In Situ Synthesis of Core-Shell Li4Ti5O12 @Polyaniline Composites with Enhanced Rate Performance for Lithium-ion Battery Anodes

Abstract

Abstract:

The core-shell Li₄Ti₅O₁₂ @polyaniline composites (LP) have been synthesized via an in situ synthesis with different mole ratios (25:1, 50:1 and 100:1, aniline:LTO). As an anode material of lithium-ion batteries, the LP-2 electrodes (50:1) exhibit a high initial reversible capacity of 205 mAh g^-1 with an initial coulombic efficiency of 97.6% at 0.1 C. Even at a high current density of 10 C, the reversible capacity of the LP-2 electrodes still remains at 102 mAh g^-1. Moreover, the LP-2 electrodes retain an impressive high capacity of 161 mAh g^-1 after 100 cycles at 1 C, with 0.11% capacity fading per cycle. The promising electrochemical performance may be attributed to the significantly decreasing charge-transfer impedance of the LP composite and reductive polarity difference between the cathode and the electrolyte.

Key words: Li4Ti5O12, Polyaniline, Lithium-ion batteries, Electrochemical property

Hui Yani,Cao Liyun,*,Xu Zhanwei,Huang** Jianfeng,Ouyang Haibo,Li Jiayin,Hu Hailing. In Situ Synthesis of Core-Shell Li4Ti5O12 @Polyaniline Composites with Enhanced Rate Performance for Lithium-ion Battery Anodes[J]. J. Mater. Sci. Technol., 2017, 33(3): 231-238.

Figures/Tables 6

Fig.1. 1.(a) XRD patterns of LTO, LP-1, LP-2, and LP-3; (b) IR spectra of LTO, PANI, LP-1, LP-2, and LP-3; (c) TGA curves of LTO, PANI, LP-1, LP-2, and LP-3 under a heating rate of 10?°C min-1 in air.

Fig.2. FESEM micrographs of (a) LTO, (b) PANI, (c) LP-1, (d) LP-2, (e) LP-3.

Fig.3. (a) TEM, (b) HRTEM, and (c) TEM element mapping images of LP-2

Fig.4. (a) Rate performances of LTO, PANI, LP-1, LP-2 and LP-3 electrodes, measured from 0.1 to 10 C; (b) initial discharge-charge curves of LTO, PANI, LP-1, LP-2 and LP-3 electrodes at 0.1 C; (c) cycle performance and corresponding coulombic efficiencies of LTO and LP-2 electrodes at 1 C; (d) continuous discharge and charge curves of LTO electrodes; (e) continuous discharge and charge curves of LP-2 electrodes (1 C?=?175?mA g-1).

Fig.5. (Cyclic voltammograms of LTO, PANI and LP-2 electrodes.

Fig.6. (a) Nyquist plots of the LTO and LP-2 electrodes, the inset figure shows the equivalent circuit for the plot fitting; (b) the relationship between Zre and ω-1/2 of LTO and LP-2 electrodes.

