Journal
JOURNAL OF MATERIALS CHEMISTRY
Volume 21, Issue 39, Pages 15369-15377Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1jm11335f
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Funding
- New Energy and Industrial Technology Department Organization (NEDO) in Japan
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X-Ray absorption fine structure (XAFS) spectroscopy was carried out on submicron sized TiO2-B, which is one of the promising candidates for negative electrode materials, in order to clarify the electronic and local structural changes during its lithium-ion insertion process. From the extended Xray absorption fine structure (EXAFS) results of lithiated LixTiO2-B, we propose the changes in lithium-ion insertion sites during electrochemical discharging. The lithium ions are inserted into the five-fold coordinated sites and/or distorted octahedral sites distributed at the vicinity of O layers parallel to the ab plane for x <= 0.5, while the lithium ions are accommodated into the five-fold coordinated site distributed at the vicinity of TiO2 layers parallel to the ab plane for x > 0.5. The interaction between the inserted lithium ion and TiO6 octahedra affects the lattice distortion of LixTiO2-B for x > 0.5, as well as the titanium reduction during discharging. It is suggested through the X-ray absorption near edge structure (XANES) spectroscopy of Ti K-, Ti L-and O K-edges that the distortion of TiO6 octahedra makes the hybridized state of O 2p and Ti 3d broad, and has a significant effect on the lithium-ion insertion properties of TiO2-B.
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