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1 2006 [ No ]19-24 Charge and discharge cycle performance of negative electrode film of lithium ion battery made of natural graphite particles of different tapping densities Katsutomo Ohzeki", Yoshie Ohsaki*, Boris Golman** and Kunio Shinohara** The relationship was experimentally investigated between the cycle performance and the packing structure of a negative electrode film made of natural graphite particles of different tapping densities. At the same packing density of the electrode film, the modal voiddiameter and volumetric resistance increased with the tapping density of graphite powder. It was considered due to the fact that contact areas among particles of massive one were smaller than these of flaky one. Though the discharge capacity of the electrodes made of high tapping density powder rapidly decreased at low packing density, these cycle performances were satisfactorily improved with small irreversible capacity at high packing density. KEYWORDS: Lithium ion battery, Natural graphite, Packing structure, Cycle performance, Tappingdensity **Division ofchemical Process Engineering, Graduate School of Engineering, Hokkaido University: West 8, North 13, Kita-ku, Sapporo, Hokkaido , Japan

2

3 [No ] Fig. 3 Relationship between tapping density and modal void diameter by mercury penetration method. Fig. 1 Hg intrusion curve for sample A and F. Fig. 2 Void size distribution by mercury penetration method. :ƒïb=1.2g/cm3, œ:ƒïh=1.8g/cm3

4 Fig. 4 Relationship between tapping density and specific surface area of void space by mercury penetration method. Fig. 6 Specific charge and discharge curves for sample A and F. (a) Sample A, ĕb=1.2g/cm3 (b) Sample A, ĕb=1.8g/cm3 (c) Sample F, ĕb=1.2g/cm3 (d) Sample F, ĕb=1.8g/cm3 : first cycle -: second cycle Fig. 5 Relationship between tapping density and film resistance. Fig. 7 Effect of packing density on irreversible capacity at 1st cycle. Fig. 8 Relationship between modal void diameter and irreversible capacity with different samples.

5 [No ] Fig. 9 Relationship between tapping density and increasing ratio of film thickness after 1st cycle. Fig. 10 Relationship between tapping density and packing density after 1st cycle in comparison with green film. Fig. 11 Effect of packing density on cycle performance. (a) ĕb=1.2g/cm3, (b) ĕb=1.5g/cm3, (c) ĕb=1.8g/cm3

6 Fig. 12 Schematic illustration of packing structure of powder bed and film. 1) K. Tatsumi, N. Iwashita, H. Sakaebe, H. Shioyama, S. Higuchi, A. Mabuchi and H. Fujimoto, J. Electrochem. Soc. 142 (1995) ) H. Fujimoto, A. Mabuchi, K. Tokumitsu and T. Kasuh, Carbon 38 (2000) ) S. Atling, K. West and T. Jacobsem, Nato conference Series. 6 Material Science (1980) ) M. Winter, P. Navk and A. Monnier, J. Electrochem. Soc. 145 (1998) ) K. Zaghib, G. Nadeau and K. Kinoshita, J. Electrochem. Soc. 147 (2000) ) K. Seino, B. Golman, K. Shinohara and K. Ohzeki, TANSO 2005 [No.216] 2-7 [in Japanese]. 10) B. Golman, T. Takikawa, K. Shinohara and K. Ohzeki, Colloids and Surface A: Physicochem. Eng. Aspects 254 (2005) ) K. Ohzeki, Y. Ohsaki, B. Golman and K. Shinohara, TANSO 2004 [No.213] [in Japanese]. 12) K. Ohzeki, Y. Saito, B. Golman and K. Shinohara, Carbon 43 (2005) ) K. Ohzeki, B. Golman and K. Shinohara, TANSO 2004 [No.217] [in Japanese]. 15) C.R. Yang, J.Y. Song, Y.Y. Wang and C.C. Wang, J. Applied Electrochem. 30 (2000) ) G. Ning, B. Haran, B. Popov, J. Power Sources 117 (2003) ) E. Peled, C. Menachem, D. Bar-Tow and A. Melman, J. Electrochem. Soc. 143 (1996) L4-L7. 19) P. Arora, M. Doyle and R.E. White, J. Electrochem. Soc. 146 (1999) ) M. Endo, Y.A. Kim, T. Hayashi, K. Nishimura, T. Matusita, K. Miyashita and M.S. Dresselhaus, Carbon 39 (2001) ) V. Manev, I. Naidenov, B. Puresheva, P. Zlatilova and G. Pistoia, J. Power sources 55 (1995) ) D. Aurbach, Y. Ein-Eli, B. Markovsky, A. Zaban, S. Luski, Y. Carmeli and H. Yamin, J. Electrochem. Soc. 142 (1995) ) D. Aurbach, Y. Talyosef, B. Markovsky, E. Markevich, E. Zinigrad, L. Asraf, J.S. Gnanaraj and H.-J. Kim, Electrochim. Acta. (2004). 30) D. Aurbach, K. Gamlosky, B. Markovsky, Y. Gofer, M. Schmidt and U. Heider, J. Electrochim. Acta. 47 (2002) ) D. Aurbach, J.S. Gnanaraj, W. Geissler and M. Scmidt, J. Electrochem. Soc. 151 (2004) A23-A30. 32) H. Ota, Y. Sakata, A. Inoue and S. Yamaguchi, J. Electrochem. Soc. 151 (2004) A ) S. Lowell and J.E. Shields, Powder Surface Area and Porosity (1984). 34) C.-W. Wang, Y.-B. Yi, A.M. Sastry, J. Shim and K.A. Steiebel, J. Electrochem. Soc. 151 (2004) A1489-A ) J. Shim and K.A. Striebel, J. Power Sources (2003) ) J. Shim and K.A. Striebel, J. Power Sources 130 (2004) ) K.A. Striebel, A. Sierra, J. Sim, C.-W. Wang and A.M. Sastry, J. Power Sources 134 (2004) ) T. Ohzuku, Y. Iwakoshi and K. Sawai, J. Electrochem. Soc. 140 (1993) ) J.H. Lee, H.M. Lee and S. Ahn, J. Power Sources (2003)

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