One-step, continuous synthesis of a spherical Li4Ti5O12/graphene composite as an ultra-long cycle life lithium-ion battery anode
Source abstract
Abstract
We report, for the first time, a one-step, continuous synthesis of spherical lithium titanate (Li4Ti5O12, LTO)/graphene composites through direct aerosolization of a graphene oxide (GO) suspension mixed with Li and Ti precursors. The resulting crumpled graphene-sphere-supported LTO nanocrystals has a three-dimensional structure with a high electrical conductivity, a high surface area and good stability in electrolyte. The LTO/CG composite, as an anode in LIBs, exhibited excellent rate capability (for example, at a high current density of 5000 mA g−1 it delivered 60% of the capacity obtained at 12.5 mA g−1) and an outstanding cycling performance (a capacity retention of 88% after 5000 cycles at 1,250 mA g−1). The one-step, continuous synthesis of the LTO/graphene composite offers a high-producing efficiency compared with conventional multi-step preparations, and can be generally applied for synthesizing lithium metal oxides/graphene (cathode or anode) materials for lithium-ion batteries. Researchers have used ‘crumpled’ graphene spheres dotted with nanocrystals to boost the safety and performance of Li-ion batteries. Lithium titanate (Li4Ti5O12 or LTO) is a promising alternative to conventional Li-ion battery anodes that is less prone to dangerous short-circuit reactions, but it suffers from poor conductivity. Junhong Chen and co-workers from the University of Wisconsin-Milwaukee have developed a one-step synthetic technique to remedy this situation. By passing aerosolized graphene oxide and LTO precursors through a high-temperature furnace, normally flat graphene sheets transformed into crumpled spheres covered with LTO nanocrystals. The hollow, three-dimensional structure of this anode significantly improved LTO conductivity by shortening distances needed for charge transfer. Furthermore, the integrated composite prevents premature nanocrystal aggregation, giving rise to long device lifespans — prototype batteries retained 88% of their capacity after 5,000 recharge cycles. A one-step and continuous method to produce a spherical Li4Ti5O12/graphene composite for the lithium-ion battery anode is reported. The high conductivity and hollow structure of the crumpled graphene sphere greatly enhance the rate capability and cycling performance of the Li4Ti5O12 anode. This method provides a new and exciting approach for high-performance anode material design and fabrication.
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Research context
OpenAlex topics: Advancements in Battery Materials · Graphene research and applications · Advanced Battery Materials and Technologies
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References (47)
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1. Ji, L., Lin, Z., Alcoutlabi, M. & Zhang, X. Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries. Energy Environ. Sci. 4, 2682–2699 (2011).10.1039/c0ee00699h ↗
2. Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).10.1038/451652a ↗
3. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).10.1038/35104644 ↗
4. Ganapathy, S. & Wagemaker, M. Nanosize storage properties in Spinel Li4Ti5O12 explained by anisotropic surface lithium insertion. ACS Nano 6, 8702–8712 (2012).10.1021/nn302278m ↗
5. Lu, X., Zhao, L., He, X., Xiao, R., Gu, L., Hu, Y. S., Li, H., Wang, Z., Duan, X., Chen, L., Maier, J. & Ikuhara, Y. Lithium storage in Li4Ti5O12 Spinel: the full static picture from electron microscopy. Adv. Mater. 24, 3233–3238 (2012).10.1002/adma.201200450 ↗
6. Yu, L., Wu, H. B. & Lou, X. W. Mesoporous Li4Ti5O12 hollow spheres with enhanced lithium storage capability. Adv. Mater. 25, 2296–2300 (2013).10.1002/adma.201204912 ↗
7. Feckl, J. M., Fominykh, K., Doeblinger, M., Fattakhova-Rohlfing, D. & Bein, T. Nanoscale porous framework of lithium titanate for ultrafast lithium insertion. Angew. Chem. Int. Ed. 51, 7459–7463 (2012).10.1002/anie.201201463 ↗
