Abstract
Unique hierarchical rutile TiO2 microspheres assembled by nanorods with nanocavities were successfully synthesized through mesoscale assembly in the tetrabutyl titanate-hydrochloric acid system followed by subsequently calcinating in air. In contrast to the classical mechanism of atom-/molecule-mediated growth of a single crystal, the particle-mediated growth and assembly mechanism was summarized as nonclassical crystallization. The particle-based crystallization pathways lead to single crystals with nanocavities via mesoscopic transformation and anti-nucleation process. The electrochemical properties were investigated by constant current discharge-charge tests and electrochemical impedance techniques. This microsphere-shaped rutile TiO2 with nanocavities exhibits excellent rate capacities (151 mAh g−1 at 2 C) and better cyclic performance than that of rutile TiO2 mesocrystals precursor at high rate.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Brabants G, Hubin M, Reichel EK, Jakoby B, Breynaert E, Taulelle F, Martens JA, Kirschhock CEA (2017) Revisiting slicalite-1 nucleation in clear solution by electrochemical impedance spectroscopy. Langmuir 33(10):2581–2589. https://doi.org/10.1021/acs.langmuir.6b04135
Bruce PG, Scrosati B, Tarascon JM (2008) Nanomaterials for rechargeable lithium batteries. Angew Chem Int Ed 47(16):2930–2946. https://doi.org/10.1002/anie.200702505
Chen JS, Liang YN, Liang YM, Yan QY, Hu X (2013) H2O-EG-assisted synthesis of uniform urchinlike rutile TiO2 with superior lithium storage properties. ACS Appl Mater Interfaces 5(20):9998–10003. https://doi.org/10.1021/am4022494
Cölfen H, Antonietti M (2005) Mesocrystals: inorganic superstructures made by highly parallel crystallization and controlled alignment. Angew Chem Int Ed 44(35):5576–5591. https://doi.org/10.1002/anie.200500496
Cölfen H, Antonietti M (2008) Mesocrystals and nonclassical crystallization. John Wiley & Sons Ltd Chichester. https://doi.org/10.1002/9780470994603
Cölfen H, Mann S (2003) Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures. Angew Chem Int Ed 42(21):2350–2365. https://doi.org/10.1002/anie.200200562
Da Silva RO, Goncalves RH, Stroppa DG, Ramirez AJ, Leite ER (2011) Synthesis of recrystallized anatase TiO2 mesocrystals with wulff shape assisted by oriented attachment. Nanoscale 3(4):1910–1916. https://doi.org/10.1039/c0nr01016b
Feinle A, Elsaesser MS, Husing N (2016) Sol-gel synthesis of monolithic materials with hierarchical porosity. Chem Soc Rev 45(12):3377–3399. https://doi.org/10.1039/C5CS00710K
Fischer MG, Hua X, Wilts BD, Gunkel I, Bennett TM, Steiner U (2017) Mesoporous titania microspheres with highly tunable pores as an anode material for lithium ion batteries. ACS Appl Mater Interfaces 9(27):22388–22397. https://doi.org/10.1021/acsami.7b03155
Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238(5358):37–38. https://doi.org/10.1038/238037a0
Ge MZ, Cao CY, Huang JY, Li SH, Chen Z, Zhang KQ, Al-Deyab SS, Lai YK (2016) A review of one-dimensional TiO2 nanostructured materials for environmental and energy applications. J Mater Chem A 4(18):6772–6801. https://doi.org/10.1039/C5TA09323F
Guo SH, Yi J, Sun Y, Zhou HS (2016) Recent advances in titanium-based electrode materials for stationary sodium-ion batteries. Energy Environ Sci 9(10):2978–3006. https://doi.org/10.1039/C6EE01807F
Han WQ, LJ W, Klie RF, Zhu Y (2007) Enhanced optical absorption induced by dense nanocavities inside titania nanorods. Adv Mater 19(18):2525–2529. https://doi.org/10.1002/adma.200700540
Kim SJ, Kargar A, Wang DL, GrahamGW PXQ (2015) Lithiation of rutile TiO2-coated Si NWs observed by in situ TEM. Chem Mater 27(20):6929–6933. https://doi.org/10.1021/acs.chemmater.5b02565
Knudsen KB, Nichols JE, Vegge T, Luntz AC, Mccloskey BD, Hjelm J (2016) An electrochemical impedance study of the capacity limitations in Na-O2 cells. J Phys Chem C 120(20):10799–10805. https://doi.org/10.1021/acs.jpcc.6b02788
Kong XY, Ding Y, Yang R, Wang ZL (2004) Single-crystal nanorings formed by epitaxial self-coiling of polar nanobelts. Science 303(5662):1348–1351. https://doi.org/10.1126/science.1092356
Kulak AN, Iddon P, Li Y, Armes SP, Cölfen H, Paris O, Wilson RM, Meldrum FC (2007) Continuous structural evolution of calcium carbonate particles: a unifying model of copolymer-mediated crystallization. J Am Chem Soc 129(12):3729–3736. https://doi.org/10.1021/ja067422e
Lan TB, Liu YB, Dou J, Hong ZS, Wei MD (2014) Hierarchically porous TiO2 microspheres as a high performance anode for lithium-ion batteries. J Mater Chem A 2(4):1102–1106. https://doi.org/10.1039/C3TA14178K
Li XL, Yan PF, Xiao XC, Woo JH, Wang CM, Liu J, Zhang JG (2017) Design of porous Si/C-graphite electrodes with long cycle stability and controlled swelling. Energy Environ Sci 10(6):1427–1434. https://doi.org/10.1039/C7EE00838D
Liu H, Li W, Shen DK, Zhao DY, Wang GX (2015) Graphitic carbon conformal coating of mesoporous TiO2 hollow spheres for high-performance lithium ion battery anodes. J Am Chem Soc 137(40):13161–13166. https://doi.org/10.1021/jacs.5b08743
Luo Y, Li J, Huang JG (2016) Bioinspired hierarchical nanofibrous silver-nanoparticle/anatase-rutile-titania composite as an anode material for lithium-ion batteries. Langmuir 32(47):12338–12343. https://doi.org/10.1021/acs.langmuir.6b01556
Madian M, Klose M, Jaumann T, Gebert A, Oswald S, Ismail N, Eychmuller A, Eckert J, Giebeler L (2016) Anodically fabricated TiO2-SnO2 nanotubes and their application in lithium ion batteries. J Mater Chem A 4(15):5542–5552. https://doi.org/10.1039/C6TA00182C
Mashimo T, Bagum R, Ogata Y, Tokuda M, Okube M, Sugiyama K, Kinemuchi Y, Isobe H, Yoshiasa A (2017) Structure of single-crystal rutile (TiO2) prepared by high-temperature ultracentrifugation. Cryst Growth Des 17(4):1460–1464. https://doi.org/10.1021/acs.cgd.6b01818
Ohzuku T, Takehara Z, Yoshizawa S (1979) Nonaqueous lithium/titanium dioxide cell. Electrochim Acta 24(2):219–222. https://doi.org/10.1016/0013-4686(79)80028-6
Onishi H, Iwasawa Y (1996) Time-resolved observation by scanning tunneling microscopy at 800 K dynamic visualization of a metal-oxide-surface/gas-phase reaction. Phys Rev Lett 76(5):791–794. https://doi.org/10.1103/PhysRevLett.76.791
Pan F, Huang QZ, Huang H, Wang Q (2016) High-energy density redox flow lithium battery with unprecedented voltage efficiency. Chem Mater 28(7):2052–2057. https://doi.org/10.1021/acs.chemmater.5b04558
Salvatierra RV, Zakhidov D, Sha JW, Kim ND, Lee S, Raji AO, Zhao NQ, Tour JM (2017) Graphene carbon nanotube carpets gown using binary catalysts for high-performance lithium-ion capacitors. ACS Nano 11(3):2724–2733. https://doi.org/10.1021/acsnano.6b07707
Shen LF, Yuan CZ, Luo HJ, Zhang XG, Yang SD, XJ L (2011a) In situ synthesis of high-loading Li4Ti5O12-graphene hybrid nanostructures for high rate lithium ion batteries. Nanoscale 3(2):572–574. https://doi.org/10.1039/C0NR00639D
Shen LF, Zhang XG, Li HS, Yuan CZ, Cao GZ (2011b) Design and tailoring of a three-dimensional TiO2-graphene-carbon nanotube nanocomposite for fast lithium storage. J Phys Chem Lett 2(24):3096–3101. https://doi.org/10.1021/jz201456p
Shimizu K, Nystrom J, Geladi P, Lindholm-Sethson B, Boily JF (2015) Electrolyte ion adsorption and charge blocking effect at the hematite/aqueous solution interface: an electrochemical impedance study using multivariate data analysis. Phys Chem Chem Phys 17(17):11560–11568. https://doi.org/10.1039/C4CP05927A
Song RQ, Cölfen H (2010) Mesocrystals-ordered nanoparticle superstructures. Adv Mater 22(12):1301–1330. https://doi.org/10.1002/adma.200901365
Song T, Paik U (2016) TiO2 as an active or supplemental material for lithium batteries. J Mater Chem A 4(1):14–31. https://doi.org/10.1039/C5TA06888F
Tian HJ, Xin FX, Tian XJ, Han WQ (2014) High lithium electroactivity of boron-doped hierarchical rutile submicrosphere TiO2. J Mater Chem A 2(27):10599–10606. https://doi.org/10.1039/C4TA01438C
Wang DH, Choi DW, Yang ZG, Viswanathan W, Nie ZM, Wang CM, Song YJ, Zhang JG, Liu J (2008) Synthesis and Li-ion insertion properties of highly crystalline mesoporous rutile TiO2. Chem Mater 20(10):3435–3442. https://doi.org/10.1021/cm8002589
Wang YQ, Gu L, Guo YG, Li H, He XQ, Tsukimoto S, Ikuhara YC, Wan LJ (2012) Rutile-TiO2 nanocoating for a high-rate Li4Ti5O12 anode of a lithium-ion battery. J Am Chem Soc 134(18):7874–7879. https://doi.org/10.1021/ja301266w
Wang XJ, Feng J, Bai YC, Zhang Q, Yin YD (2016a) Synthesis, properties, and applications of hollow micro-/nanostructures. Chem Rev 116(18):10983–11060. https://doi.org/10.1021/acs.chemrev.5b00731
Wang FX, XW W, Li CY, Zhu YS, LJ F, YP W, Liu X (2016b) Nanostructured positive electrode materials for post-lithium ion batteries. Energy Environ Sci 9(12):3570–3611. https://doi.org/10.1039/C6EE02070D
Weng ZY, Guo H, Liu XM, SL W, Yeung KWK, Chu PK (2013) Nanostructured TiO2 for energy conversion and storage. RSC Adv 3(47):24758–24775. https://doi.org/10.1039/c3ra44031a
Yang ZW, Wang B, Cui H, An H, Pan Y, Zhai JP (2015) Synthesis of crystal-controlled TiO2 nanorods by a hydrothermal method: rutile and brookite as highly active photocatalysts. J Phys Chem C 119(29):16905–16912. https://doi.org/10.1021/acs.jpcc.5b02485
Yang XY, Chen LH, Li Y, Rooke JC, Sanche C, BL S (2017) Hierarchically porous materials: synthesis strategies and structure design. Chem Soc Rev 46(2):481–558. https://doi.org/10.1039/C6CS00829A
Zhang DQ, Li GS, Wang F, JC Y (2010) Green synthesis of a self-assembled rutile mesocrystalline photocatalyst. CrystEngComm 12(6):1759–1763. https://doi.org/10.1039/b922477g
Zheng J, Liu L, Ji GB, Yang QF, Zheng LR, Zhang J (2016) Hydrogenated anatase TiO2 as lithium-ion battery anode: size-reactivity correlation. ACS Appl Mater Interfaces 8(31):20074–20081. https://doi.org/10.1021/acsami.6b05993
Zhou L, O’Brien P (2008) Mesocrystals: a new class of solid materials. Small 4(10):1566–1574. https://doi.org/10.1002/smll.200800520
Zhu SC, Xie SH, Liu ZP (2015) Nature of rutile nuclei in anatase-to-rutile phase transition. J Am Chem Soc 137(35):11532–11539. https://doi.org/10.1021/jacs.5b07734
Funding
This project was supported by the National Natural Science Foundation of China (Project No. 51602275, Project No. 51762041), Fund for One Hundred Young Doctor Program of Xinjiang Uygur Autonomous Region, as well as the Science and Technology Foundation of Xinjiang Uyghur Autonomous Region Bureau of Quality and Technical Supervision (Project No. 201609), and the Natural Science Foundation for Young Scholars Program of Xinjiang Uygur Autonomous Region (2016D01B050).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Rights and permissions
About this article
Cite this article
Chen, L., Yang, S. Hierarchical rutile TiO2 microspheres assembled by nanorods with nanocavities and their lithium-ion storage properties. J Nanopart Res 20, 32 (2018). https://doi.org/10.1007/s11051-017-4112-3
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-017-4112-3