LiNi0.4Co0.3Mn0.3O2 thin film electrode by aerosol deposition
© Kim et al; licensee Springer. 2012
Received: 19 September 2011
Accepted: 5 January 2012
Published: 5 January 2012
LiNi0.4Co0.3Mn0.3O2 thin film electrodes are fabricated from LiNi0.4Co0.3Mn0.3O2 raw powder at room temperature without pretreatments using aerosol deposition that is much faster and easier than conventional methods such as vaporization, pulsed laser deposition, and sputtering. The LiNi0.4Co0.3Mn0.3O2 thin film is composed of fine grains maintaining the crystal structure of the LiNi0.4Co0.3Mn0.3O2 raw powder. In the cyclic voltammogram, the LiNi0.4Co0.3Mn0.3O2 thin film electrode shows a 3.9-V anodic peak and a 3.6-V cathodic peak. The initial discharge capacity is 44.6 μAh/cm2, and reversible behavior is observed in charge-discharge profiles. Based on the results, the aerosol deposition method is believed to be a potential candidate for the fabrication of thin film electrodes.
Keywordsthin film aerosol deposition battery
Batteries can be applied to microelectronic and portable devices as power sources [1–3]. Also, many endeavors have been made to develop batteries for high power and energy for electric vehicles [4, 5]. Although lithium-ion batteries, among all other batteries, are the most promising type owing to their large energy storage density, commercial lithium-ion batteries contain a flammable liquid electrolyte, which has induced safety concerns. In order to mitigate the safety issue, an all-solid-state battery is a viable candidate as it is composed of thin film electrodes and a solid electrolyte. Moreover, the thin film electrode usually is composed of an active material without a binder. Owing to these advantages, many studies have been conducted to fabricate all-solid-state batteries through various methods, such as pulsed laser deposition [6–13], electrostatic spray deposition [14–16], and sputtering deposition [17–26]. Although these methods are very efficient for the preparation of thin film electrodes, they have several disadvantages, such as their complex fabrication processes, difficulty in controlling the composition of the thin film, and their low deposition rate.
Aerosol deposition method was recently developed that differs from aerosol flame deposition in which the materials are prepared through a hydrolysis reaction of aerosol precursor solutions by flame . The aerosol deposition method can be used for various applications, such as biomaterial and ceramic sensors [28–30]. In the aerosol deposition method, powder is mixed with gas to make an aerosol, and this aerosol is ejected onto the substrate to form a thin film. In other words, the aerosol deposition is a room-temperature impact-consolidation method. Thus, the aerosol deposition method has excellent advantages. These include its room temperature process, high deposition rate, high adhesion strength, easy control of the composition of the thin film, and its simple process. Furthermore, the aerosol deposition method does not require high vacuum devices, and the bare powder can be used directly without a pretreatment.
LiNi0.4Co0.3Mn0.3O2 in the LiNixCoyMnzO2 system was chosen as an active material on the account of its low cost, low toxicity, thermal stability, high capacity, and good cycle life [31, 32]. Xie et al.  recently reported a LiNi0.33Mn0.33Co0.33O2 thin film electrode prepared via a sputtering method. The LiNi0.33Mn0.33Co0.33O2 thin film electrode presented excellent results such as a high discharge capacity of more than 120 mAh/g. However, there was no report on the LiNi0.4Co0.3Mn0.3O2 thin film electrode. A complex conventional procedure was undertaken to deposit this thin film in their study. The aerosol deposition method was believed to have the ability to simplify this complex procedure, and no report has been made on using this method for the preparation of the thin film electrode.
In this study, a LiNi0.4Co0.3Mn0.3O2 thin film was prepared by aerosol deposition, and its electrochemical property was characterized. From these results, the feasibility of aerosol deposition as a new preparation method for thin film electrodes was discussed.
To investigate the crystal structures, the LiNi0.4Co0.3Mn0.3O2 powder and thin film electrodes were analyzed by an X-ray diffractometer (D8 Bruker; Karlsruhe, Germany) employing Cu Kα radiation. A field emission scanning electron microscope [FESEM] (Philips XL30S FEG; Philips, Amsterdam, Netherlands) was used for clarifying the surface morphologies. For the measurement of electrochemical properties, a Swagelok-type cell was employed. The thin film electrodes were used as working electrodes, and a lithium metallic foil was designated as counter electrode. The electrolyte solution was 1 mol LiPF6 in EC + DEC (1:1 (v/v)). The assemblies of the cells were conducted in an Ar-filled glove box. Potentiostatic tests were carried out at a sweep rate of 0.1 mV/s between 2.5 and 4.2 V for the thin film electrode, and galvanostatic tests were performed at a constant current density of 1 μA/cm2 in the same voltage range.
Results and discussions
The feasibility of the aerosol deposition method for the fabrication of thin film electrodes was investigated. LiNi0.4Co0.3Mn0.3O2 thin film electrode was prepared within 10 min and had a flat surface composed of fine particle with the α-NaFeO2 crystal structure. According to cyclic voltammogram measurement, the thin film electrode showed a 3.9-V anodic peak and a 3.6-V cathodic peak. The discharge capacity was 44.7 μAh/cm2 with a 3.6-V plateau region. Based on these results, the aerosol deposition method is a good candidate for the fabrication of thin film electrodes, which can be used in all-solid-state rechargeable batteries.
We gratefully acknowledge the financial supports from the KIMS Internal Program 'Development of Advanced Powder Materials Technology for New Growth Engine and Its Transfer to Industry' and the World Class University (WCU) program through the National Research Foundation of Korea (grant number; R32-2008-000-20093-0).
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