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Mesoporous TiO2 microparticles formed by the oriented attachment of nanocrystals: A super-durable anode material for sodium-ion batteries

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Abstract

Spindle-shaped anatase TiO2 secondary particles were successfully fabricated via the oriented attachment of primary nanocrystals. By adjusting the concentration of tetrabutyl titanate, the size of the TiO2 nanocrystals and particles could be controlled, resulting in pore evolution. Pores for the random aggregation of secondary particles gradually transformed to nanopores originating from the oriented attachment of the primary nanocrystals, resulting in an excellent micro/nanostructure that increased the performance of a sodium-ion battery. The mesoporous TiO2 microparticle anode, with its unique combination of nanocrystals and uniform nanopores, displays super durability (95 mAh/g after 11,000 cycles at 1 C), high initial efficiency (61.4%), and excellent rate performance (265 and 77 mAh/g at 0.1 and 20 C, respectively). In particular, at slow discharge (0.1 C) and fast charge (5, 50, and 100 C) rates, the anatase TiO2 shows remarkable initial charge capacities of 200, 119, and 56 mAh/g, corresponding to 172, 127, and 56 mAh/g, after 150 cycles, respectively, thus meeting the requirements for fast energy storage. This excellent performance can be attributed to the stability of the material and its high ionic conductivity, resulting from the stable architecture with a mesoporous microstructure and without the random aggregation of secondary particles. A fundamental understanding of the pore structure and controllable pore construction has been proven to be effective in increasing the rate capability and durability of nanostructured electrode materials.

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References

  1. Tarascon, J.-M. Is lithium the new gold? Nat. Chem. 2010, 2, 510–510.

    Article  Google Scholar 

  2. Yabuuchi, N.; Kubota, K.; Dahbi, M.; Komaba, S. Research development on sodium-ion batteries. Chem. Rev. 2014, 114, 11636–11682.

    Article  Google Scholar 

  3. Hong, S. Y.; Kim, Y.; Park, Y.; Choi, A.; Choi, N.-S.; Lee, K. T. Charge carriers in rechargeable batteries: Na ions vs. Li ions. Energy Environ. Sci. 2013, 6, 2067–2081.

    Article  Google Scholar 

  4. Fang, C.; Huang, Y. H.; Zhang, W. X.; Han, J. T.; Deng, Z.; Cao, Y. L.; Yang, H. X. Routes to high energy cathodes of sodium-ion batteries. Adv. Energy Mater. 2016, 6, 1501727.

    Article  Google Scholar 

  5. Ni, Q.; Bai, Y.; Wu, F.; Wu, C. Polyanion-type electrode materials for sodium-ion batteries. Adv. Sci. 2017, 4, 1600275.

    Article  Google Scholar 

  6. Li, H.; Bai, Y.; Wu, F.; Ni, Q.; Wu, C. Na-rich Na3+xV2−xNix(PO4)3/C for sodium ion batteries: Controlling the doping site and improving the electrochemical performances. ACS Appl. Mater. Interfaces 2016, 8, 27779–27787.

    Article  Google Scholar 

  7. Bai, Y.; Zhao, L. X.; Wu, C.; Li, H.; Li, Y.; Wu, F. Enhanced sodium ion storage behavior of P2-type Na2/3Fe1/2Mn1/2O2 synthesized via a chelating agent assisted route. ACS Appl. Mater. Interfaces 2016, 8, 2857–2865.

    Article  Google Scholar 

  8. You, Y.; Yu, X. Q.; Yin, Y. X.; Nam, K. W.; Guo, Y. G. Sodium iron hexacyanoferrate with high Na content as a Na-rich cathode material for Na-ion batteries. Nano Res. 2015, 8, 117–128.

    Article  Google Scholar 

  9. Chen, G. H.; Bai, Y.; Li, H.; Li, Y.; Wang, Z. H.; Ni, Q.; Liu, L.; Wu, F.; Yao, Y. G.; Wu, C. Multilayered electride Ca2N electrode via compression molding fabrication for sodium ion batteries. ACS Appl. Mater. Interfaces 2017, 9, 6666–6669.

    Article  Google Scholar 

  10. Sun, J.; Lee, H.-W.; Pasta, M.; Yuan, H. T.; Zheng, G. Y.; Sun, Y. M.; Li, Y. Z; Cui, Y. A phosphorene-graphene hybrid material as a high-capacity anode for sodium-ion batteries. Nat. Nanotechnol. 2015, 10, 980–985.

    Article  Google Scholar 

  11. Bai, Y.; Wang, Z.; Wu, C.; Xu, R.; Wu, F.; Liu, Y. C.; Li, H.; Li, Y.; Lu, J.; Amine, K. Hard carbon originated from polyvinyl chloride nanofibers as high-performance anode material for Na-ion battery. ACS Appl. Mater. Interfaces 2015, 7, 5598–5604.

    Article  Google Scholar 

  12. Roh, H.-K.; Kim, H.-K.; Kim, M.-S.; Kim, D.-H.; Chung, K. Y.; Roh, K. C.; Kim, K.-B. In situ synthesis of chemically bonded NaTi2(PO4)3/rGO 2D nanocomposite for high-rate sodium-ion batteries. Nano Res. 2016, 9, 1844–1855.

    Article  Google Scholar 

  13. Luo, W.; Shen, F.; Bommier, C.; Zhu, H. L.; Ji, X. L.; Hu, L. B. Na-ion battery anodes: Materials and electrochemistry. Acc. Chem. Res. 2016, 49, 231–240.

    Article  Google Scholar 

  14. Bai, Y.; Liu, Y. C.; Li, Y.; Ling, L. M.; Wu, F.; Wu, C. Mille-feuille shaped hard carbons derived from polyvinylpyrrolidone via environmentally friendly electrostatic spinning for sodium ion battery anodes. RSC Adv. 2017, 7, 5519–5527.

    Article  Google Scholar 

  15. Liu, G.; Yang, H. G.; Pan, J.; Yang, Y. Q.; Lu, G. Q.; Cheng, H.-M. Titanium dioxide crystals with tailored facets. Chem. Rev. 2014, 114, 9559–9612.

    Article  Google Scholar 

  16. Shoaib, A.; Ji, M. W.; Qian, H. M.; Liu, J. J.; Xu, M.; Zhang, J. T. Noble metal nanoclusters and their in situ calcination to nanocrystals: Precise control of their size and interface with TiO2 nanosheets and their versatile catalysis applications. Nano Res. 2016, 9, 1763–1774.

    Article  Google Scholar 

  17. Xiong, H.; Slater, M. D.; Balasubramanian, M.; Johnson, C. S.; Rajh, T. Amorphous TiO2 nanotube anode for rechargeable sodium ion batteries. J. Phys. Chem. Lett. 2011, 2, 2560–2565.

    Article  Google Scholar 

  18. Xu, Y.; Memarzadeh Lotfabad, E.; Wang, H. L.; Farbod, B.; Xu, Z. W.; Kohandehghan, A.; Mitlin, D. Nanocrystalline anatase TiO2: A new anode material for rechargeable sodium ion batteries. Chem. Commun. 2013, 49, 8973–8975.

    Article  Google Scholar 

  19. Huang, J. P.; Yuan, D. D.; Zhang, H. Z.; Cao, Y. L.; Li, G. R.; Yang, H. X.; Gao, X. P. Electrochemical sodium storage of TiO2(B) nanotubes for sodium ion batteries. RSC Adv. 2013, 3, 12593–12597.

    Article  Google Scholar 

  20. Pérez-Flores, J. C.; Baehtz, C.; Kuhn, A.; García-Alvarado, F. Hollandite-type TiO2: A new negative electrode material for sodium-ion batteries. J. Mater. Chem. A 2014, 2, 1825–1833.

    Article  Google Scholar 

  21. Usui, H.; Yoshioka, S.; Wasada, K.; Shimizu, M.; Sakaguchi, H. Nb-doped rutile TiO2: A potential anode material for Na-ion battery. ACS Appl. Mater. Interfaces 2015, 7, 6567–6573.

    Article  Google Scholar 

  22. Hanaor, D. A. H.; Sorrell, C. C. Review of the anatase to rutile phase transformation. J. Mater. Sci. 2010, 46, 855–874.

    Article  Google Scholar 

  23. Wang, B. F.; Zhao, F.; Du, G. D.; Porter, S.; Liu, Y.; Zhang, P.; Cheng, Z. X.; Liu, H. K.; Huang, Z. G. Boron-doped anatase TiO2 as a high-performance anode material for sodium-ion batteries. ACS Appl. Mater. Interfaces 2016, 8, 16009–16015.

    Article  Google Scholar 

  24. Hwang, J.-Y.; Myung, S.-T.; Lee, J.-H.; Abouimrane, A.; Belharouak, I.; Sun, Y.-K. Ultrafast sodium storage in anatase TiO2 nanoparticles embedded on carbon nanotubes. Nano Energy 2015, 16, 218–226.

    Article  Google Scholar 

  25. Chen, C. J.; Wen, Y. W.; Hu, X. L.; Ji, X. L.; Yan, M. Y.; Mai, L. Q.; Hu, P.; Shan, B.; Huang, Y. H. Na+ intercalation pseudocapacitance in graphene-coupled titanium oxide enabling ultra-fast sodium storage and long-term cycling. Nat. Commun. 2015, 6, 6929–6936.

    Article  Google Scholar 

  26. Henry, A.; Louvain, N.; Fontaine, O.; Stievano, L.; Monconduit, L.; Boury, B. Synthesis of titania@carbon nanocomposite from urea-impregnated cellulose for efficient lithium and sodium batteries. ChemSusChem 2016, 9, 264–273.

    Article  Google Scholar 

  27. Kim, K.-T.; Ali, G.; Chung, K. Y.; Yoon, C. S.; Yashiro, H.; Sun, Y.-K.; Lu, J.; Amine, K.; Myung, S.-T. Anatase titania nanorods as an intercalation anode material for rechargeable sodium batteries. Nano Lett. 2014, 14, 416–422.

    Article  Google Scholar 

  28. Yang, X. M.; Wang, C.; Yang, Y. C.; Zhang, Y.; Jia, X. N.; Chen, J.; Ji, X. B. Anatase TiO2 nanocubes for fast and durable sodium ion battery anodes. J. Mater. Chem. A 2015, 3, 8800–8807.

    Article  Google Scholar 

  29. Yan, D.; Yu, C. Y.; Bai, Y.; Zhang, W. F.; Chen, T. Q.; Hu, B. W.; Sun, Z.; Pan, L. K. Sn-doped TiO2 nanotubes as superior anode materials for sodium ion batteries. Chem. Commun. 2015, 51, 8261–8264.

    Article  Google Scholar 

  30. Tahir, M. N.; Oschmann, B.; Buchholz, D.; Dou, X. W.; Lieberwirth, I.; Panthöfer, M.; Tremel, W.; Zentel, R.; Passerini, S. Extraordinary performance of carbon-coated anatase TiO2 as sodium-ion anode. Adv. Energy Mater. 2016, 6, 1501489.

    Article  Google Scholar 

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

    Article  Google Scholar 

  32. Uchaker, E.; Cao, G. Z. Mesocrystals as electrode materials for lithium-ion batteries. Nanotoday 2014, 9, 499–524.

    Article  Google Scholar 

  33. Jo, M. K.; Hong, Y. S.; Choo, J.; Cho, J. Effect of LiCoO2 cathode nanoparticle size on high rate performance for Li-ion batteries. J. Electrochem. Soc. 2009, 156, A430–A434.

    Article  Google Scholar 

  34. Ge, X.; Gu, C. D.; Wang, X. L.; Tu, J. P. Correlation between microstructure and electrochemical behavior of the mesoporous Co3O4 sheet and its ionothermal synthesized hydrotalcite-like α-Co(OH)2 precursor. J. Phys. Chem. C 2014, 118, 911–923.

    Article  Google Scholar 

  35. Lee, S. H.; Yu, S.-H.; Lee, J. E.; Jin, A.; Lee, D. J.; Lee, N.; Jo, H.; Shin, K.; Ahn, T.-Y.; Kim, Y.-W. et al. Self-assembled Fe3O4 nanoparticle clusters as high-performance anodes for lithium ion batteries via geometric confinement. Nano Lett. 2013, 13, 4249–4256.

    Article  Google Scholar 

  36. Bommier, C.; Luo, W.; Gao, W.-Y.; Greaney, A.; Ma, S. Q.; Ji, X. L. Predicting capacity of hard carbon anodes in sodium-ion batteries using porosity measurements. Carbon 2014, 76, 165–174.

    Article  Google Scholar 

  37. Ye, J. F.; Liu, W.; Cai, J. G.; Chen, S.; Zhao, X. W.; Zhou, H. H.; Qi, L. M. Nanoporous anatase TiO2 mesocrystals: Additive-free synthesis, remarkable crystalline-phase stability, and improved lithium insertion behavior. J. Am. Chem. Soc. 2011, 133, 933–940.

    Article  Google Scholar 

  38. Zhang, Q.; Liu, S.-J.; Yu, S.-H. Recent advances in oriented attachment growth and synthesis of functional materials: concept, evidence, mechanism, and future. J. Mater. Chem. 2008, 19, 191–207.

    Article  Google Scholar 

  39. Qian, H. M.; Zhao, Q.; Dai, B. S.; Guo, L. J.; Zhang, J. X.; Liu, J. J.; Zhang, J. T.; Zhu, H. S. Oriented attachment of nanoparticles to form micrometer-sized nanosheets/nanobelts by topotactic reaction on rigid/flexible substrates with improved electronic properties. NPG Asia Mater. 2015, 7, e152.

    Article  Google Scholar 

  40. Crossland, E. J. W.; Noel, N.; Sivaram, V.; Leijtens, T.; Alexander-Webber, J. A.; Snaith, H. J. Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature 2013, 495, 215–219.

    Article  Google Scholar 

  41. Wang, J.; Zhou, Y. K.; Hu, Y. Y.; O’Hayre, R.; Shao, Z. P. Facile synthesis of nanocrystalline TiO2 mesoporous microspheres for lithium-ion batteries. J. Phys. Chem. C 2011, 115, 2529–2536.

    Article  Google Scholar 

  42. Zeng, L. X.; Zheng, C.; Xia, L. C.; Wang, Y. X.; Wei, M. D. Ordered mesoporous TiO2-C nanocomposite as an anode material for long-term performance lithium-ion batteries. J. Mater. Chem. A 2013, 1, 4293–4299.

    Article  Google Scholar 

  43. Grosso, D.; de A. A. Soler-Illia, G. J.; Crepaldi, E. L.; Charleux, B.; Sanchez, C. Nanocrystalline transition-metal oxide spheres with controlled multi-scale porosity. Adv. Funct. Mater. 2003, 13, 37–42.

    Article  Google Scholar 

  44. Matos, J. R.; Kruk, M.; Mercuri, L. P.; Jaroniec, M.; Zhao, L.; Kamiyama, T.; Terasaki, O.; Pinnavaia, T. J.; Liu, Y. Ordered mesoporous silica with large cage-like pores: Structural identification and pore connectivity design by controlling the synthesis temperature and time. J. Am. Chem. Soc. 2003, 125, 821–829.

    Article  Google Scholar 

  45. Yuan, C. Z.; Zhang, X. G.; Su, L. H.; Gao, B.; Shen, L. F. Facile synthesis and self-assembly of hierarchical porous NiO nano/micro spherical superstructures for high performance supercapacitors. J. Mater. Chem. 2009, 19, 5772–5777.

    Article  Google Scholar 

  46. Lou, X. W.; Deng, D.; Lee, J. Y.; Archer, L. A. Thermal formation of mesoporous single-crystal Co3O4 nano-needles and their lithium storage properties. J. Mater. Chem. 2008, 18, 4397–4401.

    Article  Google Scholar 

  47. Yu, J. G.; Su, Y. R.; Cheng, B.; Zhou, M. H. Effects of pH on the microstructures and photocatalytic activity of mesoporous nanocrystalline titania powders prepared via hydrothermal method. J. Mol. Catal. A: Chem. 2006, 258, 104–112.

    Article  Google Scholar 

  48. Zhao, X. W.; Jin, W. Z.; Cai, J. G.; Ye, J. F.; Li, Z. H.; Ma, Y. R.; Xie, J. L.; Qi, L. M. Shape- and size-controlled synthesis of uniform anatase TiO2 nanocuboids enclosed by active {100} and {001} facets. Adv. Funct. Mater. 2011, 21, 3554–3563.

    Article  Google Scholar 

  49. Yin, Y. D.; Alivisatos, A. P. Colloidal nanocrystal synthesis and the organic–inorganic interface. Nature 2005, 437, 664–670.

    Article  Google Scholar 

  50. Schliehe, C.; Juarez, B. H.; Pelletier, M.; Jander, S.; Greshnykh, D.; Nagel, M.; Meyer, A.; Foerster, S.; Kornowski, A.; Klinke, C. et al. Ultrathin PbS sheets by two-dimensional oriented attachment. Science 2010, 329, 550–553.

    Article  Google Scholar 

  51. Bai, F.; Wang, D. S.; Huo, Z. Y.; Chen, W.; Liu, L. P.; Liang, X.; Chen, C.; Wang, X.; Peng, Q.; Li, Y. D. A versatile bottom-up assembly approach to colloidal spheres from nanocrystals. Angew. Chem., Int. Ed. 2007, 46, 6650–6653.

    Article  Google Scholar 

  52. Bishop, K. J. M.; Wilmer, C. E.; Soh, S.; Grzybowski, B. A. Nanoscale forces and their uses in self-assembly. Small 2009, 5, 1600–1630.

    Article  Google Scholar 

  53. Chowdhury, I.; Walker, S. L.; Mylon, S. E. Aggregate morphology of nano-TiO2: Role of primary particle size, solution chemistry, and organic matter. Environ. Sci. Process. Impacts 2012, 15, 275–282.

    Article  Google Scholar 

  54. Liu, H. S.; Bi, Z. H.; Sun, X. G.; Unocic, R. R.; Paranthaman, M. P.; Dai, S.; Brown, G. M. Mesoporous TiO2-B microspheres with superior rate performance for lithium ion batteries. Adv. Mater. 2011, 23, 3450–3454.

    Article  Google Scholar 

  55. Ren, Y.; Hardwick, L. J.; Bruce, P. G. Lithium intercalation into mesoporous anatase with an ordered 3D pore structure. Angew. Chem., Int. Ed. 2010, 49, 2570–2574.

    Article  Google Scholar 

  56. Ge, M. Y.; Rong, J. P.; Fang, X.; Zhou, C. W. Porous doped silicon nanowires for lithium ion battery anode with long cycle life. Nano Lett. 2012, 12, 2318–2323.

    Article  Google Scholar 

  57. Li, L.; Raji, A. R. O.; Tour, J. M. Graphene-wrapped MnO2 graphene nanoribbons as anode materials for high-performance lithium ion batteries. Adv. Mater. 2013, 25, 6298–6302.

    Article  Google Scholar 

  58. Wu, L. M.; Bresser, D.; Buchholz, D.; Giffin, G. A.; Castro, C. R.; Ochel, A.; Passerini, S. Unfolding the mechanism of sodium insertion in anatase TiO2 nanoparticles. Adv. Energy Mater. 2015, 5, 1401142.

    Article  Google Scholar 

  59. Oh, S.-M.; Hwang, J.-Y.; Yoon, C. S.; Lu, J.; Amine, K.; Belharouak, I.; Sun, Y.-K. High electrochemical performances of microsphere C-TiO2 anode for sodium-ion battery. ACS Appl. Mater. Interfaces 2014, 6, 11295–11301.

    Article  Google Scholar 

  60. Xu, Y.; Zhou, M.; Wen, L. Y.; Wang, C. L.; Zhao, H. P.; Mi, Y.; Liang, L. Y.; Fu, Q.; Wu, M. H.; Lei, Y. Highly ordered three-dimensional Ni-TiO2 nanoarrays as sodium ion battery anodes. Chem. Mater. 2015, 27, 4274–4280.

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Basic Research Program of China (No. 2015CB251100), and the Program for New Century Excellent Talents in University (No. NCET-13-0033).

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Authors and Affiliations

  1. Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Liming Ling, Ying Bai, Huali Wang, Qiao Ni, Feng Wu & Chuan Wu

  2. Collaborative Innovation Center of Electric Vehicles in Beijing, Beijing, 100081, China

    Ying Bai, Feng Wu & Chuan Wu

  3. Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Jiatao Zhang

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  1. Liming Ling
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  2. Ying Bai
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Correspondence to Ying Bai or Chuan Wu.

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Mesoporous TiO2 microparticles formed by the oriented attachment of nanocrystals: A super-durable anode material for sodium-ion batteries

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Ling, L., Bai, Y., Wang, H. et al. Mesoporous TiO2 microparticles formed by the oriented attachment of nanocrystals: A super-durable anode material for sodium-ion batteries. Nano Res. 11, 1563–1574 (2018). https://doi.org/10.1007/s12274-017-1772-3

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