References

[1]	S. Aziz1, J. Zhao, C. Cain, Y. Wang J. Mater. Sci. Technol, 30(2014), pp. 427-433
[2]	B. Sun, K. Huang, X. Qi, X. Wei, J. Zhong, Adv. Funct. Mater, 25(2015), pp. 5633-5639
[3]	Y. Xu, Y. Zhu, Y. Liu, C. Wang, Adv. Energy Mater, 3(2013), pp. 128-133
[4]	Y.S. Kim, Y.L. Joo, Y.J. Kwark, J. Mater. Sci.Technol, 32(2016), pp. 195-199
[5]	C. Lin, X. Fan, Y. Xin, F. Cheng, M.O. Lai, H. Zhou, L. Lu, J. Mater. Chem.A, 2(2014), pp. 9982-9993
[6]	Z. Yu, G. Zhu, H. Xu, A. Yu, Energy Technol, 2(2014), pp. 767-772
[7]	Z. Chen, I. Belharouak, Y.K. Sun, K. Amine, Adv. Funct. Mater, 23(2013), pp. 959-969
[8]	G. Hasegawa, K. Kanamori, T. Kiyomura, H. Kurata, K. Nakanishi, T. Abe,Adv. Energy Mater, 5(2015), pp. 1400730-1400737
[9]	L. Gong, Y. Chen, H. Yu, H. Liu, C. Li, Z.Q. Liu,J. Mater. Sci.Technol, 30(2014), pp. 1092-1095
[10]	D.H. Long, M.G. Jeong, Y.S. Lee, W. Choi, J.K. Lee, I.H. Oh, H.G. Jung,ACS Appl. Mater. Int, 7(2015), pp. 10250-10257
[11]	Y. Yang, B. Qiao, X. Yang, L. Fang, C. Pan, W. Song, H. Hou, X. Ji,Adv. Funct. Mater, 24(2014), pp. 4349-4356
[12]	G.B. Xu, W. Li, L.W. Yang, X.L. Wei, J.W. Ding, J.X. Zhong, P.K. Chu,J. Power Sources, 276(2015), pp. 247-254
[13]	K.T. Kim, C.Y. Yu, C.S. Yoon, S.J. Kim, Y.K. Sun, S.T. Myung,Nano Energy, 12(2015), pp. 725-734
[14]	L. Yu, H.B. Wu, X.W.Lou
[15]	S.W. Han, S.J. Kim, E.S. Oh,J. Electrochem.Soc, 161(2014), pp. A587-A592
[16]	T.P. Zhou, X.Y. Feng, X. Guo, W.W. Wu, S. Cheng, H.F. Xiang,Electrochim. Acta, 174(2015), pp. 369-375
[17]	L. Shen, E. Uchaker, X. Zhang, G. Cao,Adv. Mater, 24(2012), pp. 6502-6506
[18]	Z. Xie, X. Li, W. Li, M. Chen, M. Qu,J. Power Sources, 273(2015), pp. 754-760
[19]	H. Ge, T. Hao, H. Osgood, B. Zhang, L. Chen, L. Cui, X.M. Song, O. Ogoke, G. Wu,ACS Appl. Mater. Interfaces, 8(2016), pp. 9162-9169
[20]	X. Liang, Y. Yang, X. Jin, J. Cheng,J. Mater. Sci.Technol, 32(2016), pp. 200-206
[21]	M.B. Radoičić, M.V. Milošević, D.S. Miličević, E.H. Suljovrujić, G.N.Ćirić-Marjanović, M.M. Radetić, Z.V. Šaponjić,Surf. Coat. Technol, 278(2015), pp. 38-47
[22]	P. Dou, A. Jiang, X. Fan, D. Ma, X. Xu,RSC Adv, 5(2015), pp. 21525-21531
[23]	H. Ding, H. Jiang, Z. Zhu, Y. Hu, F. Gu, C. Li,Electrochim. Acta, 157(2015), pp. 205-210
[24]	L. Wang, X. Lu, S. Lei, Y. Song,J. Mater. Chem.A, 2(2014), pp. 4491-4509
[25]	W. Xu, K. Zhao, C. Niu, L. Zhang, Z. Cai, C. Han, L. He, T. Shen, M. Yan, L. Qu, L. Mai,Nano Energy, 8(2014), pp. 196-204
[26]	W.L. Wang, J.Y. Park, V.H. Nguyen, E.M. Jin, H.B. Gu,Ceram. Int, 42(2016), pp. 598-606
[27]	G. Wang, J. Peng, L. Zhang, J. Zhang, B. Dai, M. Zhu, L. Xia, F. Yu,J. Mater. Chem.A, 3(2015), pp. 3659-3666
[28]	H. Yan, W. Chen, X. Wu, Y. Li,Electrochim. Acta, 146(2014), pp. 295-300
[29]	F. Ye, B. Zhao, R. Ran, Z. Shao,J. Power Sources, 290(2015), pp. 61-70
[30]	S. Zhang, S. Peng, S. Liu, L. Ren, S. Wang, J. Fu,Mater. Lett, 110(2013), pp. 168-171
[31]	Z.Q. He, L.Z. Xiong, S. Chen, X.M. Wu, W.P. Liu, K.L. Huang,Trans. Nonferrous Met. Soc. China, 20(2010), pp. s262-s266
[32]	S. Cao, X. Feng, Y. Song, X. Xue, H. Liu, M. Miao, J. Fang, L. Shi,ACS Appl. Mater. Int, 7(2015), pp. 10695-10701
[33]	M.R. Jo, Y.S. Jung, Y.M. Kang,Nanoscale, 4(2012), pp. 6870-6875
[34]	J. Lu, C. Nan, Q. Peng, Y. Li,J. Power Sources, 202(2012), pp. 246-252
[35]	A. Laumann, K.T. Fehr, M. Wachsmann, M. Holzapfel, B.B. Iversen,Solid State Ionics, 181(2010), pp. 1525-1529
[36]	Y. Hao, Q. Lai, Z. Xu, X. Liu, X. Ji,Solid State Ionics, 176(2005), pp. 1201-1206
[37]	J. Li, Y. Jin, X. Zhang, H. Yang,Solid State Ionics, 178(2007), pp. 1590-1594
[38]	Z. Lei, X. Sun, H. Wang, Z. Liu, X.S. Zhao,ACS Appl. Mater. Int, 5(2013), pp. 7501-7508
[39]	C. Murugan, E. Subramanian, D.P. Padiyan,Synthetic Met, 192(2014), pp. 106-112
[40]	Q. Wang, Y. Huang, J. Miao, Y. Zhao, Y. Wang,Appl. Surf. Sci, 258(2012), pp. 9896-9901
[41]	H. Liu, F. Zhang, W. Li, X. Zhang, C.S. Lee, W. Wang, Y. Tang,Electrochim. Acta, 167(2015), pp. 132-138
[42]	J. Huang, Z. Xu, L. Cao, Q. Zhang, H. Ouyang, J. Li,Energy Technol, 3(2015), pp. 1108-1114
[43]	B. Li, C. Han, Y.B. He, C. Yang, H. Du, Q.H. Yang, F. Kang,Energ. Environ. Sci, 5(2012), pp. 9595-9602
[44]	C. Lai, H.Z. Zhang, G.R. Li, X.P. Gao,J. Power Sources, 196(2011), pp. 4735-4740
[45]	S. Wang, L. Hu, Y. Hu, S. Jiao,Mater. Chem. Phys, 146(2014), pp. 289-294
[46]	S.R. Sivakkumar, D.W. Kim,J. Electrochem.Soc, 154(2007), pp. A134-A139
[47]	J. Wang, J. Polleux, J. Lim, B. Dunn,J. Phys. Chem.C, 111(2007), pp. 14925-14931
[48]	H. Ge, L. Chen, W. Yuan, Y. Zhang, Q. Fan, H. Osgood, D. Matera, X.M. Song, G. Wu,J. Power Sources, 297(2015), pp. 436-441
[49]	X.P. Li, J. Mao,New J. Chem, 39(2015), pp. 4430-4436
[50]	X. Xiang, Z. Huang, E. Liu, H. Shen, Y. Tian, H. Xie, Y. Wu, Z. Wu,Electrochim. Acta, 56(2011), pp. 9350-9356
[51]	C. Cheng, H. Liu, J. Li, X. Xue, H. Cao, D. Wang, L. Shi,J. Power Sources, 283(2015), pp. 237-242