8. Park, K.-S., Benayad, A., Kang, D.-J. & Doo, S.-G. Nitridation-Driven Conductive Li4Ti5O12 for Lithium Ion Batteries. J. Am. Chem. Soc. 130, 14930–14931 (2008).10.1021/ja806104n ↗
9. Amatucci, G. G., Badway, F., Du Pasquier, A. & Zheng, T. An asymmetric hybrid nonaqueous energy storage cell. J. Electrochem. Soc. 148, A930–A939 (2001).10.1149/1.1383553 ↗
10. Haetge, J., Hartmann, P., Brezesinski, K., Janek, J. & Brezesinski, T. Ordered large-pore mesoporous Li4Ti5O12 spinel thin film electrodes with nanocrystalline framework for high rate rechargeable lithium batteries: relationships among charge storage, electrical conductivity, and nanoscale structure. Chem. Mater. 23, 4384–4393 (2011).10.1021/cm202185y ↗
11. Shen, L., Li, H., Uchaker, E., Zhang, X. & Cao, G. General strategy for designing core-shell nanostructured materials for high-power lithium ion batteries. Nano Lett. 12, 5673–5678 (2012).10.1021/nl302854j ↗
12. Zhu, G.-N., Wang, Y.-G. & Xia, Y.-Y. Ti-based compounds as anode materials for Li-ion batteries. Energy Environ. Sci. 5, 6652–6667 (2012).10.1039/c2ee03410g ↗
13. Amine, K., Belharouak, I., Chen, Z., Tran, T., Yumoto, H., Ota, N., Myung, S. T. & Sun Y. K. Nanostructured Anode Material for High-Power Battery System in Electric Vehicles. Adv. Mater. 22, 3052–3057 (2010).10.1002/adma.201000441 ↗
14. Guo, J. & Liu, J. Topotactic conversion-derived Li4Ti5O12-rutile TiO2 hybrid nanowire array for high-performance lithium ion full cells. RSC Adv. 4, 12950–12957 (2014).10.1039/c4ra00111g ↗
15. Jo, M. R., Jung, Y. S. & Kang, Y.-M. Tailored Li4Ti5O12 nanofibers with outstanding kinetics for lithium rechargeable batteries. Nanoscale 4, 6870–6875 (2012).10.1039/c2nr31675g ↗
16. Chen, S., Xin, Y. & Zhou, Y. Self-supported Li4Ti5O12 nanosheet arrays for lithium ion batteries with excellent rate capability and ultralong cycle life. Energy Environ. Sci. 1924–1930 (2014).10.1039/c3ee42646g ↗
17. 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. 134, 7874–7879 (2012).10.1021/ja301266w ↗
18. Zhao, L., Hu, Y.-S., Li, H., Wang, Z. & Chen, L. Porous Li4Ti5O12 coated with N-doped carbon from ionic liquids for Li-Ion batteries. Adv. Mater. 23, 1385–1388 (2011).10.1002/adma.201003294 ↗
19. Shen, L., Yuan, C., Luo, H., Zhang, X., Yang, S. & Lu, X. In situ synthesis of high-loading Li4Ti5O12-graphene hybrid nanostructures for high rate lithium ion batteries. Nanoscale 3, 572–574 (2011).10.1039/C0NR00639D ↗
20. Jung, H.-G., Myung, S.-T., 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. 4, 1345–1351 (2011).10.1039/c0ee00620c ↗
21. Xiang, H., Tian, B., Lian, P., Li, Z. & Wang, H. Sol-gel synthesis and electrochemical performance of Li4Ti5O12/graphene composite anode for lithium-ion batteries. J. Alloy Compd. 509, 7205–7209 (2011).10.1016/j.jallcom.2011.04.065 ↗
22. Kim, H. K., Jegal, J.-P., Kim, J.-Y., Yoon, S.-B., Roh, K. C. & Kim, K.-B. In situ fabrication of lithium titanium oxide by microwave-assisted alkalization for high-rate lithium-ion batteries. J. Mater. Chem. A 1, 14849–14852 (2013).10.1039/c3ta13206d ↗
23. Mao, S., Wen, Z., Huang, T., Hou, Y. & Chen, J. High-performance bi-functional electrocatalysts of 3D crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ. Sci. 7, 609–616 (2014).10.1039/C3EE42696C ↗
24. Mao, S., Wen, Z., Kim, H., Lu, G., Hurley, P. & Chen, J. A general approach to one-pot fabrication of crumpled graphene-based nanohybrids for energy applications. ACS Nano 6, 7505–7513 (2012).10.1021/nn302818j ↗
25. Luo, J., Jang, H. D., Sun, T., Xiao, L., He, Z., Katsoulidis, A. P., Kanatzidis, M. G., Gibson, J. M. & Huang, J. Compression and aggregation-resistant particles of crumpled soft sheets. ACS Nano 5, 8943–8949 (2011).10.1021/nn203115u ↗
26. Ma, X., Zachariah, M. R. & Zangmeister, C. D. Crumpled nanopaper from graphene oxide. Nano Lett. 12, 486–489 (2012).10.1021/nl203964z ↗
27. Ruoff, R. A means to an end. Nature 483, S42–S42 (2012).10.1038/483S42a ↗
28. Luo, J., Jang, H. D. & Huang, J. Effect of sheet morphology on the scalability of graphene-based ultracapacitors. ACS Nano 7, 1464–1471 (2013).10.1021/nn3052378 ↗
