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Research Article

Confined growth of Li4Ti5O12 nanoparticles in nitrogen-doped mesoporous graphene fibers for high-performance lithium-ion battery anodes

Xilai Jia1, Yunfeng Lu3(), Fei Wei2 ()
State Key Laboratory of Heavy Oil ProcessingChina University of PetroleumBeijing102249China
Beijing Key Laboratory of Green Chemical Reaction Engineering and TechnologyDepartment of Chemical EngineeringTsinghua UniversityBeijing100084China
Department of Chemical and Biomolecular EngineeringUniversity of CaliforniaLos AngelesCA90095USA
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Abstract

Nanomaterials with electrochemical activity are always suffering from aggregations, particularly during the high-temperature synthesis processes, which will lead to decreased energy-storage performance. Here, hierarchically structured lithium titanate/nitrogen-doped porous graphene fiber nanocomposites were synthesized by using confined growth of Li4Ti5O12 (LTO) nanoparticles in nitrogen-doped mesoporous graphene fibers (NPGF). NPGFs with uniform pore structure are used as templates for hosting LTO precursors, followed by high-temperature treatment at 800 ℃ under argon (Ar). LTO nanoparticles with size of several nanometers are successfully synthesized in the mesopores of NPGFs, forming nanostructured LTO/NPGF composite fibers. As an anode material for lithium-ion batteries, such nanocomposite architecture offers effective electron and ion transport, and robust structure. Such nanocomposites in the electrodes delivered a high reversible capacity (164 mAh·g–1 at 0.3 C), excellent rate capability (102 mAh·g–1 at 10 C), and long cycling stability.

Keywords

lithium titanatenitrogen-doped porous graphene fiberslithium-ion batteries

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References

1

Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Challenges in the development of advanced Li-ion batteries: A review. Energy Environ. Sci. 2011, 4, 3243–3262.

Crossref Google Scholar
2

Scrosati, B.; Garche, J. Lithium batteries: Status, prospects and future. J. Power Sources 2010, 195, 2419–2430.

Crossref Google Scholar
3

Yi, T. -F.; Yang, S. -Y.; Xie, Y. Recent advances of Li4Ti5O12 as a promising next generation anode material for high power lithium-ion batteries. J. Mater. Chem. A 2015, 3, 5750–5777.

Crossref Google Scholar
4

Naoi, K.; Naoi, W.; Aoyagi, S.; Miyamoto, J. -I.; Kamino, T. New generation "nanohybrid supercapacitor". Acc. Chem. Res. 2013, 46, 1075–1083.

Crossref Google Scholar
5

Wang, Y. -Q.; Gu, L.; Guo, Y. -G.; Li, H.; He, X. -Q.; Tsukimoto, S.; Ikuhara, Y.; Wan, L. -J. Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. J. Am. Chem. Soc. 2012, 134, 7874–7879.

Crossref Google Scholar
6

Lim, J.; Choi, E.; Mathew, V.; Kim, D.; Ahn, D.; Gim, J.; Kang, S. -H.; Kim, J. Enhanced high-rate performance of Li4Ti5O12 nanoparticles for rechargeable Li-ion batteries. J. Electrochem. Soc. 2011, 158, A275–A280.

Crossref Google Scholar
7

Jiang, C. H.; Ichihara, M.; Honma, I.; Zhou, H. S. Effect of particle dispersion on high rate performance of nano-sized Li4Ti5O12 anode. Electrochim. Acta 2007, 52, 6470–6475.

Crossref Google Scholar
8

Haridas, A. K.; Sharma, C. S.; Rao, T. N. Donut-shaped Li4Ti5O12 structures as a high performance anode material for lithium ion batteries. Small 2015, 11, 290–294.

Crossref Google Scholar
9

Zhang, Y. L.; Hu, X. B.; Xu, Y. L.; Ding, M. L. Recent progress of Li4Ti5O12 with different morphologies as anode material. Acta Chim. Sin. 2013, 71, 1341–1353.

