Abstract #220, 221st ECS Meeting, 2012 The Electrochemical Society

Cell Voltage (V)

All-Solid Thin-Filmed Li-Ion Rechargeable Battery with Aligned Carbon Nanotube Anode M. Baba1,2, F. Izumida1,2, R. Ye2, J. Yoshida2, T. Ushirokawa2, K. Ohta2 and M. Kusunoki3 1 Graduate School of Engineering, Iwate University, Morioka 020-8551, Japan 2 Electronics Course, Iwate Industrial Technology Junior College, Yahaba, Iwate 028-3615, Japan 3 EcoTopia Science Institute, Nagoya University, Nagoya 464-8603, Japan

curves from the first to 64the cycle. These chargedischarge curves were measured after the acceleration test of 3000 cycles with a narrow voltage window as described later. Estimating from the thickness of the cathode layer, the discharge capacity density is 390mAh/cm3.
5

1st - 64th

cut-off: 4.0 - 0.5V

4

6.7A/cm

We reported the thin-filmed, solid-state rechargeable battery composed of a LiMn2O4 positive electrode, a Li3PO4 solid electrolyte and a V2O5 negative electrode.1 We have also investigated the lithium-ion (Li+) battery using porous silicon anode.2 Here, another new type of lithium-ion (Li+) battery using carbon nanotube (CNT) anode is reported, exhibiting an efficient solidstate rechargeable operation. The CNTs which were discovered by S. Iijima in 19913 are expected to be used to anode material of Li-ion rechargeable batteries4 as one of the various applications. In the present experiment, the CNT layer was formed on a SiC wafer by the SiC surface decomposition (SSD) method.5 Furthermore, the CNT surface was modified by Ar-ion sputtering method6 in order to work efficiently as an anode. Figures 1(a) and (b) show FESEM images of a surface and a cross section of a CNT layer formed on a 6H-SiC wafer after the Ar-sputter with 40W-30s under 110-4Torr. In this case, the SiC wafer was heated at 1700 C for 30min in a vacuum (110- 4 Torr) and thereafter the CNT layer was sputtered at RT for 30s under 110- 4 Torr of Ar pressure. In Fig.1(a), the surface becomes grainy more with diameter of ~30 nm and in Fig.1(b), such grainy bundle consisting of several CNTs were aligned vertical to the SiC wafer with a height of ~220nm and the top surface was modified smoothly.

(a)
0 0. 0

(b)
0. 5 1. 0 1. 5 2. 0

Charge-discharge Time (h)

Fig.2 Overview (a) and charge-discharge characteristics (b) of a thin-filmed CNT battery. Figure 3(a) shows Charge and discharge characteristics of the thin-filmed CNT battery after a long-term cyclic performance under the acceleration test. This figure contains 230 curves from the 1831st to 2030the cycle. The test condition is as follows; chargedischarge current is 0.4A, and cut-offs of 4.0V for charge and 20min for discharge, resulting a voltage window range is between 4.0 and 3.75V. Figure 3(b) shows a cell voltage at the each discharge end under the acceleration test during 2000 cycles. The good cycleability of the thin-filmed CNT battery was obtained.
4. 5

1st - 230th (1831st - 2030th)

cut-off: 4V/20min

6.7A/cm

Cell Voltage at Discharge End (V)

cut-off: 4V/20min
4

6.7A/cm

Cell Voltage (V)

4. 0

3. 5

3. 0

(a)
2. 5 0 5 10 15 20

0 0

(b)
500 1000 1500 2000

Cycle Number

Cycle Number

Fig.3 Charge and discharge characteristics (a) and cell voltage at the discharge end (b) under the acceleration test of a thin-filmed CNT battery. In conclusion, we found out for the first time that a carbon nanotube layer efficiently intercalates and deintercalates Li ions and as a result, it acts well as an anode of a Li-ion rechargeable battery. The CNT anode of the present battery gives excellent properties of high Liaccommodation, efficient release of a volume change, a good role common between a negative active material and a electrical contact, and a potential use as a monolithic power source to integrated circuits on a SiC tip. M. Baba, et al, Electrochem. & Solid-State Lett. 2, 320 (1999). 2 M. Baba, T. Ushirokawa, R. Ye and K. Ohta, 216th ECS Meeting, Vienna, Austria (2009). 3 S. Iijima, Nature 354, 56 (1991). 4 B. Gao, A. Kleinhammes, X.P. Tang, C. Bower, L. Fleming, Y. Wu, and O. Zhou, Chem. Phys. Lett. 307, 153 (1999). 5 M. Kusunoki, J. Shibata, M. Rokkaku, and T. Hirayama, Jpn. J. Appl. Phys. 37, L605 (1998). 6 F. Izumida, R. Ye, K. Ohta, M. Baba and M. Kusunoki, Physics Procedia 14, 164-166 (2011). 7 M. Baba, et al, J. Power Sources 97-98, 798 (2001). 8 Tang Xin-cun, et al, Trans. Nonferrous Met. Soc. China 16(2006).
1

(a)

(b)

Fig.1 FE-SEM images of a surface (a) and a cross section (b) of a CNT layer on a 6H-SiC wafer. A Li3PO4 film (300nm thick) and then a LiMn2O4 film (350nm thick) were deposited on the CNT layer by a magnetron RF sputtering method7, and finally a Ti metal film (160nm thick) in order to keep an electrical contact was deposited by a magnetron DC sputtering method. Figure 2(a) shows a typical thin-filmed Li-ion rechargeable battery with CNT anode ( thin-filmed CNT battery). The operating area of the present battery is 6mm2. Figure 2(b) shows charge-discharge characteristic curves of the thin-filmed CNT battery with chargedischarge current of 0.4A (current density of 6.7A/cm2) and cut-off voltages of 4.0 and 0.5V. Here, judging from the large difference8 of the intercalation/de-intercalation potentials of a Li+ ion between LiMn2O4 cathode and Clike CNT anode, such a high voltage plateau around 4.0 3.6V is reasonable for the present battery. In addition, this figure which seems to be only a few lines contains 64