29. Mao, S., Wen, Z., Bo, Z., Chang, J., Huang, X. & Chen, J. Hierarchical nanohybrids with porous cnt-networks decorated crumpled graphene balls for supercapacitors. ACS Appl. Mater. Interfaces 6, 9881–9889 (2014).10.1021/am502604u ↗
30. Choi, S. H. & Kang, Y. C. Fe3O4-decorated hollow graphene balls prepared by spray pyrolysis process for ultrafast and long cycle-life lithium ion batteries. Carbon 79, 58–66 (2014).10.1016/j.carbon.2014.07.042 ↗
31. Choi, S. H. & Kang, Y. C. Crumpled graphene-molybdenum oxide composite powders: preparation and application in lithium-ion batteries. Chemsuschem 7, 523–528 (2014).10.1002/cssc.201300838 ↗
32. Choi, S. H., Ko, Y. N., Lee, J.-K. & Kang, Y. C. Rapid continuous synthesis of spherical reduced graphene ball-nickel oxide composite for lithium ion batteries. Sci. Rep. 4, 5786 (2014).10.1038/srep05786 ↗
33. Luo, J., Zhao, X., Wu, J., Jang, H. D., Kung, H. H. & Huang, J. Crumpled Graphene-Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes. J. Phys. Chem. Lett. 3, 1824–1829 (2012).10.1021/jz3006892 ↗
34. Zhou, G.-W., Wang, J., Zhou, G.-W., Gao, P., Yang, X., He, Y.-S., Liao, X.-Z., Yang, J. & Ma, Z.-F. Facile spray drying route for the three-dimensional graphene-encapsulated Fe2O3 nanoparticles for lithium ion battery anodes. Ind. Eng. Chem. Res. 52, 1197–1204 (2013).10.1021/ie302469b ↗
35. Ma, X., Zachariah, M. R. & Zangmeister, C. D. Reduction of Suspended Graphene Oxide Single Sheet Nanopaper: The Effect of Crumpling. J. Phys. Chem. C 117, 3185–3191 (2013).10.1021/jp400237m ↗
36. Ferrari, A. C., Meyer, J. C., Scardaci, V., Casiraghi, C., Lazzeri, M., Mauri, F., Piscanec, S., Jiang, D., Novoselov, K. S., Roth, S. & Geim, A. K. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006).10.1103/PhysRevLett.97.187401 ↗
37. Stankovich, S., Dikina, D. A., Pinera, R. D., Kohlhaasa, K. A., Kleinhammesc, A., Jiac, Y., Wuc, Y., Nguyenb, SB. T. & Ruoffa, S.R Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45, 1558–1565 (2007).10.1016/j.carbon.2007.02.034 ↗
38. Bo, Z., Shuai, X., Mao, S., Yang, H., Qian, J., Chen, J., Yan, J. & Cen, K. Green preparation of reduced graphene oxide for sensing and energy storage applications. Sci. Rep. 4, 4684 (2014).10.1038/srep04684 ↗
39. 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 196, 8610–8617 (2011).10.1016/j.jpowsour.2011.06.002 ↗
40. Chen, W. N., Jiang, H., Hu, Y. J., Dai, Y. H. & Li, C. Z. Mesoporous single crystals Li4Ti5O12 grown on rGO as high-rate anode materials for lithium-ion batteries. Chem. Commun. 50, 8856–8859 (2014).10.1039/C4CC02886D ↗
41. Ni, H. F., Song, W. L. & Fan, L. Z. A strategy for scalable synthesis of Li(4)Ti(5)O(12)/reduced graphene oxide toward high rate lithium-ion batteries. Electrochem. Commun. 40, 1–4 (2014).10.1016/j.elecom.2013.12.016 ↗
42. 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. 22, 11257–11260 (2012).10.1039/c2jm30624g ↗
43. Yang, Y. C., Qiao, B., Yang, X., Fang, L., Pan, C., Song, W., Hou, H. & Xiaobo, J. Lithium titanate tailored by cathodically induced graphene for an ultrafast lithium ion battery. Adv. Funct. Mater. 24, 4349–4356 (2014).10.1002/adfm.201304263 ↗
44. Oh, Y., Nam, S., Wi, S., Kang, J., Hwang, T., Lee, S., Park, H. H., Kim, C. & B., Park Effective wrapping of graphene on individual Li4Ti5O12 grains for high-rate Li-ion batteries. J. Mater. Chem. A 2, 2023–2027 (2014).10.1039/C3TA14347C ↗
45. Prakash, A. S., Manikandan, P., Ramesha, K., Sathiya, M., Tarascon, J. -M. & Shukla, A. K. Solution-combustion synthesized nanocrystalline Li4Ti5O12 as high-rate performance Li-Ion battery anode. Chem. Mater. 22, 2857–2863 (2010).10.1021/cm100071z ↗
46. Wagemaker, M., Simon, D. R., Kelder, E. M., Schoonman, J., Ringpfeil, C., Haake, D., Lützenkirchen-Hecht,, D. & Frahm, F. M. A kinetic two-phase and equilibrium solid solution in spinel Li4+xTi5O12. Adv. Mater. 18, 3169–3173 (2006).10.1002/adma.200601636 ↗
47. Huang, X. K., Yang, J., Mao, S., Chang, J., Hallac, P. B., Fell, C. R., Metz, B., Jiang, J., Hurley, P. T. & Chen, J. Controllable synthesis of hollow Si anode for long-cycle-life lithium-ion batteries. Adv. Mater. 26, 4326–4332 (2014).10.1002/adma.201400578 ↗