Crossref Google Scholar
10

Jung, H. -G.; Myung, S. -T.; Yoon, C. S.; Son, S. -B.; Oh, K. H.; Amine, K.; Scrosati, B.; Sun, Y. -K. Microscale spherical carbon-coated Li4Ti5O12 as ultra high power anode material for lithium batteries. Energy Environ. Sci. 2011, 4, 1345–1351.

Crossref Google Scholar
11

Ganapathy, S.; Wagemaker, M. Nanosize storage properties in spinel Li4Ti5O12 explained by anisotropic surface lithium insertion. ACS Nano 2012, 6, 8702–8712.

Crossref Google Scholar
12

Bruce, P. G.; Scrosati, B.; Tarascon, J. M. Nanomaterials for rechargeable lithium batteries. Angew. Chem., Int. Ed. 2008, 47, 2930–2946.

Crossref Google Scholar
13

Cheng, J.; Che, R. C.; Liang, C. Y.; Liu, J. W.; Wang, M.; Xu, J. J. Hierarchical hollow Li4Ti5O12 urchin-like microspheres with ultra-high specific surface area for high rate lithium ion batteries. Nano Res. 2014, 7, 1043–1053.

Crossref Google Scholar
14

Wang, X. F.; Liu, B.; Hou, X. J.; Wang, Q. F.; Li, W. W.; Chen, D.; Shen, G. Z. Ultralong-life and high-rate web-like Li4Ti5O12 anode for high-performance flexible lithium-ion batteries. Nano Res. 2014, 7, 1073–1082.

Crossref Google Scholar
15

Xu, H. H.; Hu, X. L.; Sun, Y. M.; Luo, W.; Chen, C. J.; Liu, Y.; Huang, Y. H. Highly porous Li4Ti5O12/C nanofibers for ultrafast electrochemical energy storage. Nano Energy 2014, 10, 163–171.

Crossref Google Scholar
16

Feckl, J. M.; Fominykh, K.; Döblinger, M.; Fattakhova-Rohlfing, D.; Bein, T. Nanoscale porous framework of lithium titanate for ultrafast lithium insertion. Angew. Chem. , Int. Ed. 2012, 51, 7459–7463.

Crossref Google Scholar
17

Shen, L. F.; Uchaker, E.; Zhang, X. G.; Cao, G. Z. Hydrogenated Li4Ti5O12 nanowire arrays for high rate lithium ion batteries. Adv. Mater. 2012, 24, 6502–6506.

Crossref Google Scholar
18

Chen, S.; Xin, Y. L.; Zhou, Y. Y.; Ma, Y. R.; Zhou, H. H.; Qi, L. M. Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life. Energy Environ. Sci. 2014, 7, 1924–1930.

Crossref Google Scholar
19

Liu, J.; Song, K. P.; van Aken, P. A.; Maier, J.; Yu, Y. Self-supported Li4Ti5O12-C nanotube arrays as high-rate and long-life anode materials for flexible Li-ion batteries. Nano Lett. 2014, 14, 2597–2603.

Crossref Google Scholar
20

Kang, E.; Jung, Y. S.; Kim, G. H.; Chun, J.; Wiesner, U.; Dillon, A. C.; Kim, J. K.; Lee, J. Highly improved rate capability for a lithium-ion battery nano-Li4Ti5O12 negative electrode via carbon-coated mesoporous uniform pores with a simple self-assembly method. Adv. Funct. Mater. 2011, 21, 4349–4357.

Crossref Google Scholar
21

Sorensen, E. M.; Barry, S. J.; Jung, H. -K.; Rondinelli, J. M.; Vaughey, J. T.; Poeppelmeier, K. R. Three-dimensionally ordered macroporous Li4Ti5O12: Effect of wall structure on electrochemical properties. Chem. Mater. 2006, 18, 482–489.

