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Nano Research 2019, 12(5): 1193-1197 https://doi.org/10.1007/s12274-019-2381-0
Research Article | Issue | Published: 02 April 2019

One-pot synthesis of highly conductive nickel-rich phosphide/CNTs hybrid as a polar sulfur host for high-rate and long-cycle Li-S battery

Show Author's Information Xiao-Fei Yu,  Dong-Xu Tian,  Wen-Cui Li,  Bin He,  Yu Zhang,  Zhi-Yuan Chen,  An-Hui Lu( )
State Key Laboratory of Fine Chemicals,School of Chemical Engineering, Dalian University of Technology,Dalian,116024,China;
Keywords:
carbon nanotube, lithium sulfur battery, high conductivity, Ni-rich phosphides, catalytic effect
Topics:
Carbon nanotubesCathodesLithium batteriesLithium compoundsNickel compoundsPhosphorus compoundsPolysulfidesRedox reactionsVirtual storage
Cite this article:
Yu X-F, Tian D-X, Li W-C, et al. One-pot synthesis of highly conductive nickel-rich phosphide/CNTs hybrid as a polar sulfur host for high-rate and long-cycle Li-S battery. Nano Research, 2019, 12(5): 1193-1197. https://doi.org/10.1007/s12274-019-2381-0
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Abstract Full text Electronic supplementary material About this article

Lithium sulfur battery has been identified as a promising candidate for next storage devices attributing to ultrahigh energy density. However, non-conductive nature of sulfur and shuttling effect of soluble lithium polysulfides are intractable remaining problems. Herein, we develop a highly conductive nickel-rich Ni12P5/CNTs hybrid with high specific surface area as sulfur host to address these issues. The polar nature of Ni12P5/CNTs can significantly relieve the shuttle effect by means of a strong affinity towards lithium polysulfides and enhance kinetics of polysulfides redox reactions. In addition, the Ni12P5/CNTs with a superior conductivity (500 S·m-1) and high surface area of 395 m2·g-1 enables the effective electron transfer and expedited interfacial reaction. As a result, Ni12P5/CNTs hosted sulfur cathode exhibits high rate capability (784 mAh·g-1 at 4 C) and stable cycling performance with a negligible capacity fading of 0.057 % per cycle over 1, 000 cycles at 0.5 C. This work paves an alternative way for designing high performance sulfur cathodes involved metal-rich phosphides.


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About this article

One-pot synthesis of highly conductive nickel-rich phosphide/CNTs hybrid as a polar sulfur host for high-rate and long-cycle Li-S battery

Show Author's information Xiao-Fei Yu, Dong-Xu Tian, Wen-Cui Li, Bin He, Yu Zhang, Zhi-Yuan Chen, An-Hui Lu( )
State Key Laboratory of Fine Chemicals,School of Chemical Engineering, Dalian University of Technology,Dalian,116024,China;

Abstract

Lithium sulfur battery has been identified as a promising candidate for next storage devices attributing to ultrahigh energy density. However, non-conductive nature of sulfur and shuttling effect of soluble lithium polysulfides are intractable remaining problems. Herein, we develop a highly conductive nickel-rich Ni12P5/CNTs hybrid with high specific surface area as sulfur host to address these issues. The polar nature of Ni12P5/CNTs can significantly relieve the shuttle effect by means of a strong affinity towards lithium polysulfides and enhance kinetics of polysulfides redox reactions. In addition, the Ni12P5/CNTs with a superior conductivity (500 S·m-1) and high surface area of 395 m2·g-1 enables the effective electron transfer and expedited interfacial reaction. As a result, Ni12P5/CNTs hosted sulfur cathode exhibits high rate capability (784 mAh·g-1 at 4 C) and stable cycling performance with a negligible capacity fading of 0.057 % per cycle over 1, 000 cycles at 0.5 C. This work paves an alternative way for designing high performance sulfur cathodes involved metal-rich phosphides.

Keywords: carbon nanotube, lithium sulfur battery, high conductivity, Ni-rich phosphides, catalytic effect

References(38)

1

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

Manthiram, A.; Fu, Y. Z.; Chung, S. H.; Zu, C. X.; Su, Y. S. Rechargeable lithium–sulfur batteries. Chem. Rev. 2014, 114, 11751–11787.
DOI Google Scholar
3

Yin, Y. X.; Xin, S.; Guo, Y. G.; Wan, L. J. Lithium–sulfur batteries: Electrochemistry, materials, and prospects. Angew. Chem. , Int. Ed. 2013, 52, 13186–13200.
DOI Google Scholar
4

Goodenough, J. B.; Kim, Y. Challenges for rechargeable Li batteries. Chem. Mater. 2010, 22, 587–603.
DOI Google Scholar
5

Larcher, D.; Tarascon, J. M. Towards greener and more sustainable batteries for electrical energy storage. Nat. Chem. 2015, 7, 19–29.
DOI Google Scholar
6

Urbonaite, S.; Poux, T.; Novák, P. Progress towards commercially viable Li–S battery cells. Adv. Energy Mater. 2015, 5, 1500118.
DOI Google Scholar
7

Yang, Y.; Zheng, G. Y.; Cui, Y. Nanostructured sulfur cathodes. Chem. Soc. Rev. 2013, 42, 3018–3032.
DOI Google Scholar
8

Moon, S.; Jung, Y. H.; Jung, W. K.; Jung, D. S.; Choi, J. W.; Kim, D. K. Encapsulated monoclinic sulfur for stable cycling of Li–S rechargeable batteries. Adv. Mater. 2013, 25, 6547–6553.
DOI Google Scholar
9

Zhang, S. S. Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions. J. Power Sources 2013, 231, 153–162.
DOI Google Scholar
10

Zhang, Z.; Wu, D. H.; Zhou, Z.; Li, G. R.; Liu, S.; Gao, X. P. Sulfur/nickel ferrite composite as cathode with high-volumetric-capacity for lithium-sulfur battery. Sci. China Mater. 2019, 62, 74–86, DOI: 10.1007/s40843-018-9292-7.
DOI Google Scholar
11

He, B.; Li, W. C.; Yang, C.; Wang, S. Q.; Lu, A. H. Incorporating sulfur inside the pores of carbons for advanced lithium–sulfur batteries: An electrolysis approach. ACS Nano 2016, 10, 1633–1639.
DOI Google Scholar
12

Zhao, M. Q.; Zhang, Q.; Huang, J. Q.; Tian, G. L.; Nie, J. Q.; Peng, H. J.; Wei, F. Unstacked double-layer templated graphene for high-rate lithium–sulphur batteries. Nat. Commun. 2014, 5, 3410.
DOI Google Scholar
13

Hu, G. J; Xu, C.; Sun, Z. H.; Wang, S. G.; Cheng, H. M.; Li, F.; Ren, W. C. 3D graphene-foam-reduced-graphene-oxide hybrid nested hierarchical networks for high-performance Li-S batteries. Adv. Mater. 2016, 28, 1603–1609.
DOI Google Scholar
14

Zhao, M. Q.; Peng, H. J.; Tian, G. L.; Zhang, Q.; Huang, J. Q.; Cheng, X. B.; Tang, C.; Wei, F. Hierarchical vine-tree-like carbon nanotube architectures: In-situ CVD self-assembly and their use as robust scaffolds for lithium-sulfur batteries. Adv. Mater. 2014, 26, 7051–7058.
DOI Google Scholar
15

Zhao, Y.; Wu, W.; Li, J.; Xu, Z.; Guan, L. Encapsulating MWNTs into hollow porous carbon nanotubes: A tube-in-tube carbon nanostructure for high-performance lithium-sulfur batteries. Adv. Mater. 2014, 26, 5113–5118.
DOI Google Scholar
16

