In situ X-ray absorption spectroscopy study of lithium insertion in a new disordered manganese oxi-iodide

被引:14
作者
Ibarra-Palos, A
Strobel, P
Proux, O
Hazemann, JL
Anne, M
Morcrette, M
机构
[1] CNRS, Cristallog Lab, F-38042 Grenoble 9, France
[2] Lab Geophys Interne & Techtonophys, F-38400 St Martin Dheres, France
[3] Univ Picardie, Lab Reactivite & Chim Solide, F-80039 Amiens, France
关键词
lithium batteries; manganese oxide; in-situ measurements; X-ray absorption;
D O I
10.1016/S0013-4686(02)00236-0
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Mn K-edge X-ray absorption measurements were carried out on an amorphous manganese oxi-iodide (Li0.60Na0.16MnO2.33Iapproximate to0.05) as cathode material in plastic lithium batteries. X-ray absorption spectroscopy experiments were performed in situ for every lithium intercalation increment Deltax approximate to 0.10 per formula unit along a discharge with 0 less than or equal to x less than or equal to 0.67. The X-ray absorption near edge structure (XANES) spectra demonstrate a smooth decrease of Mn valence with in-situ reduction, confirmed by a monotonous increase in Mn-O distance from extended X-ray absorption fine structure (EXAFS). The first-shell octahedral coordination of manganese is hardly affected by lithium insertion, while the evolution of the Mn-Mn coordinence shows a trend towards the formation of MnOn polyhedra chains on deep discharge. The material discharged to an average manganese valence 3.25+ showed negligible static Jahn-Teller effect. Together with the inherent flexibility of disordered structures towards intercalation and bond length changes, this is probably a major cause of the stability of this oxi-iodide on cycling in lithium batteries. (C) 2002 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:3171 / 3178
页数:8
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