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The effects of nanosized ZnO on the microstructure, the free volume and the ionic conductivity of poly ethylene oxide (PEO) nanocomposite electrolytes (PEO)8-ZnO-LiClO4 are systematically studied by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy and positron annihilation lifetime spectroscopy (PALS), respectively. The experimental results show that the presence of the nanosized ZnO brings about a reduction in the crystallinity of the PEO phase and a very marked increase in ionic conductivity. PALS discrete analysis shows that the free volume size, the free volume concentration and the relative free volume fraction significantly increase with the increase of nano-ZnO. Specially, it is the first time to observe the occurrence of peaks of the free volume distribution split after nano-ZnO has been filled, which indicates that the ZnO added into (PEO)8-LiClO4 has an important effect on the microstructure for nanocomposites due to the interaction between the nano-ZnO and matrix. A direct correlation between the free volume fraction and the ionic conductivity is observed, and the ionic conductivity mechanism is discussed.
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Keywords:
- positron annihilation lifetime spectroscopy /
- nanocomposite polymer electrolytes /
- ionic conductivity /
- free volume
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[2] Ahmad S 2009 Ionics 15 309
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[52] Hu L, Tang Z, Zhang Z 2007 J. Power Sources 166 226
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[60] Dlubek G, Saarinen K, Fretwell H M 1998 J. Polym. Sci. B 36 1513
[61] [62] [63] Wang H M, Chen Z, Fang P F, Wang S J, Xu Y Z, Fang Z P 2008 J. Appl. Polym. Sci. 108 1557
[64] [65] Ji K S, Moon H S, Kim J W, Park J W 2003 J. Power Sources 117 124
[66] Murday J S, Cotts R M 1968 J. Chem. Phys. 48 4938
[67] -
[1] Manuel S A, Nahm K S 2006 Polymer 47 5952
[2] Ahmad S 2009 Ionics 15 309
[3] [4] [5] Fergus J W 2010 J. Power Sources 195 4554
[6] [7] Fenton D E, Parker J M, Wright P V 1973 Polymer 14 589
[8] Croce F, Appetecchi G B, Persi L, Scrosati B 1998 Nature 394 456
[9] [10] [11] Forsyth M, MacFarlane D R, Best A, Adebahr J, Jacobsson P, Hill A J 2002 Solid State Ionics 147 203
[12] Adebahr J, Ciccosillo N, Shekibi Y, MacFarlane D R, Hill A J, Forsyth M 2006 Solid State Ionics 177 827
[13] [14] Kim J W, Ji K S, Lee J P, Park J W 2003 J. Power Sources 119-121 415
[15] [16] Agrawal S, Singh M, Tripathi M, Dwivedi M, Pandey K 2009 J. Mater. Sci. 44 6060
[17] [18] Kster T K J, Wllen V L 2010 Solid State Ionics 181 489
[19] [20] [21] Xiong H M, Zhao X, Chen J S 2001 J. Phys. Chem. B 105 10169
[22] [23] Bhattacharya S, Ghosh A 2008 J. Nanosci. Nanotechnol. 8 1922
[24] [25] Lin D,Wang S J 1992 Acta Phys. Sin. 41 668 (in Chinese)[林 东、王少阶 1992 物理学报 41 668]
[26] [27] Wang B, Wang Z F, Zhang M, Liu W H, Wang S J 2002 Macromolecules 35 3993
[28] [29] Zhou W, Wang J J, Gong Z L, Gong J, Qi N, Wang B 2009 Appl. Phys. Lett. 94 021904
[30] Kobayashi Y, Zheng W, Meyer E F, McGervey J D, Jamieson A M, Simha R 1989 Macromolecules 22 2302
[31] [32] Jean Y C 1990 Microchem. J. 42 72
[33] [34] Suzuki T, Oki Y, Numajiri M, Miura T, Kondo K, Ito Y 1992 J. Polym. Sci. B 30 517
[35] [36] Peng Z L, Wang B, Li S Q, Wang S J, Liu H, Xie H Q 1994 Phys. Lett. A 194 228
[37] [38] [39] Wang B, Peng Z L, Wu W, Li S Q, Wang S J, Liu H, Xie H Q 1996 Acta Phys. Sin. 45 153 (in Chinese)[王 波、彭治林、吴 弯、李世清、王少阶、刘 浩、谢洪泉 1996 物理学报 45 153]
[40] [41] Stephan A M, Kumar T P, Kulandainathan M A, Lakshmi N A 2009 J. Phys. Chem. B 113 1963
[42] [43] Li Z R, Meng Q A, Guan D H, Wang G 1999 Acta Phys. Sin. 48 1175 (in Chinese)[李子荣、孟庆安、管荻华、王 刚 1999 物理学报 48 1175]
[44] [45] Wang L, Yang W, Wang J, Evans D G 2009 Solid State Ionics 180 392
[46] [47] Przyluski J, Siekierski M,Wieczorek W 1995 Electrochim. Acta 40 2101
[48] Wieczorek W, Zalewska A, Siekierski M, Przyluski J 1996 Solid State Ionics 86-88 357
[49] [50] [51] Kao H M, Tsai Y Y, Chao S W 2005 Solid State Ionics 176 1261
[52] Hu L, Tang Z, Zhang Z 2007 J. Power Sources 166 226
[53] [54] Wu R J 1987 Modern Analytical Techniques in Polymer Application (Shanghai: Shanghai Science and Technology Press) p300 (in Chiese) [吴人杰 1987现代分析技术在高聚物中的应用 (上海:上海科学技术出版社) 第300页]
[55] [56] Wieczorek W, Lipka P, Z ukowska G, Wyci Dś lik H 1998 J. Phys. Chem. B 102 6968
[57] [58] [59] Wieczorek W, Raducha D, Zalewska A, Stevens J R 1998 J. Phys. Chem. B 102 8725
[60] Dlubek G, Saarinen K, Fretwell H M 1998 J. Polym. Sci. B 36 1513
[61] [62] [63] Wang H M, Chen Z, Fang P F, Wang S J, Xu Y Z, Fang Z P 2008 J. Appl. Polym. Sci. 108 1557
[64] [65] Ji K S, Moon H S, Kim J W, Park J W 2003 J. Power Sources 117 124
[66] Murday J S, Cotts R M 1968 J. Chem. Phys. 48 4938
[67]
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