Hostname: page-component-586b7cd67f-2plfb Total loading time: 0 Render date: 2024-11-23T00:08:56.990Z Has data issue: false hasContentIssue false

Structure and optical absorption of combustion-synthesized nanocrystalline LiCoO2

Published online by Cambridge University Press:  03 March 2011

Paromita Ghosh
Affiliation:
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute, Kolkata 700 032, India
S. Mahanty
Affiliation:
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute, Kolkata 700 032, India
M.W. Raja
Affiliation:
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute, Kolkata 700 032, India
R.N. Basu*
Affiliation:
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute, Kolkata 700 032, India
H.S. Maiti
Affiliation:
Fuel Cell and Battery Section, Electroceramics Division, Central Glass and Ceramic Research Institute, Kolkata 700 032, India
*
a) Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

Nanocrystalline LiCoO2 powders (10–50 nm) were synthesized by a citrate-nitrate combustion process followed by calcination at different temperatures (300–800 °C) in air. Thermogravimetric analyses indicated a sharp combustion at a low temperature of 225 °C, producing fine crystallites. Quantitative phase analyses from the x-ray diffractograms showed that while annealing at 500 °C produced mixed phases of cubic and rhombohedral LiCoO2, annealing at 800 °C resulted in single-phase rhombohedral LiCoO2. Electronic transitions related to the Co 3d bands were investigated by ultraviolet-visible reflectance spectra in absorbance mode and were ascribed to the Co 3d intra-band transition involving t2g and eg orbitals. The d-d transitions underwent a blue shift of about 0.3 eV as the cubic LiCoO2 transformed into the rhombohedral structure with band gap values of about 1.4 and 1.7 eV.

