Journal Home > Volume 9 , Issue 2
Nano Research 2016, 9(2): 353-362 https://doi.org/10.1007/s12274-015-0914-8
Research Article | Issue | Published: 18 November 2015

Remarkable anodic performance of lead titanate 1D nanostructures via in-situ irreversible formation of abundant Ti3+ as conduction pathways

Show Author's Information Zhiyong Shi1,  Jin Wang1( ),  Wenxi Wang2,  Yixiang Zhang1,  Bo Li1,  Zhouguang Lu2,  Yadong Li3
Division of Energy and Environment in Graduate School at ShenzhenTsinghua UniversityShenzhen518055China
Department of Materials Science and EngineeringSouth University of Science and Technology of ChinaShenzhen518055China
Department of ChemistryTsinghua UniversityBeijing100084China
Keywords:
PbTiO3 nanowires, lithium ion anode materials, amorphous Ti3+-rich matrix, composite structure
Cite this article:
Shi Z, Wang J, Wang W, et al. Remarkable anodic performance of lead titanate 1D nanostructures via in-situ irreversible formation of abundant Ti3+ as conduction pathways. Nano Research, 2016, 9(2): 353-362. https://doi.org/10.1007/s12274-015-0914-8
Download citation
EndNote(RIS)
BibTeX

482

Views

23

Downloads

Citations

7

Crossref

N/A

WoS

6

Scopus

1

CSCD

Abstract Full text About this article

PX-phase PbTiO3 (PT) nanowires with open channels running along the length direction have been investigated as an anode material for lithium ion batteries. This material shows a stabilized reversible specific capacity of about 410 mAh·g–1 up to 200 cycles with a charge/discharge voltage plateau of around 0.3–0.65 V. In addition, it exhibits superior high-rate performance, with 90% and 77% capacity retention observed at 1 and 2 A·g–1, respectively. At a very high current rate of 10 A·g–1, a specific capacity of over 170 mAh·g–1 is retained up to 100 cycles, significantly outperforming the rate capability reported for Pb and Pb oxides. The results of X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses along with the cyclic voltammogram results reveal that the PX-phase PT nanowires undergo irreversible structural amorphization and reduction reactions during the initial cycle, which allow them to transform into a composite structure composed of 2–5 nm Pb nanoparticles uniformly dispersed in the 1D amorphous Li2O·TiO2·LiTiO2 matrix. In this composite structure, the presence of abundant amounts of Ti3+ in both the charged and discharged states enhances the electrical conductance of the system, whereas the presence of ultrafine Pb nanoparticles imparts high reversible capacity. The structurally stable TiO2-based amorphous matrix can also considerably buffer the volume variation during the charge/discharge process, thereby facilitating extremely stable cycling performance. This compound combines the high specific capacity of Pb-based materials and the good rate capability of Ti3+-based wiring. Our results might furnish a possible route for achieving superior cycling and rate performance and contribute towards the search for next-generation anode materials.


menu
Abstract
Full text
Outline
About this article

Remarkable anodic performance of lead titanate 1D nanostructures via in-situ irreversible formation of abundant Ti3+ as conduction pathways

Show Author's information Zhiyong Shi1, Jin Wang1( ), Wenxi Wang2, Yixiang Zhang1, Bo Li1, Zhouguang Lu2, Yadong Li3
Division of Energy and Environment in Graduate School at ShenzhenTsinghua UniversityShenzhen518055China
Department of Materials Science and EngineeringSouth University of Science and Technology of ChinaShenzhen518055China
Department of ChemistryTsinghua UniversityBeijing100084China

Abstract

PX-phase PbTiO3 (PT) nanowires with open channels running along the length direction have been investigated as an anode material for lithium ion batteries. This material shows a stabilized reversible specific capacity of about 410 mAh·g–1 up to 200 cycles with a charge/discharge voltage plateau of around 0.3–0.65 V. In addition, it exhibits superior high-rate performance, with 90% and 77% capacity retention observed at 1 and 2 A·g–1, respectively. At a very high current rate of 10 A·g–1, a specific capacity of over 170 mAh·g–1 is retained up to 100 cycles, significantly outperforming the rate capability reported for Pb and Pb oxides. The results of X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses along with the cyclic voltammogram results reveal that the PX-phase PT nanowires undergo irreversible structural amorphization and reduction reactions during the initial cycle, which allow them to transform into a composite structure composed of 2–5 nm Pb nanoparticles uniformly dispersed in the 1D amorphous Li2O·TiO2·LiTiO2 matrix. In this composite structure, the presence of abundant amounts of Ti3+ in both the charged and discharged states enhances the electrical conductance of the system, whereas the presence of ultrafine Pb nanoparticles imparts high reversible capacity. The structurally stable TiO2-based amorphous matrix can also considerably buffer the volume variation during the charge/discharge process, thereby facilitating extremely stable cycling performance. This compound combines the high specific capacity of Pb-based materials and the good rate capability of Ti3+-based wiring. Our results might furnish a possible route for achieving superior cycling and rate performance and contribute towards the search for next-generation anode materials.