Zhang, X. Q.; He, B.; Li, W. C.; Lu, A. H. Hollow carbon nanofibers with dynamic adjustable pore sizes and closed ends as hosts for high-rate lithium-sulfur battery cathodes. Nano Res. 2018, 11, 1238–1246.
DOI Google Scholar
17

Zhou, G. M.; Li, L.; Wang, D. W.; Shan, X. Y.; Pei, S. F.; Li, F.; Cheng, H. M. Flexible sulfur-graphene-polypropylene separator integrated electrode for advanced Li-S batteries. Adv. Mater. 2015, 27, 641–647.
DOI Google Scholar
18

Sun, Q.; He, B.; Zhang, X. Q.; Lu, A. H. Engineering of hollow core–shell interlinked carbon spheres for highly stable lithium–sulfur batteries. ACS Nano 2015, 9, 8504–8513.
DOI Google Scholar
19

Zhang, L. H.; He, B.; Li, W. C.; Lu, A. H. Surface free energy-induced assembly to the synthesis of grid-like multicavity carbon spheres with high level in-cavity encapsulation for Lithium–Sulfur cathode. Adv. Energy Mater. 2017, 7, 1701518.
DOI Google Scholar
20

Li, D.; Han, F.; Wang, S.; Cheng, F.; Sun, Q.; Li, W. C. High sulfur loading cathodes fabricated using peapodlike, large pore volume mesoporous carbon for Lithium–Sulfur battery. ACS Appl. Mater. Interfaces 2013, 5, 2208–2213.
DOI Google Scholar
21

Song, J. X.; Gordin, M. L.; Xu, T.; Chen, S. R.; Yu, Z. X.; Sohn, H.; Lu, J.; Ren, Y.; Duan, Y. H.; Wang, D. H. Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium–sulfur battery cathodes. Angew. Chem., Int. Ed. 2015, 127, 4399–4403.
DOI Google Scholar
22

Yang, C. P.; Yin, Y. X.; Ye, H; Jiang, K. C.; Zhang, J.; Guo, Y. G. Insight into the effect of boron doping on sulfur/carbon cathode in lithium–sulfur batteries. ACS Appl. Mater. Interfaces 2014, 6, 8789–8795.
DOI Google Scholar
23

Zhou, G. M.; Yin, L. C.; Wang, D. W.; Li, L.; Pei, S. F.; Gentle, I. R.; Li, F.; Cheng, H. M. Fibrous hybrid of graphene and sulfur nanocrystals for high-performance Lithium–Sulfur batteries. ACS Nano 2013, 7, 5367–5375.
DOI Google Scholar
24

Pang, Q.; Tang, J. T.; Huang, H.; Liang, X.; Hart, C.; Tam, K. C.; Nazar, L. F. A nitrogen and sulfur dual-doped carbon derived from polyrhodanine@cellulose for advanced lithium-sulfur batteries. Adv. Mater. 2015, 27, 6021–6028.
DOI Google Scholar
25

Gu, X. X.; Tong, C. J.; Lai, C.; Qiu, J. X.; Huang, X. X.; Yang, W. L.; Wen, B.; Liu, L. M.; Hou, Y. L.; Zhang, S. Q. A porous nitrogen and phosphorous dual doped graphene blocking layer for high performance Li–S batteries. J. Mater. Chem. A 2015, 3, 16670–16678.
DOI Google Scholar
26

Liang, X.; Hart, C.; Pang, Q.; Garsuch, A.; Weiss, T.; Nazar, L. F. A highly efficient polysulfide mediator for lithium–sulfur batteries. Nat. Commun. 2015, 6, 5682.
DOI Google Scholar
27

Seh, Z. W.; Li, W. Y.; Cha, J. J.; Zheng, G. Y.; Yang, Y.; McDowell, M. T.; Hsu, P. C.; Cui, Y. Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries. Nat. Commun. 2013, 4, 1331.
DOI Google Scholar
28

