Enhancing the electrochemical properties of LT-LiCoO2 in lithium cells by doping with Mn

被引:29
作者
Caballero, A
Hernán, L
Morales, J
Castellón, ER
Santos, J
机构
[1] Univ Cordoba, Fac Ciencias, Dept Quim Inorgan & Ingn Quim, E-14071 Cordoba, Spain
[2] Univ Malaga, Dept Quim Inorgan, E-29071 Malaga, Spain
[3] Univ Balearic Isl, Dept Quim, E-07071 Palma de Mallorca, Spain
关键词
lithium batteries; lithium-cobalt-manganese oxides;
D O I
10.1016/j.jpowsour.2003.09.061
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
Nearly stoichiometric LiCo1-xMnxO2 mixed oxides (x = 0, 0.2) were prepared by using a sol-gel method and their electrochemical properties as lithium cell cathodes were examined. Gels of the two samples fired at 400degreesC exhibited the same structure as LT-LiCoO2, with the transition elements in a tervalent state as revealed by XPS spectroscopy. A modified spinel structure model is proposed to account for the X-ray diffraction data. Substitution of Co by Mn ions has the following favorable effects on the electrochemical properties: (i) a decrease in polarization between the charge and discharge curves; (ii) an increase in capacity delivered by the cell; (iii) a marked improvement in the cycling properties of the cell, particularly when the calcining temperature is raised to 600degreesC. The enhanced cell performance is ascribed to lithium occupying in an orderly manner available positions in the modified spinel structure adopted. The presence of Mn enhances cation ordering, thus increasing the reversibility of the lithium reaction. (C) 2003 Elsevier B.V. All rights reserved.
引用
收藏
页码:286 / 291
页数:6
相关论文
共 33 条
[1]   CoO2, the end member of the LixCoO2 solid solution [J].
Amatucci, GG ;
Tarascon, JM ;
Klein, LC .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (03) :1114-1123
[2]   IN-SITU GROWTH OF LAYERED, SPINEL, AND ROCK-SALT LICOO2 BY LASER-ABLATION DEPOSITION [J].
ANTAYA, M ;
CEARNS, K ;
PRESTON, JS ;
REIMERS, JN ;
DAHN, JR .
JOURNAL OF APPLIED PHYSICS, 1994, 76 (05) :2799-2806
[3]   The layered intercalation compounds Li(Mn1-yCoy)O2:: Positive electrode materials for lithium-ion batteries [J].
Armstrong, AR ;
Robertson, AD ;
Gitzendanner, R ;
Bruce, PG .
JOURNAL OF SOLID STATE CHEMISTRY, 1999, 145 (02) :549-556
[4]  
ARMSTRONG AR, 1996, NATURE, V61, P309
[5]   ELECTRONIC-STRUCTURE OF 3D-TRANSITION-METAL COMPOUNDS BY ANALYSIS OF THE 2P CORE-LEVEL PHOTOEMISSION SPECTRA [J].
BOCQUET, AE ;
MIZOKAWA, T ;
SAITOH, T ;
NAMATAME, H ;
FUJIMORI, A .
PHYSICAL REVIEW B, 1992, 46 (07) :3771-3784
[6]   Influence of chemical prehistory on the phase formation and electrochemical performance of LiCoO2 materials [J].
Brylev, OA ;
Shlyakhtin, OA ;
Kulova, TL ;
Skundin, AM ;
Tretyakov, YD .
SOLID STATE IONICS, 2003, 156 (03) :291-299
[7]   Identification of cathode materials for lithium batteries guided by first-principles calculations [J].
Ceder, G ;
Chiang, YM ;
Sadoway, DR ;
Aydinol, MK ;
Jang, YI ;
Huang, B .
NATURE, 1998, 392 (6677) :694-696
[8]   An overview of the Li(Ni,M)O2 systems:: syntheses, structures and properties [J].
Delmas, C ;
Ménétrier, M ;
Croguennec, L ;
Saadoune, I ;
Rougier, A ;
Pouillerie, C ;
Prado, G ;
Grüne, M ;
Fournès, L .
ELECTROCHIMICA ACTA, 1999, 45 (1-2) :243-253
[9]   Lithium intercalation/deintercalation in transition metal oxides investigated by X-ray photoelectron spectroscopy [J].
Dupin, JC ;
Gonbeau, D ;
Martin-Litas, I ;
Vinatier, P ;
Levasseur, A .
JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 2001, 120 (1-3) :55-65
[10]   CHARACTERIZATION OF LT-LIXCO1-YNIYO2 ELECTRODES FOR RECHARGEABLE LITHIUM CELLS [J].
GUMMOW, RJ ;
THACKERAY, MM .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1993, 140 (12) :3365-3368