Keywords: PbTiO3 nanowires, lithium ion anode materials, amorphous Ti3+-rich matrix, composite structure

References(32)

1

Armand, M.; Tarascon, J. -M. Building better batteries. Nature 2008, 451, 652–657.
DOI Google Scholar
2

Park, D. -Y.; Sun, Y. -K.; Myung, S. -T. Carbothermal synthesis of molybdenum(Ⅳ) oxide as a high rate anode for rechargeable lithium batteries. J. Power Sources 2015, 280, 1–4.
DOI Google Scholar
3

Liang, J. W.; Li, X. N.; Zhu, Y. C.; Guo, C.; Qian, Y. T. Hydrothermal synthesis of nano-silicon from a silica sol and its use in lithium ion batteries. Nano Res. 2015, 8, 1497–1504.
DOI Google Scholar
4

Im, H. S.; Cho, Y. J.; Lim, Y. R.; Jung, C. S.; Jang, D. M.; Park, J.; Shojaei, F.; Kang, H. S. Phase evolution of tin nanocrystals in lithium ion batteries. ACS Nano 2013, 7, 11103–11111.
DOI Google Scholar
5

Chen, M. H.; Liu, J. L.; Chao, D. L.; Wang, J.; Yin, J. H.; Lin, J. Y.; Fan, H. J.; Shen, Z. X. Porous a-Fe2O3 nanorods supported on carbon nanotubes-graphene foam as superior anode for lithium ion batteries. Nano Energy 2014, 9, 364–372.
DOI Google Scholar
6

Deng, D.; Kim, M. G.; Lee, J. Y.; Cho, J. Green energy storage materials: Nanostructured TiO2 and Sn-based anodes for lithium-ion batteries. Energy Environ. Sci. 2009, 2, 818–837.
DOI Google Scholar
7

Plylahan, N.; Letiche, M.; Samy Barr, M. K.; Ellis, B.; Maria, S.; Phan, T. N. T.; Bloch, E.; Knauth, P.; Djenizian, T. High energy and power density TiO2 nanotube electrodes for single and complete lithium-ion batteries. J. Power Sources 2015, 273, 1182–1188.
DOI Google Scholar
8

Su, D. W.; Dou, S. X.; Wang, G. X. Mesocrystal Co3O4 nanoplatelets as high capacity anode materials for Li-ion batteries. Nano Res. 2014, 7, 794–803.
DOI Google Scholar
9

Jiang, J.; Li, Y. Y.; Liu, J. P.; Huang, X. T.; Yuan, C. Z.; Lou, X. W. Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage. Adv. Mater. 2012, 24, 5166–5180.
DOI Google Scholar
10

Li, H.; Wang, Z. X.; Chen, L. Q. Huang, X. J. Research on advanced materials for Li-ion batteries. Adv. Mater. 2009, 21, 4593–4607.
DOI Google Scholar
11

Konstantinov, K.; Ng, S. H.; Wang, J. Z.; Wang, G. X.; Wexler, D.; Liu, H. K. Nanostructured PbO materials obtained in situ by spray solution technique for Li-ion batteries. J. Power Sources 2006, 159, 241–244.
DOI Google Scholar
12

Pan, Q. M.; Wang, Z. J.; Liu, J.; Yin, G. P.; Gu, M. PbO@C core–shell nanocomposites as an anode material of lithiumion batteries. Electrochem. Commun. 2009, 11, 917–920.
DOI Google Scholar
13

Martos, M.; Morales, J.; Sánchez, L. Lead-based systems as suitable anode materials for Li-ion batteries. Electrochim. Acta 2003, 48, 615–621.
DOI Google Scholar
14

Wang, J.; Schenk, K.; Carvalho, A.; Wylie-van Eerd, B.; Trodahl, J.; Sandu, C. S.; Bonin, M. Gregora, I.; He, Z. B.; Yamada, T. et al. Structure determination and compositional modification of body-centered tetragonal PX-phase lead titanate. Chem. Mater. 2011, 23, 2529–2535.
DOI Google Scholar
15

Yu, X. Y.; Wu, H. B.; Yu, L.; Ma, F. X.; Lou, X. W. Rutile TiO2 submicroboxes with superior lithium storage properties. Angew. Chem., Int. Ed. 2015, 54, 4001–4004.
DOI Google Scholar
16

Tian, M.; Wang, W.; Liu, Y.; Jungjohann, K. L.; Thomas Harris, C.; Lee, Y. -C.; Yang, R. G. A three-dimensional carbon nano-network for high performance lithium ion batteries. Nano Energy 2015, 11, 500–509.
DOI Google Scholar
17

Ji, L. W.; Lin, Z.; Alcoutlabi, M.; Zhang, X. W. Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries. Energy Environ. Sci. 2011, 4, 2682–2699.
DOI Google Scholar
18

Henningsson, A.; Rensmo, H.; Sandell, A.; Siegbahn, H.; Södergren, S.; Lindström, H.; Hagfeldt, A. Electronic structure of electrochemically Li-inserted TiO2 studied with synchrotron radiation electron spectroscopies. J. Chem. Phys. 2003, 118, 5607–5612.
DOI Google Scholar
19

Li, X. H.; He, Y. B.; Miao, C.; Qin, X. Y.; Lv, W.; Du, H. D.; Li, B. H.; Yang, Q. H.; Kang, F. Y. Carbon coated porous tin peroxide/carbon composite electrode for lithium-ion batteries with excellent electrochemical properties. Carbon 2015, 81, 739–747.
DOI Google Scholar
20

Ohzuku, T.; Shimamoto, T.; Hirai, T. Lead oxides as cathode for lithium non-aqueous cells. Electrochim. Acta 1981, 26, 751–754.
DOI Google Scholar
21

Kim, K. -T.; Yu, C. -Y.; Kim, S. -J.; Sun, Y. -K.; Myung, S. -T. Carbon-coated anatase titania as a high rate anode for lithium batteries. J. Power Sources 2015, 281, 362–369.
DOI Google Scholar
22

Myung, S. T.; Takahashi, N.; Komaba, S.; Yoon, C. S.; Sun, Y. K.; Amine, K.; Yashiro, H. Nanostructured TiO2 and its application in lithium-ion storage. Adv. Funct. Mater. 2011, 21, 3231–3241.
DOI Google Scholar
23

Liu, S. H.; Jia, H. P.; Han, L.; Wang, J. L.; Gao, P. F.; Xu, D. D.; Yang, J.; Che, S. N. Nanosheet-constructed porous TiO2–B for advanced lithium ion batteries. Adv. Mater. 2012, 24, 3201–3204.
DOI Google Scholar
24

Menéndez, R.; Alvarez, P.; Botas, C.; Nacimiento, F.; Alcántara, R.; Tirado, J. L.; Ortiz, G. F. Self-organized amorphous titania nanotubes with deposited graphene film like a new heterostructured electrode for lithium ion batteries. J. Power Sources 2014, 248, 886–893.
DOI Google Scholar
25

Hegde, R. I.; Sainkar, S. R.; Badrinarayanan, S.; Sinha, A. P. B. A study of dilute tin alloys by X-ray photoelectron spectroscopy. J. Electron. Spectrosc. Relat. Phenom. 1981, 24, 19–25.
DOI Google Scholar
26

Dementjev, A. P.; Ivanova, O. P.; Vasilyev, L. A.; Naumkin, A. V.; Nemirovsky, D. M.; Shalaev, D. Y. Altered layer as sensitive initial chemical state indicator. J. Vac. Sci. Technol. A 1994, 12, 423–425.
DOI Google Scholar
27

Bach, S.; Pereira-Ramos, J. P.; Willman, P. Investigation of lithium diffusion in nano-sized rutile TiO2 by impedance spectroscopy. Electrochim. Acta 2010, 55, 4952–4959.
DOI Google Scholar
28

Gao, Q.; Gu, M.; Nie, A. M.; Mashayek, F.; Wang, C. M.; Odegard, G. M.; Shahbazian-Yassar, R. Direct evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes. Chem. Mater. 2014, 26, 1660–1669.
DOI Google Scholar
29

Chen, Z. X.; Cao, Y. L.; Qian, J. F.; Ai, X. P.; Yang, H. X. Pb-sandwiched nanoparticles as anode material for lithiumion batteries. J Solid State Electr. 2012, 16, 291–295.
DOI Google Scholar
30

Shu, J.; Ma, R.; Shao, L. Y.; Shui, M.; Wang, D. J.; Wu, K. G.; Long, N. B.; Ren, Y. L. Hydrothermal fabrication of lead hydroxide chloride as a novel anode material for lithiumion batteries. Electrochim. Acta 2013, 102, 381–387.
DOI Google Scholar
31

Wang, D. J.; Wu, K. Q.; Shao, L. Y.; Shui, M.; Ma, R.; Lin, X. T.; Long, N. B.; Ren, Y. L.; Shu, J. Facile fabrication of Pb(NO3)2/C as advanced anode material and its lithium storage mechanism. Electrochim. Acta 2014, 120, 110–121.
DOI Google Scholar
32

Wood, S. M.; Powell, E. J.; Heller, A.; Mullins, C. B. Lithiation and delithiation of lead sulfide (PbS). J. Electrochem. Soc. 2015, 162, A1182–A1185.
DOI Google Scholar
Publication history
Copyright
Acknowledgements

Publication history

Received: 28 July 2015
Revised: 22 September 2015
Accepted: 05 October 2015
Published: 18 November 2015
Issue date: February 2016

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2015

Acknowledgements

Acknowledgements

This work is supported by National Natural Science Foundation of China (No. 51302143), Shenzhen Special Fund for the Development of Emerging Industries (No. JCYJ20140417115840233), and Shenzhen Peacock Plan (No. KQCX20140521161756228).

Return