Crossref Google Scholar
22

Kubiak, P.; Garcia, A.; Womes, M.; Aldon, L.; Olivier- Fourcade, J.; Lippens, P. -E.; Jumas, J. -C. Phase transition in the spinel Li4Ti5O12 induced by lithium insertion: Influence of the substitutions Ti/V, Ti/Mn, Ti/Fe. J. Power Sources 2003, 119–121, 626–630.

Crossref Google Scholar
23

Chen, C. H.; Vaughey, J. T.; Jansen, A. N.; Dees, D. W.; Kahaian, A. J.; Goacher, T.; Thackeray, M. M. Studies of Mg-substituted Li4−xMgxTi5O12 spinel electrodes (0 ≤ x ≤ 1) for lithium batteries. J. Electrochem. Soc. 2001, 148, A102– A104.

Crossref Google Scholar
24

Li, B. H.; Han, C. P.; He, Y. -B.; Yang, C.; Du, H. D.; Yang, Q. -H.; Kang, F. Y. Facile synthesis of Li4Ti5O12/C composite with super rate performance. Energy Environ. Sci. 2012, 5, 9595–9602.

Crossref Google Scholar
25

Zhu, G. -N.; Wang, C. -X.; Xia, Y. -Y. A comprehensive study of effects of carbon coating on Li4Ti5O12 anode material for lithium-ion batteries. J. Electrochem. Soc. 2011, 158, A102–A109.

Crossref Google Scholar
26

Zhang, Z. H.; Li, G. C.; Peng, H. R.; Chen, K. Z. Hierarchical hollow microspheres assembled from N-doped carbon coated Li4Ti5O12 nanosheets with enhanced lithium storage properties. J. Mater. Chem A 2013, 1, 15429–15434.

Crossref Google Scholar
27

Pan, H. L.; Zhao, L.; Hu, Y. -S.; Li, H.; Chen, L. Q. Improved Li-storage performance of Li4Ti5O12 coated with C-N compounds derived from pyrolysis of urea through a low-temperature approach. ChemSusChem 2012, 5, 526–529.

Crossref Google Scholar
28

Shen, L. F.; Zhang, X. G.; Uchaker, E.; Yuan, C. Z.; Cao, G. Z. Li4Ti5O12 nanoparticles embedded in a mesoporous carbon matrix as a superior anode material for high rate lithium ion batteries. Adv. Energy Mater. 2012, 2, 691–698.

Crossref Google Scholar
29

Shen, L. F.; Li, H. S.; Uchaker, E.; Zhang, X. G.; Cao, G. Z. General strategy for designing core–shell nanostructured materials for high-power lithium ion batteries. Nano Lett. 2012, 12, 5673–5678.

Crossref Google Scholar
30

Kim, K. -T.; Yu, C. -Y.; Yoon, C. S.; Kim, S. -J.; Sun, Y. -K.; Myung, S. -T. Carbon-coated Li4Ti5O12 nanowires showing high rate capability as an anode material for rechargeable sodium batteries. Nano Energy 2015, 12, 725–734.

Crossref Google Scholar
31

Li, H. Q.; Zhou, H. S. Enhancing the performances of Li- ion batteries by carbon-coating: Present and future. Chem. Commun. 2012, 48, 1201–1217.

Crossref Google Scholar
32

Yuan, T.; Cai, R.; Shao, Z. P. Different effect of the atmospheres on the phase formation and performance of Li4Ti5O12 prepared from ball-milling-assisted solid-phase reaction with pristine and carbon-precoated TiO2 as starting materials. J. Phys. Chem. C 2011, 115, 4943–4952.

Crossref Google Scholar
33

Jia, X. L.; Kan, Y. F.; Zhu, X.; Ning, G. Q.; Lu, Y. F.; Wei, F. Building flexible Li4Ti5O12/CNT lithium-ion battery anodes with superior rate performance and ultralong cycling stability. Nano Energy 2014, 10, 344–352.

