Journal of Chemistry

Volume 2014 (2014), Article ID 824083, 5 pages

http://dx.doi.org/10.1155/2014/824083

Research Article

Structural and Electrochemical Properties of Lithium Nickel Oxide Thin Films

Gyu-bong Cho,¹ Tae-hoon Kwon,¹ Tae-hyun Nam,¹ Sun-chul Huh,² Byeong-keun Choi,² Hyo-min Jeong,² and Jung-pil Noh²

¹School of Materials Science and Engineering and RIGECT, Gyeongsang National University, No. 501, Jinju-daero, Jinju, Gyeongnam 660-701, Republic of Korea

²Department of Energy and Mechanical Engineering and Institute of Marine Industry, Gyeongsang National University, No. 38, Cheondaegukchi-gil, Tongyeong, Gyenognam 650-160, Republic of Korea

Received 19 June 2014; Revised 28 July 2014; Accepted 28 July 2014; Published 27 August 2014

Academic Editor: Yu Xin Zhang

Copyright © 2014 Gyu-bong Cho et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

LiNiO₂ thin films were fabricated by RF magnetron sputtering. The microstructure of the films was determined by X-ray diffraction and field-emission scanning electron microscopy. The electrochemical properties were investigated with a battery cycler using coin-type half-cells. The LiNiO₂ thin films annealed below 500°C had the surface carbonate. The results suggest that surface carbonate interrupted the Li intercalation and deintercalation during charge/discharge. Although the annealing process enhanced the crystallization of LiNiO₂, the capacity did not increase. When the annealing temperature was increased to 600°C, the FeCrNiO₄ oxide phase was generated and the discharge capacity decreased due to an oxygen deficiency in the LiNiO₂ thin film. The ZrO₂-coated LiNiO₂ thin film provided an improved discharge capacity compared to bare LiNiO₂ thin film suggesting that the improved electrochemical characteristic may be attributed to the inhibition of surface carbonate by ZrO₂ coating layer.

1. Introduction

In an attempt to miniaturize high performance portable electronic equipment, batteries with high power and energy density are required. Thin film batteries have been developed in an attempt to satisfy this requirement [1–3]; however, improving the performance of the cathode films is critical for advancing the use of electrochemical thin film batteries. Among the possible materials that could be used for a cathode film, LiCoO₂, owing to its high theoretical specific capacity and ease of preparation, is a promising candidate [4–6]. However, the high cost and toxicity of cobalt limit the use of LiCoO₂ in thin film batteries. Therefore, it is necessary to develop less expensive cathode materials for thin film battery applications. LiNiO₂ has emerged as a useful cathode material owing to its low cost and high energy density [7–10].

In the current study, LiNiO₂ thin films were deposited by using RF magnetron sputtering. The microstructure of the films was measured by X-ray diffraction and field-emission scanning electron microscopy. Finally, the electrochemical properties were investigated with a battery cycler using coin-type half-cells, in the potential range of 3.0 V–4.2 V.

2. Experimental

Bare and ZrO₂-coated LiNiO₂ thin films have been deposited onto stainless steel (STS 304) foil substrates held at a distance of 6 cm away from the target. The STS304 substrate was ultrasonically cleaned with acetone, alcohol, and distilled water in that order. The LiNiO₂ and ZrO₂ targets were made by Pascal Co. (Japan). A base vacuum of 5 × 10⁻⁶ Torr was obtained with a cryopump. Gas flow rate of Ar/O₂ was 4/1 with a total gas flow amount of 150 sccm. Deposition pressure was maintained at 2 × 10⁻³ Torr during deposition. The LiNiO₂ target was presputtered for 30 min and the deposition time was 360 min at 100 W RF power. ZrO₂ coating layer was deposited for 10 min at 100 W RF power. Figures 1(a) and 1(b) show the surface and cross-section images of bare LiNiO₂ thin film deposited on Si wafer substrate. As seen in Figure 1(a), a uniform distribution of clusters of ~50 nm was seen. The calculated deposition rates of LiNiO₂ were approximately 1.7 nm/min. The deposited thin films were annealed from 400°C to 600°C in air to obtain the crystalline film.

(a)

(b)

Figure 1: FE-SEM images of (a) surface and (b) cross-section images of LiNiO₂ thin film deposited on Si wafer substrate.

The structure of the LiNiO₂ thin films was investigated by X-ray diffractometry (XRD, Rigaku, Miniflex). The XRD measurements were performed using Cu Kα radiation ( Å) and phase identification was made by comparing the diffraction patterns with the JCPDS references. The morphology of the deposited films was studied by field-emission scanning electron microscopy (FE-SEM, Jeol, JSM-6701F).

In order to examine the electrochemical properties of cathode thin films, coin-type cells were assembled with lithium foils as the counter and reference electrode and 1 M LiPF₆ in ethylene carbonate (EC) : diethyl carbonate (DEC) (1 : 1, vol.%) electrolytic solution. The charge-discharge test was carried out with a battery cycler (Won A Tech, WDCS3000s) at a constant current density of 5 μA/cm² in the potential range of 3.0–4.2 V.

