High-pressure synthesis and electrochemical behavior of layered (1-a)LiNi1-yAlyO2 center dot aLi[Li1/3Ni2/3]O-2 oxides.

Shinova, E. and Zhecheva, E. and Stoyanova, R. and Bromiley, G. D. and Alcantara, R. and Tirado, J. L. (2005) High-pressure synthesis and electrochemical behavior of layered (1-a)LiNi1-yAlyO2 center dot aLi[Li1/3Ni2/3]O-2 oxides. Journal of Solid State Chemistry, 178 (9). pp. 2692-2700. DOI 10.1016/j.jssc.2005.06.006

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Abstract

Layered ð1 aÞLiNi1yAlyO2 aLi½Li1=3Ni2=3O2 oxides, 0pao0:4, have been prepared by solid state reaction between NiO, Al2O3 and Li2O2 under high pressure. The structural characterization of the layered oxides was performed using powder XRD, IR spectroscopy and EPR spectroscopy at 9.23 and 115 GHz. It has been found that the high-pressure favors Al substitution for Ni in the NiO2-layers of layered LiNiO2. A random Al/Ni distribution in the layer was found. The incorporation of extra Li in the Ni1yAlyO2-layer starts at a precursor composition Li=ðNi þ AlÞ41:2. While pure NiO2-layers are able to incorporate under highpressure up to 1/3Li, the appearance of Al in the NiO2-layers hinders Liþ dissolution ðLioð1 yÞ=3Þ. In addition, with increasing Al content there is a strong cationic mixing between the layers. High-frequency EPR of Ni3þ indicates that the structural interaction of LiAlyNi1yO2 with Li½Li1=3Ni2=3O2 proceeds via the formation of domains comprising different amount of Ni3þ ions. The use of Li1:08Al0:09Ni0:83O2 as a cathode material in a lithium ion cells displays a first irreversible Li extraction at 4.8 V, after which a reversible lithium insertion/extraction between 3.0 and 4.5V is observed on further cycling.

Item Type: Article
Uncontrolled Keywords: 2005 AREP 2005 P IA49
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Journal of Solid State Chemistry
Volume: 178
Page Range: pp. 2692-2700
Identification Number: 10.1016/j.jssc.2005.06.006
Depositing User: Sarah Humbert
Date Deposited: 17 Aug 2010 13:30
Last Modified: 23 Jul 2013 09:59
URI: http://eprints.esc.cam.ac.uk/id/eprint/1824

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