Crossref Google Scholar
34

Yuan, T.; Li, W. -T.; Zhang, W. M.; He, Y. -S.; Zhang, C. M.; Liao, X. -Z.; Ma, Z. -F. One-pot spray-dried graphene sheets- encapsulated nano-Li4Ti5O12 microspheres for a hybrid BatCap system. Ind. Eng. Chem. Res. 2014, 53, 10849–10857.

Crossref Google Scholar
35

Zhu, G. -N.; Liu, H. -J.; Zhuang, J. -H.; Wang, C. -X.; Wang, Y. -G.; Xia, Y. -Y. Carbon-coated nano-sized Li4Ti5O12 nanoporous micro-sphere as anode material for high-rate lithium-ion batteries. Energy Environ. Sci. 2011, 4, 4016–4022.

Crossref Google Scholar
36

Vujković, M.; Stojković, I.; Mitrić, M.; Mentus, S.; Cvjetićanin, N. Hydrothermal synthesis of Li4Ti5O12/C nanostructured composites: Morphology and electrochemical performance. Mater. Res. Bull. 2013, 48, 218–223.

Crossref Google Scholar
37

Liu, T. T.; Ni, H. F.; Song, W. -L.; Fan, L. -Z. Enhanced electrochemical performance of Li4Ti5O12 as anode material for lithium-ion batteries with different carbons as support. J. Alloys Compd. 2015, 646, 189–194.

Crossref Google Scholar
38

Shi, Y.; Wen, L.; Li, F.; Cheng, H. -M. Nanosized Li4Ti5O12/ graphene hybrid materials with low polarization for high rate lithium ion batteries. J. Power Sources 2011, 196, 8610– 8617.

Crossref Google Scholar
39

Li, N.; Chen, Z. P.; Ren, W. C.; Li, F.; Cheng, H. -M. Flexible graphene-based lithium ion batteries with ultrafast charge and discharge rates. Proc. Natl. Acad. Sci. USA 2012, 109, 17360–17365.

Crossref Google Scholar
40

Bonaccorso, F.; Colombo, L.; Yu, G.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R. S.; Pellegrini, V. Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science 2015, 347, 1246501.

Crossref Google Scholar
41

Zhao, B. T.; Ran, R.; Liu, M. L.; Shao, Z. P. A comprehensive review of Li4Ti5O12-based electrodes for lithium-ion batteries: The latest advancements and future perspectives. Mater. Sci. Eng. : R 2015, 98, 1–71.

Crossref Google Scholar
42

Naoi, K.; Ishimoto, S.; Isobe, Y.; Aoyagi, S. High-rate nano-crystalline Li4Ti5O12 attached on carbon nano-fibers for hybrid supercapacitors. J. Power Sources 2010, 195, 6250–6254.

Crossref Google Scholar
43

Tang, Y. F.; Huang, F. Q.; Zhao, W.; Liu, Z. Q.; Wan, D. Y. Synthesis of graphene-supported Li4Ti5O12 nanosheets for high rate battery application. J. Mater. Chem. 2012, 22, 11257–11260.

Crossref Google Scholar
44

Ni, H. F.; Fan, L. -Z. Nano-Li4Ti5O12 anchored on carbon nanotubes by liquid phase deposition as anode material for high rate lithium-ion batteries. J. Power Sources 2012, 214, 195–199.

Crossref Google Scholar
45

Shi, Y.; Gao, J.; Abruña, H. D.; Liu, H. K.; Li, H. J.; Wang, J. Z.; Wu, Y. P. Rapid synthesis of Li4Ti5O12/graphene composite with superior rate capability by a microwave- assisted hydrothermal method. Nano Energy 2014, 8, 297–304.

Crossref Google Scholar
46

Shen, L. F.; Yuan, C. Z.; Luo, H. J.; Zhang, X. G.; Yang, S. D.; Lu, X. J. In situ synthesis of high-loading Li4Ti5O12- graphene hybrid nanostructures for high rate lithium ion batteries. Nanoscale 2011, 3, 572–574.