Type
Articles
Copyright
Copyright © Materials Research Society 2007

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1Nagaura, T. and Tozawa, K.: Lithium ion rechargeable battery. Prog. Batt. Sol. Cells 9, 209 (1990).Google Scholar
2Kalyani, P., Jagannathan, R., Gopukumar, S., and Lu, C-H.: Luminescence in some lithiated transition metal oxide cathodes. J. Power Sources 109, 301 (2002).CrossRefGoogle Scholar
3Mizushima, K., Jones, P.C., Wiseman, P.J., and Goodenough, J.B.: LixCoO2 (0 < x < −1): A new cathode material for batteries of high energy density. Mater. Res. Bull. 15, 783 (1980).CrossRefGoogle Scholar
4Gummow, R.J., Liles, D.C., Thackeray, M.M., and David, W.I.F.: A reinvestigation of the structures of lithium cobalt oxide with neutron diffraction data. Mater. Res. Bull. 28, 1177 (1993).Google Scholar
5Kushida, K. and Kuriyama, K.: Narrowing of the Co-3d band related to the order-disorder phase transition in LiCoO2. Solid State Commun. 123, 349 (2002).Google Scholar
6Rossen, E., Reimers, J.N., and Dann, J.R.: Synthesis and electrochemistry of spinel LT-LiCoO2. Solid State Ionics 62, 53 (1993).Google Scholar
7Kang, S.G., Kang, S.Y., Ryn, K.S., and Chang, S.H.: Electrochemical and structural properties of HT-LiCoO2 and LT-LiCoO2 prepared by the citrate sol-gel method. Solid State Ionics 120, 155 (1999).Google Scholar
8Gummow, R.J., Thakeray, M.M., David, W.I.F., and Hull, S.: Structure and electrochemistry of lithium cobalt oxide synthesized at 400 °C. Mater. Res. Bull. 27, 327 (1992).CrossRefGoogle Scholar
9Horn, Y.S., Hackney, S.A., Kahain, A.J., and Thackeray, M.M.: Structural stability of LiCoO2 at 400 °C. J. Solid State Chem. 168, 60 (2002).Google Scholar
10Santiago, E.I., Andrade, A.V.C., Paira-Santos, C.O., and Bulhoẽes, L.O.S.: Structural and electrochemical properties of LiCoO2 prepared by combustion synthesis. Solid State Ionics 158, 91 (2003).Google Scholar
11Antolini, E.: LiCoO2: Formation, structure, lithium and oxygen nonstoichiometry, electrochemical behavior and transport properties. Solid State Ionics 170, 159 (2004).Google Scholar
12Kushida, K. and Kuriyama, K.: Mott-type hopping conduction in the ordered and disordered phases of LiCoO2. Solid State Comm. 129, 525 (2004).Google Scholar
13Aydinol, M.K., Kohan, A.F., and Ceder, G.: Ab initio study of lithium intercalation in metal dichalcogenides. Phys. Rev. B 56, 1354 (1997).Google Scholar
14Czyzyk, M.T., Potze, R., and Sawatzky, G.A.: Band-theory description of high-energy spectroscopy and the electronic structure of LiCoO2. Phys. Rev. B 46, 3729 (1992).CrossRefGoogle ScholarPubMed
15Shao-Horn, Y., Hackney, S.A., Johnson, C.S., Kahaian, A.J., and Thackeray, M.M.: Structural features of low-temperature LiCoO2 and acid-delithiated products. J. Solid State Chem. 140, 116 (1998).Google Scholar
16Van Elp, J., Wieland, J.L., Eskes, H., Kuiper, P., and Sawatzky, G.A.: Electronic structure of CoO, Li-doped CoO and LiCoO2. Phys. Rev. B 44, 6090 (1991).Google Scholar
17Rosolen, J.M. and Decker, F.: Photoelectrochemical behavior of LiCoO2 membrane electrode. J. Electroanal. Chem. 501, 253 (2001).CrossRefGoogle Scholar
18Kushida, K. and Kuriyama, K.: Optical absorption related to Co-3d bands in sol-gel grown LiCoO2 films. Solid State Commun. 118, 615 (2001).CrossRefGoogle Scholar
19Basu, R.N., Fietz, F., Wessel, E., Buchkremer, H.P., and Stöver, D.: Microstructure and electrical conductivity of LaNi0.6Fe0.4O3 prepared by combustion synthesis routes. Mater. Res. Bull. 39, 1335 (2004).Google Scholar
20Konstantinov, K., Wang, G.X., Yao, J., Liu, H.K., and Dou, S.X.: Stoichiometry-controlled high-performance LiCoO2 electrode materials prepared by a spray solution technique. J. Power Sources 119–121, 195 (2003).Google Scholar
21Greenwood, N.N. and Earnshaw, A.: Chemistry of the Elements, 1st ed. (Pergamon Press, Oxford, UK, 1984), pp. 12961297.Google Scholar
22 JCPDS Data File No. 00-043-1004, ICDD, PDF-2 Release 2003, US.Google Scholar
23Choi, S. and Manthiram, A.: Synthesis and electrochemical properties of LiCo2O4 spinel cathodes. J. Electrochem. Soc. 149, A162 (2002).Google Scholar
24Julien, C.: Local cationic environment in lithium nickel–cobalt oxides used as cathode materials for lithium batteries. Solid State Ionics 136–137, 887 (2000).Google Scholar
25Julien, C.: Local structure and electrochemistry of lithium cobalt oxides and their doped compounds. Solid State Ionics 157, 57 (2003).CrossRefGoogle Scholar
26Ceder, G. and Aydinol, M.K.: The electrochemical stability of lithium-metal oxides against metal reduction. Solid State Ionics 109, 151 (1998).Google Scholar
27Choi, S. and Manthiram, A.: Chemical synthesis and properties of spinel Li1−xCo2O4−δ. J. Solid State Chem. 164, 332 (2002).Google Scholar
28Kalyani, P., Kalaiselvi, N., and Muniyandi, N.: A new solution combustion route to synthesize LiCoO2 and LiMn2O4. J. Power Sources 111, 232 (2002).CrossRefGoogle Scholar
29Goodenough, J.B.: Design considerations. Solid State Ionics 69, 184 (1994).CrossRefGoogle Scholar
30Lithium Batteries Science and Technology, edited by Nazri, G-A. and Pistoia, G. (Kluwer Academic Publishers, MA, 2004), p. 47.Google Scholar
31Plitcha, E., Slane, S., Uchiyama, M., Salomon, M., Chua, D., Ebner, W.B., and Lin, H.W.: An improved Li/LixCoO2 rechargeable cell. J. Electrochem. Soc. 136, 1865 (1989).Google Scholar