On the behavior of the LixNiO2 system:: an electrochemical and structural overview

被引:282
作者
Delmas, C
Peres, JP
Rougier, A
Demourgues, A
Weill, F
Chadwick, A
Broussely, M
Perton, F
Biensan, P
Willmann, P
机构
[1] Inst Chim Matiere Condensee Bordeaux, ICMCB, CNRS, F-33608 Pessac, France
[2] Ecole Natl Super Chim & Phys Bordeaux, F-33608 Pessac, France
[3] Univ Kent, Chem Lab, Canterbury CT2 7NH, Kent, England
[4] SAFT, Adv Battery Div, F-86060 Poitiers, France
[5] Ctr Natl Etud Spatiales, F-31055 Toulouse, France
关键词
lithium; nickel oxides; intercalation;
D O I
10.1016/S0378-7753(97)02664-5
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
Lithium nickel oxide exhibits a departure from stoichiometry (Li1-zNi1+zO2) consisting in the presence of extra-nickel ions within the lithium sites. Using optimized experimental synthesis conditions, compositions very close to the ideal stoichiometry (z = 0.02) can be obtained. By using the sensitivity of the lithium site isotropic temperature factor to the stoichiometry, the amount of extra-nickel ions can be determined in a very precise way. The loss of reversibility at the first cycle is mainly related to the change in the oxidation state of the extra-nickel ions, which induces a local collapse of the structure and makes difficult the lithium re-intercalation, A systematic structural study of LixNiO2 phases has been performed by extended X-ray absorption fine structure (EXAFS) as well as X-ray and electron diffraction. In the case of the starting Li0.98Ni1.02O2 phase, a local distortion of the NiO6 octahedra, resulting from a dynamic Jahn-Teller effect of low spin trivalent nickel ions has been evidenced from the EXAFS study. For the partially de-intercalated materials (0.50 < x < 0.75) which crystallize in the monoclinic system, the EXAFS study shows that the NiO6 octahedra are only slightly distorted due to the occurrence of a hopping phenomenon between Ni-IV and Ni-III. Electron diffraction experiments show the existence of a superstructure due to a peculiar lithium-ion ordering. Systematic electrochemical studies have shown that this ordering is strongly sensititve to the presence of extra-nickel ions. (C) 1997 Elsevier Science S.A.
引用
收藏
页码:120 / 125
页数:6
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