Crossref Google Scholar
47

Jia, X. L.; Zhang, G. L.; Wang, T. H.; Zhu, X.; Yang, F.; Li, Y. F.; Lu, Y. F.; Wei, F. Monolithic nitrogen-doped graphene frameworks as ultrahigh-rate anodes for lithium ion batteries. J. Mater. Chem. A 2015, 3, 15738–15744.

Crossref Google Scholar
48

Zhao, L.; Hu, Y. -S.; Li, H.; Wang, Z. X.; Chen, L. Q. Porous Li4Ti5O12 coated with N-doped carbon from ionic liquids for Li-ion batteries. Adv. Mater. 2011, 23, 1385–1388.

Crossref Google Scholar
49

Jia, X. L.; Cheng, Y. H.; Lu, Y. F.; Wei, F. Building robust carbon nanotube-interweaved-nanocrystal architecture for high-performance anode materials. ACS Nano 2014, 8, 9265–9273.

Crossref Google Scholar
50

Augustyn, V.; Come, J.; Lowe, M. A.; Kim, J. W.; Taberna, P. -L.; Tolbert, S. H.; Abruña, H. D.; Simon, P.; Dunn, B. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 2013, 12, 518–522.

Crossref Google Scholar
51

Xu, G. B.; Li, W.; Yang, L. W.; Wei, X. L.; Ding, J. W.; Zhong, J. X.; Chu, P. K. Highly-crystalline ultrathin Li4Ti5O12 nanosheets decorated with silver nanocrystals as a high- performance anode material for lithium ion batteries. J. Power Sources 2015, 276, 247–254.

Crossref Google Scholar
52

Yang, Y. C.; Qiao, B. H.; Yang, X. M.; Fang, L. B.; Pan, C. C.; Song, W. X.; Hou, H. S.; Ji, X. B. Lithium titanate tailored by cathodically induced graphene for an ultrafast lithium ion battery. Adv. Funct. Mater. 2014, 24, 4349–4356.

Crossref Google Scholar
53

Rakhi, R. B.; Chen, W.; Cha, D.; Alshareef, H. N. Nanostructured ternary electrodes for energy-storage applications. Adv. Energy Mater. 2012, 2, 381–389.

Crossref Google Scholar
54

Jia, X. L.; Chen, Z.; Suwarnasarn, A.; Rice, L.; Wang, X. L.; Sohn, H. S.; Zhang, Q.; Wu, B. M.; Wei, F.; Lu, Y. F. High- performance flexible lithium-ion electrodes based on robust network architecture. Energy Environ. Sci. 2012, 5, 6845– 6849.

Crossref Google Scholar
55

Song, M. -S.; Benayad, A.; Choi, Y. -M.; Park, K. -S. Does Li4Ti5O12 need carbon in lithium ion batteries? Carbon-free electrode with exceptionally high electrode capacity. Chem. Commun. 2012, 48, 516–518.

Crossref Google Scholar
56

Young, D.; Ransil, A.; Amin, R.; Li, Z.; Chiang, Y. -M. Electronic conductivity in the Li4/3Ti5/3O4–Li7/3Ti5/3O4 system and variation with state-of-charge as a Li battery anode. Adv. Energy Mater. 2013, 3, 1125–1129.

Crossref Google Scholar
57

Zhang, Z. H.; Li, G. C.; Peng, H. R.; Chen, K. Z. Hierarchical hollow microspheres assembled from N-doped carbon coated Li4Ti5O12 nanosheets with enhanced lithium storage properties. J. Mater. Chem. A 2013, 1, 15429–15434.

Crossref Google Scholar
Nano Research
Volume 9 Issue 1,
January 2016
Pages 230-239
DOI: 10.1007/s12274-016-1001-5
Cite this article:
Jia X, Lu Y, Wei F. Confined growth of Li4Ti5O12 nanoparticles in nitrogen-doped mesoporous graphene fibers for high-performance lithium-ion battery anodes. Nano Research, 2016, 9(1): 230-239. https://doi.org/10.1007/s12274-016-1001-5
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