processes related to the particle/SEI interface, and the SEI/electrolyte interface. (iii) A semi-in finite Warburg-type element, reflecting solid state Li-ion diffusion. (iv) An intercalation capacitance reflecting the accumulation of lithium into the particle. The resistance for Li-ion conduction in the solid electrolyte interphase (SEI) film was found to be independent of the potential, On the other hand, the charge transfer resistance deereased/increased monotonously when the electrode potential shifted to cathodic/anodic direction. This behavior is due to an activation process. The apparent chemical diffusion coefficient of lithium in the MCMB particle was found to be within the range 10(-6-)10(-10) cm(2) s(-1), varying as a function of electrode potential with minima at the potentials corresponding to the voltammetric peaks. (C) 2001 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:885 / 890
页数:6
相关论文
共 36 条
[1]   THE STUDY OF ELECTROLYTE-SOLUTIONS BASED ON ETHYLENE AND DIETHYL CARBONATES FOR RECHARGEABLE LI BATTERIES .2. GRAPHITE-ELECTRODES [J].
AURBACH, D ;
EINELI, Y ;
MARKOVSKY, B ;
ZABAN, A ;
LUSKI, S ;
CARMELI, Y ;
YAMIN, H .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1995, 142 (09) :2882-2890
[2]   A study of highly oriented pyrolytic graphite as a model for the graphite anode in Li-ion batteries [J].
Bar-Tow, D ;
Peled, E ;
Burstein, L .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (03) :824-832
[3]  
Bard A. J., 1980, ELECTROCHEMICAL METH
[4]   FILMING MECHANISM OF LITHIUM-CARBON ANODES IN ORGANIC AND INORGANIC ELECTROLYTES [J].
BESENHARD, JO ;
WINTER, M ;
YANG, J ;
BIBERACHER, W .
JOURNAL OF POWER SOURCES, 1995, 54 (02) :228-231
[5]   A NONLINEAR LEAST-SQUARES FIT PROCEDURE FOR ANALYSIS OF IMMITTANCE DATA OF ELECTROCHEMICAL SYSTEMS [J].
BOUKAMP, BA .
SOLID STATE IONICS, 1986, 20 (01) :31-44
[6]   PHASE-DIAGRAM OF LIXC6 [J].
DAHN, JR .
PHYSICAL REVIEW B, 1991, 44 (17) :9170-9177
[7]   Kinetic characterization of single particles of LiCoO2 by AC impedance and potential step methods [J].
Dokko, K ;
Mohamedi, M ;
Fujita, Y ;
Itoh, T ;
Nishizawa, M ;
Umeda, M ;
Uchida, I .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2001, 148 (05) :A422-A426
[8]   THE DEPENDENCE OF THE PERFORMANCE OF LI-C INTERCALATION ANODES FOR LI-ION SECONDARY BATTERIES ON THE ELECTROLYTE SOLUTION COMPOSITION [J].
EINELI, Y ;
MARKOVSKY, B ;
AURBACH, D ;
CARMELI, Y ;
YAMIN, H ;
LUSKI, S .
ELECTROCHIMICA ACTA, 1994, 39 (17) :2559-2569
[9]   NEW STRUCTURAL PARAMETERS FOR CARBON - COMPREHENSIVE CRYSTALLIZATION INDEX AND CAVITY INDEX [J].
FUJIMOTO, H ;
TOKUMITSU, K ;
MABUCHI, A ;
KASUH, T ;
SHIRAISHI, M .
CARBON, 1994, 32 (07) :1249-1252
[10]   Stage transformation of lithium-graphite intercalation compounds caused by electrochemical lithium intercalation [J].
Funabiki, A ;
Inaba, M ;
Abe, T ;
Ogumi, Z .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (07) :2443-2448