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In Situ XAFS Analysis of Li(Mn, M)2O4 (M=Cr, Co, Ni) 5V Cathode Materials for Lithium-Ion Secondary Batteries

✍ Scribed by Yasuko Terada; Kenji Yasaka; Fumishige Nishikawa; Tokuzo Konishi; Masaki Yoshio; Izumi Nakai


Publisher
Elsevier Science
Year
2001
Tongue
English
Weight
169 KB
Volume
156
Category
Article
ISSN
0022-4596

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✦ Synopsis


Chemical states and structural changes accompanying the electrochemical Li deintercalation of Li 1؊x (Mn, M) 2 O 4 (M ‫؍‬ Cr, Co, Ni) were studied by the in situ X-ray absorption 5ne structure (XAFS) technique. The X-ray absorption near-edge structures (XANES) of Mn and M as a function of x showed that the high voltage ( &5 V) in the cathode materials of an Li secondary battery is due to the oxidation of M 3؉ to M 4؉ (M ‫؍‬ Cr, Co) and M 2؉ to M 4؉ (in the case of M ‫؍‬ Ni), while the origin of the low voltage (3.9+4.3 V) can be ascribed to the oxidation of Mn 3؉ to Mn 4؉ . The extended X-ray absorption 5ne structure (EXAFS) analysis of Li 1؊x (Mn, Ni) 2 O 4 revealed that Ni 2؉ is oxidized to Ni 4؉ via the Ni 3؉ state with a Jahn+Teller distorted Ni 3؉ +O octahedron.