Abstract
Ti-substituted LiMn2O4 (LiMn2−x Ti x O4, x=0, 0.15, 0.30, 0.45, 0.60, and 0.75) has been synthesized using solid-state reactions. Their crystal and electronic structures were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). XRD data suggested that the lattice parameters of LiMn2−x Ti x O4 increase due to the replacement of Mn by Ti ions. XPS results indicated that the substituted Ti ions were in +4 oxidation state; consequently, the normal oxidation state of Mn ions has been detected by measuring the binding energy splitting of Mn 3s states, which decreases with the content of substituted Ti. The valence band spectra suggested that the intensity of e g level of Mn 3d orbitals increased due to the increase of the Mn3+/Mn4+ ratio.
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References
M.M. Thackeray, Prog. Batteries Battery Mater. 14, 1 (1995)
Y. Gao, K. Myrtle, M. Zhang, J.N. Reimers, J.K. Dahn, Phys. Rev. B 54, 16670 (1996)
M.M. Thackeray, J. Electrochem. Soc. 142, 2558 (1995)
L. Hernan, J. Morales, L. Sanchez, J. Santos, E. Rodriguez-Castellon, Solid State Ionics 133, 179 (2000)
C. Sigala, D. Guyomard, A. Verbaere, Y. Piffard, M. Tournoux, Solid State Ionics 81, 167 (1995)
H. Kawai, M. Nagata, H. Tukamoto, A.R. West, Electrochem. Solid-State Lett. 1, 212 (1998)
W. Cho, W. Ra, J. Shirakawa, J. Solid State Chem. 178, 3534 (2006)
G. Li, H. Ikuta, T. Uchida, M. Wakihara, J. Electrochem. Soc. 143, 178 (1996)
R.J. Gummow, A. de Kock, M.M. Thackeray, Solid State Ionics 69, 59 (1994)
B.L. He, S.J. Bao, Y.Y. Liang, W.J. Zhou, H. Li, H.L. Li, J. Solid State Chem. 178, 897 (2005)
Q.-H. Wu, J.-M. Xu, Q.-C. Zhuang, S.-G. Sun, Solid State Ionics 177, 1483 (2006)
F. Le Cras, D. Bloch, M. Anne, P. Strobel, Solid State Ionics 89, 203 (1996)
J. Breger, M. Jiang, N. Dupre, Y.S. Meng, Y. Shao-Horn, C.P. Grey, J. Solid State Chem. 178, 2575 (2005)
Q. Zhong, A. Bonakdarpour, M. Zhang, Y. Gao, J.R. Dahn, J. Electrochem. Soc. 144, 205 (1997)
S.-J. Hwang, H.-S. Park, J.-H. Choy, J. Phys. Chem. B 104, 7612 (2000)
Y.J. Wei, L.Y. Yan, C.Z. Wang, X.G. Xu, F. Wu, G. Chen, J. Phys. Chem. B 108, 18547 (2004)
D.H. Jang, S.M. Oh, J. Electrochem. Soc. 144, 3342 (1997)
M. Wakihara, G. Li, H. Ikuta, Lithium Ion Batteries (Koudansha, New York, 1998), Chap. 2
R.J. Gummow, A. de Kock, M.M. Thackeray, Solid State Ionics 69, 59 (1994)
A. Shi, D.-S. Wang, S. Meng, L. Chen, X. Huang, Phys. Rev. B 67, 115130 (2003)
Y.-S. Lee, Y.-K. Sun, K.-S. Nahm, Solid State Ionics 109, 285 (1998)
Ch. Cardinaud, G. Lemperiere, M.C. Peignon, P.Y. Jouan, Appl. Surf. Sci. 68, 595 (1993)
A. Luches, A. Perrone, B. Dubreuil, B. Rousseau, C. Boulmer-Leborgne, G. Blondiaux, H. Estrade, J. Hermann, J.L. Debrun, M.L. Degiorgi, M. Martino, P. Brault, Appl. Surf. Sci. 54, 349 (1992)
A. Casagrande, A. Glisenti, E. Lanzoni, E. Tondello, L. Mirenghi, M. Casarin, R. Bertoncello, Surf. Interface Anal. 18, 525 (1992)
Y.-L. Lin, T.-J. Wang, Y. Jin, Powder Technol. 123, 194 (2002)
W. Gopel, J.A. Anderson, D. Frankel, M. Jaehnig, K. Philips, J.A. Schafer, G. Rocker, Surf. Sci. 139, 333 (1984)
M.A. Arillo, G. Cuello, M.L. Lopez, P. Martin, C. Pico, M.L. Veiga, Solid State Sci. 7, 25 (2005)
K.M. Shaju, G.V.S. Rao, B.V.R. Chowdari, Solid State Ionics 152–153, 69 (2002)
C.D. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder, G.E. Mullenberg, Handbook of X-ray Photoelectron Spectroscopy (Perkin-Elmer Corporation, Physical Electronic Division, Eden Prairie, 1979)
J.W. Murray, J.G. Dillard, R. Giovanoli, H. Moers, W. Stumm, Geochim. Cosmochim. Acta 49, 463 (1985)
Q.-H. Wu, A. Thissen, W. Jaegermann, Chin. Phys. Lett. 8, 2202 (2006)
R.P. Gupta, S.K. Sen, Phys. Rev. B 10, 71 (1974)
V.A.M. Brabers, F.M. van Setten, P.S.A. Knapen, J. Solid State Chem. 49, 93 (1983)
C. Allen, S.J. Harris, J.A. Jutson, J.M. Dyke, Appl. Surf. Sci. 37, 117 (1989)
M. Oku, K. Hirolawa, S. Ikeda, J. Electron Spectrosc. Relat. Phenom. 7, 465 (1975)
R.J. Lad, V.E. Henrich, Phys. Rev. B 38, 10860 (1988)
A. Orendorz, J. Wusten, C. Ziegler, H. Gnaser, Appl. Surf. Sci. 252, 85 (2005)
Q.-H. Wu, M. Liu, W. Jaegermann, Mater. Lett. 59, 1480 (2005)