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Nano Research 2019, 12(4): 829-836 https://doi.org/10.1007/s12274-019-2298-7
Research Article | Issue | Published: 25 January 2019

Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries

Show Author's Information Xintao Zuo1,  Mengmeng Zhen1,2( ),  Cheng Wang1( )
Tianjin Key Laboratory of Advanced Functional Porous Materials and Center for Electron Microscopy,Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology,Tianjin,300071,China;
Tianjin Key Laboratory of Clean Energy and Pollution Control,School of Energy and Environmental Engineering, Hebei University of Technology,Tianjin,300401,China;
Keywords:
lithium-sulfur batteries, self-assembled hierarchical architecture, confined Ni nanoparticles, abundant carbon nanocages, modified separator
Topics:
Carbon nanotubesDoping (additives)ElectrodesElectrolytesEnergy efficiencyGrapheneIon batteriesLithiumLithium compoundsNanoparticlesNanosheetsNickel compoundsPolysulfides
Cite this article:
Zuo X, Zhen M, Wang C. Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries. Nano Research, 2019, 12(4): 829-836. https://doi.org/10.1007/s12274-019-2298-7
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Abstract Full text Electronic supplementary material About this article

Lithium-sulfur batteries (LSBs) have been regarded as one of the most promising energy storage systems to break through the upper limit of lithium-ion batteries. However, the rampant diffusions of soluble lithium polysulfides (LiPSs) in the electrolyte induced the shuttle effect between anode and cathode, resulting in low sulfur utilization, low energy efficiency and short cycling life. Herein, we prove the rational design and construction of Ni nanoparticles filled in vertically grown N-doped bamboo-like carbon nanotubes (CNTs) on graphene nanosheets (Ni@NG-CNTs) as efficient polysulfide barrier for high-performance LSBs. The unique design integrates graphene nanosheets and CNTs into hierarchical architectures with one-dimensional (1D) CNTs, two-dimensional (2D) ultrathin nanosheets and abundant carbon nanocages. This design provides large surface area for lithium polysulfides (LiPSs) adsorption, accelerates electron transport and enhances electrochemical redox of LiPSs. Benefiting from the unique structural features, the LSBs with the Ni@NG-CNTs as polysulfide barrier keep high reversible specific capacities of 309.1 and 265.0 mAh·g−1 at 5 and 10 C rates after 500 cycles. This work provides a new strategy for constructing self-assembled hybrids of CNTs and graphene nanosheets with abundant carbon nanocages for high-performance LSBs.


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Electronic supplementary material
About this article

Ni@N-doped graphene nanosheets and CNTs hybrids modified separator as efficient polysulfide barrier for high-performance lithium sulfur batteries

Show Author's information Xintao Zuo1, Mengmeng Zhen1,2( ), Cheng Wang1( )
Tianjin Key Laboratory of Advanced Functional Porous Materials and Center for Electron Microscopy,Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology,Tianjin,300071,China;
Tianjin Key Laboratory of Clean Energy and Pollution Control,School of Energy and Environmental Engineering, Hebei University of Technology,Tianjin,300401,China;

Abstract

Lithium-sulfur batteries (LSBs) have been regarded as one of the most promising energy storage systems to break through the upper limit of lithium-ion batteries. However, the rampant diffusions of soluble lithium polysulfides (LiPSs) in the electrolyte induced the shuttle effect between anode and cathode, resulting in low sulfur utilization, low energy efficiency and short cycling life. Herein, we prove the rational design and construction of Ni nanoparticles filled in vertically grown N-doped bamboo-like carbon nanotubes (CNTs) on graphene nanosheets (Ni@NG-CNTs) as efficient polysulfide barrier for high-performance LSBs. The unique design integrates graphene nanosheets and CNTs into hierarchical architectures with one-dimensional (1D) CNTs, two-dimensional (2D) ultrathin nanosheets and abundant carbon nanocages. This design provides large surface area for lithium polysulfides (LiPSs) adsorption, accelerates electron transport and enhances electrochemical redox of LiPSs. Benefiting from the unique structural features, the LSBs with the Ni@NG-CNTs as polysulfide barrier keep high reversible specific capacities of 309.1 and 265.0 mAh·g−1 at 5 and 10 C rates after 500 cycles. This work provides a new strategy for constructing self-assembled hybrids of CNTs and graphene nanosheets with abundant carbon nanocages for high-performance LSBs.

Keywords: lithium-sulfur batteries, self-assembled hierarchical architecture, confined Ni nanoparticles, abundant carbon nanocages, modified separator

References(51)

1

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
2

Jiang, J.; Zhu, J. H.; Ai, W.; Wang, X. L.; Wang, Y. L.; Zou, C. J.; Huang, W.; Yu, T. Encapsulation of sulfur with thin-layered nickel-based hydroxides for long-cyclic lithium-sulfur cells. Nat. Commun. 2015, 6, 8622.
DOI Google Scholar
3

Tikekar, M. D.; Choudhury, S.; Tu, Z. Y.; Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 2016, 1, 16114.
DOI Google Scholar
4

Fang, R. P.; Zhao, S. Y.; Pei, S. F.; Cheng, Y. X.; Hou, P. X.; Liu, M.; Cheng, H. M.; Liu, C.; Li, F. An integrated electrode/separator with nitrogen and nickel functionalized carbon hybrids for advanced lithium/polysulfide batteries. Carbon 2016, 109, 719–726.
DOI Google Scholar
5

Pang, Q.; Liang, X.; Kwok, C. Y.; Nazar, L. F. Advances in lithium-sulfur batteries based on multifunctional cathodes and electrolytes. Nat. Energy 2016, 1, 16132.
DOI Google Scholar
6

Ji, X. L.; Lee, K. T.; Nazar, L. F. A highly ordered nanostructured carbon- sulphur cathode for lithium-sulphur batteries. Nat. Mater. 2009, 8, 500–506.
DOI Google Scholar
7

Luo, L.; Chung, S. H.; Manthiram, A. A three-dimensional self-assembled SnS2-nano-dots@graphene hybrid aerogel as an efficient polysulfide reservoir for high-performance lithium-sulfur batteries. J. Mater. Chem. A 2018, 6, 7659–7667.
DOI Google Scholar
8

Zhu, S. Y.; Wang, Y. Q.; Jiang, J. C.; Yan, X.; Sun, D. Y.; Jin, Y. C.; Nan, C. W.; Munakata, H.; Kanamura, K. Good low-temperature properties of nitrogen-enriched porous carbon as sulfur hosts for high-performance Li-S batteries. ACS Appl. Mater. Interfaces 2016, 8, 17253–17259.
DOI Google Scholar
9

Bai, S. Y.; Liu, X. Z.; Zhu, K.; Wu, S. C.; Zhou, H. S. Metal–organic framework-based separator for lithium–sulfur batteries. Nat. Energy 2016, 1, 16094.
DOI Google Scholar
10

Cao, J.; Chen, C.; Zhao, Q.; Zhang, N.; Lu, Q. Q.; Wang, X. Y.; Niu, Z. Q.; Chen, J. A flexible nanostructured paper of a reduced graphene oxide-sulfur composite for high-performance lithium-sulfur batteries with unconventional configurations. Adv. Mater. 2016, 28, 9629–9636.
DOI Google Scholar
11

Gnana Kumar, G.; Chung, S. H.; Raj Kumar, T.; Manthiram, A. Three-dimensional graphene-carbon nanotube-Ni hierarchical architecture as a polysulfide trap for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 20627–20634.
DOI Google Scholar
12

Chung, S. H.; Chang, C. H.; Manthiram, A. A core-shell electrode for dynamically and statically stable Li–S battery chemistry. Energy Environ. Sci. 2016, 9, 3188–3200.
DOI Google Scholar
13

Chen, C. Y.; Peng, H. J.; Hou, T. Z.; Zhai, P. Y.; Li, B. Q.; Tang, C.; Zhu, W. C.; Huang, J. Q.; Zhang, Q. A quinonoid-imine-enriched nanostructured polymer mediator for lithium-sulfur batteries. Adv. Mater. 2017, 29, 1606802.
DOI Google Scholar
14

Cui, Z. M.; Zu, C. X.; Zhou, W. D.; Manthiram, A.; Goodenough, J. B. Mesoporous titanium nitride-enabled highly stable lithium-sulfur batteries. Adv. Mater. 2016, 28, 6926–6931.
DOI Google Scholar
15

Wang, L.; Yang, