Scalable Synthesis of Hierarchical Antimony/Carbon Micro-/Nanohybrid Lithium/Sodium-Ion Battery Anodes Based on Dimethacrylate Monomer

doi:10.1007/s40195-018-0733-5

Abstract

Abstract:

A facile scalable synthesis of hierarchical Sb/C micro-/nanohybrid has been addressed in this work, which possesses the advantages of both micrometer and nanometer scale structures as lithium-ion battery anode. Difunctional methacrylate monomers are used as solvent and carbon source as well. Liquid precursor of antimony(III) n-butoxide is dissolved in the resin monomer solution, and further incorporated into the cross-linking polymer network via photo polymerization. Through calcination in argon/hydrogen atmosphere, antimony nanoparticles are in situ formed by carbothermal reduction, and homogeneously embedded in the in situ formed micrometer sized carbon matrix. The morphology, structure, crystallinity, spatial dispersion, composition, and electrochemical performance of the Sb/C micro-/nanohybrid are systematically investigated. The cyclic and rate performance of the Sb/C micro-/nanohybrid anode have been effectively improved compared to the pure carbon anode. A reversible capacity of 362 mAh g^-1 is achieved with a reasonable mass loading density after 300 cycles at 66 mA g^-1, corresponding to capacity retention of 79%. With reducing mass loading density, the reversible capacity reaches 793 mAh g^-1 after 100 cycles. Moreover, the electrochemical performance of Sb/C micro-/nanohybrid as sodium-ion battery anode is also investigated in this study.

Key words: Antimony/carbon micro-/nanohybrid, Lithium-ion battery, Sodium-ion battery, Anode, Methacrylate, Photo polymerization, Thermosetting resin

Su-Zhe Liang, Xiao-Yan Wang, Yong-Gao Xia, Sen-Lin Xia, Ezzeldin Metwalli, Bao Qiu, Qing Ji, Shan-Shan Yin, Shuang Xie, Kai Fang, Lu-Yao Zheng, Mei-Mei Wang, Xiu-Xia Zuo, Ru-Jiang Li, Zhao-Ping Liu, Jin Zhu, Peter Müller-Buschbaum, Ya-Jun Cheng. Scalable Synthesis of Hierarchical Antimony/Carbon Micro-/Nanohybrid Lithium/Sodium-Ion Battery Anodes Based on Dimethacrylate Monomer[J]. Acta Metallurgica Sinica (English Letters), 2018, 31(9): 910-922.

Figures/Tables 13

Scheme 1 Synthesis of the Sb/C hierarchical micro-/nanohybrid using dental methacrylate monomers as solvent and carbon source via photo polymerization.

Fig. 1 Low magnification a, c and high magnification b, d SEM images of the Sb/C micro-/nanohybrid a, b, pure carbon c, d.

Fig. 2 TEM images of the Sb/C micro-/nanohybrid a, b, pure carbon c, d. Inset: SEAD pattern (in a) and local crystal plane of the antimony particles (in b) .

Fig. 3 STEM a, c, e and EDX b, d, f images of the Sb/C micro-/nanohybrid: TEM image a and SEM image b, elemental mapping of carbon c, d, Sb e, f.

Fig. 4 XRD a, Raman b, TGA c profiles of the Sb/C micro-/nanohybrid (red) and pure carbon (black), TGA d profile of commercial antimony powders.

Fig. 5 Nitrogen adsorption-desorption isotherms a, corresponding pore size distribution b of the Sb/C micro-/nanohybrid (red) and pure carbon (black) .

Fig. 6 Small angle X-ray scattering (SAXS) profiles of the Sb/C micro-/nanohybrid (red) and pure carbon (black) .

Fig. 7 Cyclic voltammetry profiles of the pure carbon a and Sb/C micro-/nanohybrid b. The curves with black, red, and blue colors refer to the 1st, 2nd, and 3rd cycle, respectively.

Fig. 8 Galvanostatic discharge/charge curves of the pure carbon a and Sb/C micro-/nanohybrid b. The 1st, 2nd, 50th, and 200th cycles are displayed by the black, blue, red, and cyan curves, respectively.

Fig. 9 Cycling performance at the current density of 66 mA g-1 a and rate performance b of the pure carbon (black) and Sb/C micro-/nanohybrid (red), hollow circle represents charge process and solid circle represents discharge process.

Fig. 10 Electrochemical impedance spectra of the Sb/C micro-/nanohybrid (red) and pure carbon (black) .

Fig. 11 Galvanostatic discharge-charge curves a and cycling performance b of the Sb/C micro-/nanohybrid electrode with a mass loading density of 0.14 mg cm-2 at the current density of 66 mA g-1. The curves with the black, blue, red, and dark cyan color in image are referred to the 1st, 2nd, 50th, and 100th cycles, respectively.

Fig. 12 Cycling performance at the current density of 66 mA g-1 a and rate performance b of the pure carbon (magenta) and Sb/C micro-/nanohybrid (blue) as NIB anodes. Hollow circle: charge process, solid circle: discharge process.

References

[1]	W.J. Zhang,J. Power Sources 196, 13 (2011)
[2]	N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Chem. Rev. 114, 11636(2014)
[3]	M.S. Whittingham, Chem. Rev. 104, 4271(2004)
[4]	S.Y. Hong, Y. Kim, Y. Park, A. Choi, N.S. Choi, K.T. Lee, Energy Environ. Sci. 6, 2067 (2013)
[5]	B. Kang, G. Ceder, Nature 458, 190 (2009)
[6]	M.N. Obrovac, V.L. Chevrier, Chem. Rev. 114, 11444(2014)
[7]	Z.H.A.L.Y. Yang, J. Mater.Sci .Technol. 20, 743(2004)
[8]	N. Wang, Z. Bai, Y. Qian, J. Yang, Adv. Mater. 28, 4126(2016)
[9]	Z. Liu, X.Y. Yu, X.W. Lou, U. Paik, Energy Environ.Sci. 9, 2314(2016)
[10]	X. Hou, S. Hu, W. Peng, Z. Zhang, Q. Ru, Acta Metall. Sin. (Engl. Lett.) 23, 363(2010)
[11]	C. Chen, K. Fu, Y. Lu, J. Zhu, L. Xue, Y. Hu, X. Zhang, RSC Adv. 5, 30793(2015)
[12]	H. Kim, J. Cho, Chem. Mater. 20, 1679(2008)
[13]	H. Hou, M. Jing, Y. Yang, Y. Zhu, L. Fang, W. Song, C. Pan, X. Yang, X. Ji, A.C.S. Appl, Mater. Interfaces 6, 16189 (2014)
[14]	L. Wu, X. Hu, J. Qian, F. Pei, F. Wu, R. Mao, X. Ai, H. Yang, Y. Cao, Energy Environ.Sci. 7, 323(2014)
[15]	Z. Yi, Q. Han, P. Zan, Y. Wu, Y. Cheng, L. Wang, J.Power Sources 331, 16 (2016)
[16]	M. Wang, Z. Yang, J. Wang, W. Li, L. Gu, Y. Yu, Small 11, 5381 (2015)
[17]	T. Yang, H. Wang, J. Xu, L. Wang, W.C. Song, Y. Mao, J. Ma, RSC Adv. 6, 78959(2016)
[18]	W. Luo, S. Lorger, B. Wang, C. Bommier, X. Ji, Chem. Commun. (Camb.) 50, 5435(2014)
[19]	Y. Yi, H.W. Shim, S.D. Seo, M.A. Dar, D.W. Kim, Mater. Res. Bull. 76, 338(2016)
[20]	Y.N. Ko, Y.C. Kang, Chem. Commun. (Camb.) 50, 12322(2014)
[21]	L. Fan, J. Zhang, J. Cui, Y. Zhu, J. Liang, L. Wang, Y. Qian, J. Mater. Chem.A 3, 3276 (2015)
[22]	L. Hu, X. Zhu, Y. Du, Y. Li, X. Zhou, J. Bao, Chem. Mater. 27, 8138(2015)
[23]	K. Li, D. Su, H. Liu, G. Wang, Electrochim. Acta 177, 304 (2015)
[24]	X. Zhao, S.A. Vail, Y. Lu, J. Song, W. Pan, D.R. Evans, J.J. Lee, A.C.S. Appl, Mater.Interfaces 8, 13871 (2016)
[25]	W. Luo, P. Zhang, X. Wang, Q. Li, Y. Dong, J. Hua, L. Zhou, L. Mai, J.Power Sources 304, 340 (2016)
[26]	S. Qiu, X. Wu, L. Xiao, X. Ai, H. Yang, Y. Cao, A.C.S. Appl, Mater.Interfaces 8, 1337 (2016)
[27]	J.L.Gómez-Cámer, C. Villevieille, P. Novák, J. Mater. Chem A 1, 13011 (2013)
[28]	Y. Zhang, J. Xie, T. Zhu, G. Cao, X. Zhao, S. Zhang, J.Power Sources 247, 204 (2014)
[29]	N. Wang, Z. Bai, Y. Qian, J. Yang, A.C.S. Appl, Mater.Interfaces 9, 447 (2017)
[30]	J. Liu, L. Yu, C. Wu, Y. Wen, K. Yin, F.K. Chiang, R. Hu, J. Liu, L. Sun, L. Gu, J. Maier, Y. Yu, M. Zhu, Nano Lett. 17, 2034 (2017)
[31]	J. Xie, X.B. Zhao, G.S. Cao, M.J. Zhao, J. Mater. Sci.Technol. 22, 31(2006)
[32]	C. Jiang, J. Zhang, J. Mater. Sci.Technol. 29, 97(2013)
[33]	J. Wang, J. Yang, W. Yin, S.I. Hirano, J. Mater.Chem A 5, 20623 (2017)
[34]	T. Wu, H. Hou, C. Zhang, P. Ge, Z. Huang, M. Jing, X. Qiu, X. Ji, A.C.S. Appl, Mater.Interfaces 9, 26118 (2017)
[35]	Q. Yang, J. Zhou, G. Zhang, C. Guo, M. Li, Y. Zhu, Y. Qian, J. Mater.Chem A 5, 12144 (2017)
[36]	L. Thang Van, N. Ha Tran, L. Anh Tuan, T. Man Van, L. Phung Loan My, Acta Metall. Sin. (Engl. Lett.) 28, 122(2015)
[37]	P.G. Bruce, B. Scrosati, J.M. Tarascon, Angew. Chem.Int. Edit. 47, 2930(2008)
[38]	J. Ban, P. Yang, Y. Xiaa, M. Wang, X. Wang, Y. Xiao, B. Qiu, L. Yang, Z. Liu, C. Zhu, Dig. J. Nanomater.Biostruct. 11, 223(2016)
[39]	M. Wang, Y. Xia, X. Wang, Y. Xiao, R. Liu, Q. Wu, B. Qiu, E. Metwalli, S. Xia, Y. Yao, G. Chen, Y. Liu, Z. Liu, J.Q. Meng, Z. Yang, L.D. Sun, C.H. Yan, P. Muller-Buschbaum, J. Pan, Y.J. Cheng, A.C.S. Appl, Mater.Interfaces 8, 13982 (2016)
[40]	M. Wang, Y. Xia, X. Wang, Y. Xiao, Q. Zhang, R. Liu, B. Qiu, Q. Wu, G. Chen, Y. Liu, Dig. J. Nanomater.Biostruct. 11, 567(2016)
[41]	X. Wang, J.Q. Meng, M. Wang, Y. Xiao, R. Liu, Y. Xia, Y. Yao, E. Metwalli, Q. Zhang, B. Qiu, Z. Liu, J. Pan, L.D. Sun, C.H. Yan, P. Muller-Buschbaum, Y.J. Cheng, A.C.S. Appl, Mater.Interfaces 7, 24247 (2015)