Li, C. X.; Xi, Z. C.; Guo, D. X.; Chen, X. J.; Yin, L. W. Chemical immobilization effect on Lithium polysulfides for lithium–sulfur batteries. Small 2018, 14, 1701986.
DOI Google Scholar
29

Ma, L. B.; Chen, R. P.; Zhu, G. Y.; Hu, Y.; Wang, Y. R.; Chen, T.; Liu, J; Jin, Z. Cerium oxide nanocrystal embedded bimodal micromesoporous nitrogen-rich carbon nanospheres as effective sulfur host for lithium-sulfur batteries. ACS Nano 2017, 11, 7274–7283.
DOI Google Scholar
30

Wang, H. Q.; Zhang, W. C.; Xu, J. Z.; Guo, Z. P. Advances in polar materials for lithium–sulfur batteries. Adv. Funct. Mater. 2018, 28, 1707520.
DOI Google Scholar
31

Tao, X. Y.; Wang, J. G.; Liu, C.; Wang, H. T.; Yao, H. B.; Zheng, G. Y.; Seh, Z. W.; Cai, Q. X.; Li, W. Y.; Zhou, G. M. et al. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design. Nat. Commun. 2016, 7, 11203.
DOI Google Scholar
32

Xu, Y. Y.; Duan, S. B.; Li, H. Y.; Yang, M.; Wang, S. J.; Wang, X.; Wang, R. M. Au/Ni12P5 core/shell single-crystal nanoparticles as oxygen evolution reaction catalyst. Nano Res. 2017, 10, 3103–3112.
DOI Google Scholar
33

Shi, Y. M.; Zhang, B. Recent advances in transition metal phosphide nanomaterials: Synthesis and applications in hydrogen evolution reaction. Chem. Soc. Rev. 2016, 45, 1529–1541.
DOI Google Scholar
34

Ji, P. H.; Shang, B.; Peng, Q. M.; Hu, X. B.; Wei, J. W. α-MoO3 spheres as effective polysulfides adsorbent for high sulfur content cathode in lithium-sulfur batteries. J. Power Sources 2018, 400, 572–579.
DOI Google Scholar
35

Balamurugan, J.; Thanh, T. D.; Kim, N. H.; Lee, J. H. Facile synthesis of 3D hierarchical N-doped graphene nanosheet/cobalt encapsulated carbon nanotubes for high energy density asymmetric supercapacitors. J. Mater. Chem. A 2016, 4, 9555–9565.
DOI Google Scholar
36

Zhou, T. H.; Lv, W.; Li, J.; Zhou, G. M.; Zhao, Y.; Fan, S. X.; Liu, B. L.; Li, B. H.; Kang, F. Y.; Yang, Q. H. Twinborn TiO2–TiN heterostructures enabling smooth trapping-diffusion-conversion of polysulfides towards ultralong life lithium-sulfur batteries. Energy Environ. Sci. 2017, 10, 1694–1703.
DOI Google Scholar
37

Xu, Z. L.; Lin, S. H.; Onofrio, N.; Zhou, L. M.; Shi, F. Y.; Lu, W.; Kang, K.; Zhang, Q.; Lau, S. P. Exceptional catalytic effects of black phosphorus quantum dots in shuttling-free lithium sulfur batteries. Nat. Commun. 2018, 9, 4164.
DOI Google Scholar
38

He, B.; Li, W. C.; Zhang, Y.; Yu, X. F.; Zhang, B. S.; Li, F.; Lu, A. H. Paragenesis BN/CNTs hybrid as a monoclinic sulfur host for high rate and ultra-long life lithium–sulfur battery. J. Mater. Chem. A 2018, 6, 24194–24200.
DOI Google Scholar
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Publication history
Copyright
Acknowledgements

Publication history

Received: 03 January 2019
Revised: 25 February 2019
Accepted: 12 March 2019
Published: 02 April 2019
Issue date: May 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

Acknowledgements

The authors are grateful to the financial support by the National Natural Science Foundation of China (Nos. 21776041 and 21875028), and Cheung Kong Scholars Programme of China (No. T2015036).

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