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Thin Film Electrode Materials Li4Ti5O12 and LiCoO2 Prepared by Spray Pyrolysis Method

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2011 IOP Conf. Ser.: Mater. Sci. Eng. 18 122004 (http://iopscience.iop.org/1757-899X/18/12/122004) View the table of contents for this issue, or go to the journal homepage for more

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ICC3: Symposium 9A: Ceramics for Electricity, Energy Conversion and Storage IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 122004 doi:10.1088/1757-899X/18/12/122004

Thin Film Electrode Materials Li4Ti5O12 and LiCoO2 Prepared by Spray Pyrolysis Method
M Takahashi1, J Tani, H Kido, Osaka Municipal Technical Research Institute, 1-6-50 Morinomiya, Joto-ku, Osaka 536-8553, Japan A Hayashi, K Tadanaga, and M Tatsumisago Osaka Prefecture University, 1-1 Gakuen-cho, naka-ku, Sakai, Osaka 599-8531, Japan E-mail: masataka@omtri.or.jp
Abstract The Li4Ti5O12 and the LiCoO2 have been considered as promising candidates of electrode materials for all-solid-state lithium secondary batteries. The spray pyrolysis method is a useful economical technique to prepare various thicknesses of oxide films though have not been intensively studied for fabrication of thin film lithium batteries. Thin films of Li4Ti5O12 and LiCoO2 electrode materials about 100-400 nm were prepared on quartz and gold substrates by the spray pyrolysis method by using Liacac and, TiO(acac)4 or Co(acac)3 with DMF solvent as starting materials. Electric properties as electrode materials for lithium batteries were estimated by using 3 probe liquid cells with liquid electrolyte LiPF6 in EC-DMC and Li metal as reference and counter electrodes. Structure and morphology of the films were investigated by XRD and SEM. Crystalline Li4Ti5O12 and LiCoO2 thin films were found to be prepared over 700 of substrate temperature. Cyclic voltammograms of the Li4Ti5O12 electrode thin films showed sharp oxidation and reduction peaks around 1.6 and 1.5 V, respectively. Chargedischarge curves for both Li4Ti5O12 and LiCoO2 electrode thin films showed discharge plateaus around 1.4 and 3.8 V with about 80 mAhg-1 of capacity. These results showed that these electrode thin films prepared by the spray pyrolysis method are electrochemically active and spray pyrolysis method is a promising technique to prepare thin film electrode materials.

1. Introduction Lithium secondary batteries composed of all-solid-state inorganic materials have been widely studied as new energy storage devices with high safety and high reliability. Fabrication of film batteries is useful to improve the safety and reliability, and also of interest for perspective use of MEMS, sensors, actuators, smart cards, and sheet devices. Li4Ti5O12 and LiCoO2 have been already successfully used as electrodes materials in commercial lithium batteries using liquid electrolyte. The Li4Ti5O12 anode materials show no volume change during charge discharge process and long cycle times.[1] The LiCoO2 cathode materials show relatively high conductivity and high energy density relative to other lithiated oxides.[2] Thus, these electrode materials can be considered as promising candidate of electrode materials of thin film all-solid-state lithium batteries.[3,4]
1

To whom any correspondence should be addressed.

c 2011 Ceramic Society of Japan.

Published under licence by IOP Publishing Ltd

ICC3: Symposium 9A: Ceramics for Electricity, Energy Conversion and Storage IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 122004 doi:10.1088/1757-899X/18/12/122004

The sol-gel method and the sputtering method are one of the useful techniques to prepare thin films of these materials. Spray pyrolysis method is also useful to prepare various thicknesses of porous oxide films [5-7] by the control of amount of mist or repetition of spraying. Moreover it is possible to economically prepare multi-component film, though have not been intensively studied. The work report here focuses on the preparation of thin films of Li4Ti5O12 and LiCoO2 electrode materials by the spray pyrolysis method and estimates electric properties for all-solid-state thin-film lithium batteries. 2. Experimental Spray solution for Li4Ti5O12 have been prepared using titanil-acetil acetonate (TiO(acac)4) and lithium-acetyl acetonate (Liacac) with di-methyl formamide (DMF) solvent as starting materials. Each acetyl acetonate compounds has been dissolved into DMF solution separately and mixed into a concentration of 3-5wt% Li4Ti5O12 composition with irradiating ultrasonic wave and stirred 16h at 40. Spray solution for LiCoO2 have been prepared in same manner using cobalt(III)-acetyl acetonate (Co(acac)3). These solutions of 3ml were sprayed onto rotating hot substrates heated at 800 : deposition area for gold substrate is limited to 1cm2 by using cover mask). In order to increase thickness of the films the spray deposition of the solution have been repeated total 10-15 times after each post heat treatment at 700 for 5 min. Structure and morphology of the films were investigated by XRD and SEM.

Figure 1. Flow of the procedure to prepare LiCoO2 and Li4Ti5O12 films.

Figure 2. Schematic diagram of the spray pyrolysis method. Merits of the method were in parentheses.

Thin films deposited by 0.1 mg of active materials on gold substrates have been used for electrochemical measurements by using 3 probe liquid cells. The thin film has been used as working electrodes, and Li metal on Ni mesh has been adopted as a reference and a counter electrode as illustrated in figure 3. As a liquid electrolyte 1M LiPF6 in Ethylene carbonate - Dimethyl carbonate (EC-DMC) have been used. Assemble of the cell was performed under N2 atmosphere. Cyclic voltammogram have been measured with 10 mVmin-1 and the charge discharge curves were measured 0.1mA cm-2. These measurement were achieved in incubator at 25 3. Results and discussion Figure 4 shows XRD patterns of the Li4Ti5O12 thin films with different post heating temperature; the heating temperatures are 700, 750, 800 as shown in the figure. Diffraction peaks observed in heated

ICC3: Symposium 9A: Ceramics for Electricity, Energy Conversion and Storage IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 122004 doi:10.1088/1757-899X/18/12/122004

films at 700 and 750 can be identified to crystalline Li4Ti5O12 though heating at 800 caused crystallization of quartz glass. Preferable heating temperature is 700 as post annealing. Figure.5 shows morphology of Li4Ti5O12 thin films. The films deposited on quartz glass substrate look transparent clear from photo image but relatively rough from SEM image. On the other hand the films deposited on gold substrate looks relatively smooth from SEM image. Figure 6 shows cyclic voltammogram of the Li4Ti5O12 thin films. Typical oxydation and reduction peaks around 1.6 and 1.5V were observed. It shows that the films Li4Ti5O12 is electrochemically active. Figure 7 show charge-discharge curves for Li4Ti5O12 thin films. Flat plateaus around 1.6 and 1.5 V were observed and the capacity of the film was observed about 80 mAh g-1. The observed capacity is relatively small. Origin of it is unrevealed. More investigation is requied.

Figure 3. Schematic diagram of the 3 prove beaker cell.

Figure 4. XRD patterns of the Li4Ti5O12 thin films with different post heating temperature; the heating temperatures are 700, 750, 800 .

Figure 5. Morphology of Li4Ti5O12 negative electrodes thin films prepared by the spray pyrolysis method.

0.15
10 mV min -1

2.2
Oxydize

0.1 0.05 0 -0.05 -0.1 1 1.2 1.4 1.6

2
E/V vs. Li/Li+

1.8 1.6 1.4 1.2 1

Charge
2nd5th cycle Discharge
0.1mA cm-1

Redox

1.8

2.2

20

40

60

80

100

E/V vs. Li/Li +

Capacity / mAhg-1

Figure 6. Cyclic voltammogram for the Li4Ti5O12 thin films.

Figure 7. Charge discharge curves for the Li4Ti5O12 thin films.

ICC3: Symposium 9A: Ceramics for Electricity, Energy Conversion and Storage IOP Publishing IOP Conf. Series: Materials Science and Engineering 18 (2011) 122004 doi:10.1088/1757-899X/18/12/122004

Figure 8 shows XRD pattern of the LiCoO2 film. Diffraction peaks can be identified to crystalline LiCoO2. Peak at 19from (003) plane is observed relatively strong showing oriented to C-axis. Thin film on quartz glass looks transparent brown from photo image but has porous morphology with roughness from SEM image. It can be thought that large surface area can work effectively for the electrode materials because it is useful to increase capacity and to accelerate the charge discharge rate performance. Figure 9 shows charge discharge curves for LiCoO2 thin film. Plateaus are observed in close value around 4V. It means that the electrode thin films can work as good electrode materials and spray pyrolysis method is a useful technique to prepare thin film electrode materials.
5 0.1mA cm-2 4.5 1st11 th cycle

E/V vs. Li/Li+

4 3.5 3 2.5 0 20 40 60 80 100

Capacity / mAhg -1

Figure 8. X-ray diffraction pattern and morphology of the LiCoO2 thin films prepared by the spray pyrolysis method.

Figure 9. Charge discharge curves for the LiCoO2 thin films.

4. Conclusions Crystalline Li4Ti5O12 and LiCoO2 thin films were prepared by the spray pyrolysis method. Cyclic voltammogram for the Li4Ti5O12 electrode thin films has shown typical sharp peaks around 1. 6 V and 1.5 V due to the oxidation and the reduction. Charge discharge curves for Li4Ti5O12 and LiCoO2 have shown flat plateaus and capacity about 80 mAh g-1. These results showed that these electrode thin films can work as good electrode materials and spray pyrolysis method is a useful technique to prepare thin film electrode materials. References [1] Ohzuku T, Ueda A, and Yamamoto N, 1995 J. Electrochem. Soc. 142 1431 [2] Nagaura T, Tozawa K 1990 Prog. Batteries Solar Cells 9 209 [3] Tatsumisago M, Mizuno F, and Hayashi A 2006 J. Power Sources 159 193 [4] Park Y, Lee S R, Lee Y J, Cho B W, Cho W I 2005 Mater. Chem. Phys. 93 70 [5] Takahashi M, Mita K, Toyuki H, Kume M 1987 J. Mater. Sci. 24 243 [6] Conde-Gallardo A, Guerrero M, Castillo N, Soto A B, Fragoso R, Cabanas-Moreno J G 2005 Thin Solid films 473 68 [7] Vigue J C, Spitz J 1975 J. Electrochem. Soc. :Solid State Science and Technol. 122 585 Acknowledgement This work was financially supported by a Gran-in-Aid for Scientific Research (C) 20560637, and Osaka Central Area Industry-Government-Academia Collaboration Project on City Area Program sponsored by MEXT, 2007-2009