[42]	Y. Xiao, X. Wang, Y. Xia, Y. Yao, E. Metwalli, Q. Zhang, R. Liu, B. Qiu, M. Rasool, Z. Liu, J.Q. Meng, L.D. Sun, C.H. Yan, P. Muller-Buschbaum, Y.J. Cheng, A.C.S. Appl, Mater.Interfaces 6, 18461 (2014)
[43]	T. Ramireddy, N. Sharma, T. Xing, Y. Chen, J. Leforestier, A.M. Glushenkov, A.C.S. Appl, Mater.Interfaces 8, 30152 (2016)
[44]	J.S. Lannin, J.M. Calleja, M. Cardona, Phys. Rev. B 12, 585 (1975)
[45]	X. Wang, K. Kunc, I. Loa, U. Schwarz, K. Syassen, Phys. Rev. B 74, 134305 (2006)
[46]	A.C. Ferrari, Solid State Commun. 143, 47(2007)
[47]	W. Li, L. Zeng, Z. Yang, L. Gu, J. Wang, X. Liu, J. Cheng, Y. Yu, Nanoscale 6, 693 (2014)
[48]	T. Xing, L.H. Li, L. Hou, X. Hu, S. Zhou, R. Peter, M. Petravic, Y. Chen, Carbon 57, 515 (2013)
[49]	Y. Cheng, Z. Yi, C. Wang, L. Wang, Y. Wu, L. Wang, Chem-Asian J.11, 2173 (2016)
[50]	K.S. Sing, Pure Appl.Chem. 57, 603(1985)
[51]	J. Liu, S.Z. Qiao, S. Budi Hartono, G.Q. Lu, Angew. Chem. Int. Edit. Engl. 49, 4981(2010)
[52]	Y. Xia, Z. Xiao, X. Dou, H. Huang, X. Lu, R. Yan, Y. Gan, W. Zhu, J. Tu, W. Zhang, X. Tao, ACS Nano 7, 7083 (2013)
[53]	L. Shen, C. Yuan, H. Luo, X. Zhang, K. Xu, Y. Xia, J. Mater. Chem. 20, 6998(2010)
[54]	H. Lv, S. Qiu, G. Lu, Y. Fu, X. Li, C. Hu, J. Liu, Electrochim. Acta 151, 214 (2015)
[55]	A. Dailly, J. Ghanbaja, P. Willmann, D. Billaud, Electrochim. Acta 48, 977 (2003)
[56]	D. Chang, H. Huo, K.E. Johnston, M. Ménétrier, L. Monconduit, C.P. Grey, A. Van der Ven, J. Mater. Chem. A 3, 18928 (2015)
[57]	Y. Yang, X. Yang, Y. Zhang, H. Hou, M. Jing, Y. Zhu, L. Fang, Q. Chen, X. Ji, J.Power Sources 282, 358 (2015)
[58]	K.C. Hewitt, L.Y. Beaulieu, J.R. Dahn, J. Electrochem. Soc. 148, A402(2001)
[59]	H. Li, X. Huang, L. Chen, Solid State Ion. 123, 189(1999)
[60]	J. Xiang, W. Lv, C. Mu, J. Zhao, B. Wang, J. Alloys Compd. 701, 870(2017)
[61]	F.A. Soto, P. Yan, M.H. Engelhard, A. Marzouk, C. Wang, G. Xu, Z. Chen, K. Amine, J. Liu, V.L. Sprenkle, F. El-Mellouhi, P.B. Balbuena, X. Li, Adv. Mater. 29, 1606860(2017)
[62]	N. Liu, Z. Lu, J. Zhao, M.T. McDowell, H.W. Lee, W. Zhao, Y. Cui.Nat. Nanotechnol. 9, 187(2014)
[63]	H. Wu, G. Chan, J.W. Choi, I. Ryu, Y. Yao, M.T. McDowell, S.W. Lee, A. Jackson, Y. Yang, L. Hu, Y. Cu.Nat. Nanotechnol. 7, 310(2012)
[64]	H. Wu, G. Yu, L. Pan, N. Liu, M.T. McDowell, Z. Bao, Y. Cui, Nat. Commun.4, 1943 (2013)