3. Results and Discussion

Figure 2 shows the XRD patterns of as-deposited and annealed LiNiO₂ thin films at various temperatures at 10 min. Crystallization peaks of LiNiO₂ were not seen in the as-deposited films. However, the XRD pattern of the 400°C annealed film exhibited broad (104) LiNiO₂ and lithium carbonate (Li₂CO₃) reflection peaks. The degree of crystallization of LiNiO₂ was enhanced at 500°C because the (104) reflection became stronger as the annealing temperature was increased. The intensity of the Li₂CO₃ peak also increased. However, after annealing at 600°C, the reflection peaks of LiNiO₂ and Li₂CO₃ disappeared and impurity peaks of NiCrFeO₄, which was considered an oxide layer of the STS304 substrate, were observed (Figure 2(d)).

Figure 2: XRD patterns of (a) as-deposited, (b) 400°C, (c) 500°C, and (d) 600°C annealed LiNiO₂ thin films. The annealing time was 10 minutes.

Surface images of the annealed LiNiO₂ thin films are shown in Figure 3. The 400°C annealed film had a rough surface with no cracks and some surface impurities (Figure 3(a)). When the annealing temperature was increased to 500°C, the size of the surface impurities grew and became angular. After annealing at 600°C, complete removal of the surface impurities was achieved and the surface had a smooth morphology compared with that of the 400°C annealed film. The XRD (Figure 2) and FE-SEM (Figure 3) results suggest that the angulated surface impurity, which disappeared at an annealing temperature of 600°C, was lithium carbonate (Li₂CO₃).

(a)

(b)

(c)

Figure 3: FE-SEM images of LiNiO₂ thin film with various annealing temperatures at (a) 400°C, (b) 500°C, and (c) 600°C, respectively. The annealing time was 10 minutes.

Figure 4 shows the initial discharge curves of the as-deposited and annealed LiNiO₂ thin films. All of these films were tested at a current density of 5 μA/cm² between 3.0 V and 4.2 V and a plateau was observed in the 400°C annealed films. When the annealing temperature was increased to 500°C, the plateau was more clearly exhibited and indicated a phase transition of crystalline LiNiO₂ [11, 12]; the discharge capacity, however, did not increase. These results suggest that the surface carbonate interrupts the lithium intercalation and deintercalation during charge/discharge, affecting the discharge capacity. The 600°C annealed films exhibited a lower initial discharge capacity compared with the other annealed films. This may be attributed to the formation of an intermediate oxide layer between the substrate and active material film. The intermediate oxide layer that formed may lead to an oxygen deficiency in the annealed LiNiO₂ thin films. In order for the LiNiO₂ film to obtain good electrochemical characteristics, the deposited LiNiO₂ thin films should be annealed at a temperature that prevents the formation of an intermediate oxide layer. In addition, it is necessary to remove the surface carbonate. It has been previously reported that surface coatings enhance the electrochemical properties of cathode materials without sacrificing the specific capacity of the respective cathode [13].

Figure 4: Initial discharge curves of LiNiO₂ thin film with various annealing temperatures. The annealing time was 10 minutes.

Figure 5 shows the XRD patterns of bare and ZrO₂-coated LiNiO₂ thin films annealed at 500°C for 10 min. As seen in Figure 5(a), the diffraction peak of the surface carbonate disappeared in the coated thin film, suggesting that the ZrO₂ coating prevents the formation of surface carbonate during the annealing process.

Figure 5: XRD patterns of (a) noncoated and (b) ZrO₂-coated LiNiO₂ thin films. The films were annealed in 10 min at 500°C.

Figure 6 shows the first discharge curves and cycle stability of bare and ZrO₂-coated LiNiO₂ thin films. As seen in Figures 6(a) and 6(b), a single plateau was observed in both of the films, corresponding to the phase transition of crystalline LiNiO₂. Therefore, this would indicate that both films are crystallized. However, the first discharge capacity is slightly different such that the first discharge capacity of ZrO₂-coated film is higher than that of the bare LiNiO₂ thin film. The capacity retention rate is similar in both thin films as seen in Figure 6(b).

(a)

(b)

Figure 6: (a) Initial discharge behavior and (b) cyclic performance of LiNiO₂ thin films. The films were annealed in 10 min at 500°C.

4. Summary

LiNiO₂ thin films were fabricated by RF magnetron sputtering. Crystallization began at annealing temperatures above 400°C; however, the films that were annealed below 500°C exhibited surface carbonate (in the form of Li₂CO₃) identified by XRD. Surface carbonate interrupts the Li intercalation and deintercalation during charge/discharge and therefore the capacity did not increase, although the degree of LiNiO₂ crystallization was enhanced. When the annealing temperature was increased to 600°C, the FeCrNiO₄ oxide phase was generated and the discharge capacity decreased due to the oxygen deficiency in the LiNiO₂ thin film. The ZrO₂-coated LiNiO₂ thin film provided an improved discharge capacity compared to the bare LiNiO₂ thin film at an annealing temperature of 500°C. Therefore, the improvement in electrochemical characteristics can be attributed to the inhibition of surface carbonate by the ZrO₂ coating layer.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.

Acknowledgment

This research was supported by the Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2012-R1A1A2008821 and 2012-R1A2A1A01006546).

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