Application of Electro-polymerized Conducting Polymers to Secondary Battery Material Research and development work on cathode material for rechargeabl
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1 Application of Electro-polymerized Conducting Polymers to Secondary Battery Material Research and development work on cathode material for rechargeable lithium batteries has been reviewed with particular emphasis on battery systems using electro-deposited conducting polymers. The general features of Li+ -intercalation compounds and anion-doping conducting polymers are described in the light of their application to in lithium cells, and the criteria for lithium/polymer cells are then summarized to allow appropriate material selection. Examples are also introduced to show of how electro-polymerizing affects the electrochemical properties of deposited polypyrrole film and the charge-discharge performances of Li/LiClO4/polypyrrole battery. In addition, a technique for the optimization of electrochemical properties of polypyrrole has been suggested, along with a method of morphology orientation using insulating NBR films. Key Words: Secondary Lithium Battery, Conducting Polymer, Polypyrrole Fig. 1 Gravimetric energy density of Lithium/positive material cell systems. -2-
2 Table 1 Performances of some rechargeable lithium batteries developed by Japanese companies. Fig. 2 Equivalent weight vs. theoretical specific energy density characteristics of various cell systems. -3-
3 -4-
4 Fig. 3 Classification of organic conducting polymers in terms of the chemical structure. Table 2 Various types of lithium/polymer batteries. -5-
5 Fig. 4 Ĕ and Ĕ* energy levels of some typical conjugated polymers. Table 3 Doping levels of various conducting polymers. polymer batteries. Table 4 Performances of several types of lithium/ -6-
6 Fig. 5 Comparison of the performances of various lithium /polymer batteries. -7- Fig. 6 Cyclic voltammograms for polypyrrole films formed at a) 0.32V and b) 0.84V vs. Ag/Ag+ with various thicknesses at 5mVs-1. The formation charges [C cm-2] are represented in the figure.
7 Fig. 8 Formation charge dependence of apparent diffusion coefficient (Dapp) and concentration (Co*) of dopants within polypyrrole films formed at different potentials. Fig. 9 Dependence of polymerization potential on the doping charge of polypyrrole films as a function of formation charge [Ccm-2]. -8-
8 Fig. 10 Polymerization scheme for polypyrrole formation. Fig. 11 a) Charge-discharge curves for Li/LiClO4(1M)/ polypyrrole batteries, where polypyrrole films were formed at 0.32 and 0.84V with various amount of charges. b) Coulombic efficiency vs. formation charge dependence for the charge - discharge curves for a). -9-
9 Fig. 13 Schematic model for preparation procedure of NBR-guided grown polypyrrole films. Fig. 12 a) Typical charge-discharge curves for Li/LiClO4 (1M)/polypyrrole (5Ccm-2) batteries at 1.0 macm-2 when charged to 45% of doping level. b) Charge-depth dependence of the coulombic yield (Č), where polypyrrole films were formed with various anions. Fig. 14 a) Relationship between anodic current peak (ipa) and scan rate (v) (for cyclic voltammograms) for polypyrrole and NBR -guided grown polypyrrole films as a function of NBR thickness. b) Depend- of NBR thickness on the slopes of a), where ence the thickness regions (A, B, C) are indicated at the top. c) Schematic models for polypyrrole growth at various NBR thicknesses. -10-
10 Fig. 15 SEM micrographs of normal polypyrrole and NBR (20ƒÊm)-guided grown polypyrrole films formed with 10Ccm-2. Fig. 16 Comparison of charge-discharge performance of a) Li/LiClO4 (1M)/polypyrrole and b) Li/LiC èo4 (1 M)/(NBR/polypyrrole) batteries. -11-
11 4) N. Koshiba, T. Ikehata, H. Hayama and K. Momose; Ext. Abs., 3rd IMLB (International Meeting on Lithium Battery), p. 256 (1986) 30) A.G. MacDiarmid; Chem. Eng. News, 62, 38 (1984) 6) D.W. Murphy, S. Shinha; Ext. Abs., 3rd IMLB, p ) D. Macinnes, M.A. Druy, P.J. Nigrey, D.P. Nairns A.G. (1986) MacDiarmid, A.J. Heeger; JCS Chem. Commun., 1981, 7) G. Pistoia, M. Pasquali, M. Tocci, R.V. Moshtev, V. Maner; J. Electrochem. Soc., 132, 281 (1985) 8) T. Tsuchida, K. Shinoda, Y. Hino, H. Takayanagi, 33) P. Buttel, M. Matstragostino, S. Panero, B. Scrosati; Electrochimica Acta, 31, 783 (1986) 9) M. Wakihara, T. Uchida, H. Hinode, T. Morishita, K. Watanabe, M. Taniguchi; Ext Abs., 3rd IMLB, p. 297 (1986) 10) Y. Matsuda; Ext. Abs., 3rd IMLB, p. 319 (1986) 11) D.H. Shen, S.S. Rao, S.P.S. Yen, R.B. Somoano; J. Pow. Sourc., 18, 127 (1986) 12) J.A. Stiles; Ext. Abs., 3rd IMLB, p. 189 (1986) K. Brandt; J. Pow. Sourc., 17, 153 (1986) 38) T. Osaka, K. Naoi, H. Sakai, S. Ogano; J. Electrochem. Soc., 134, 285 (1987) 14) H. Shirakawa, E.J. Louis, A.G. MacDiarmid; JCS Chem. Commun., 1977, 578 (1977) 15) P.J. Nigrey, A.G. MacDiarmid, A.J. Heeger; JCS Chem. Commun., 1979, 574 (1979) (1987) 41) K. Naoi, A. Ishijima, T. Osaka; J. Electroanal. Chem., 217, 203 (1987) 42) T. Osaka, S. Ogano, K. Naoi; J. Electrochem. Soc., 135, 539 (1988) 43) T. Osaka, K. Naoi, T. Hirabayashi; J. Electrochem. Soc., 134, 2645 (1987) 34) T. Osaka, K. Naoi, H. Sakai, S. Ogano; J. Eelectrochem. Soc., 134, 285 (1987) 36) T. Osaka, K. Naoi, S. Ogano, S. Nakamura; Chem. Lett., 1986, 1687 (1986) 37) T. Osaka, K. Naoi, S. Ogano, S. Nakamura; J. Electrochem. Soc., 134, 2096 (1987) 39) T. Osaka, K. Naoi, S. Ogano; J. Electrochem. Soc., 135, 1072 (1988) 40) K. Naoi, T. Osaka; J. Electrochem. Soc., 134,
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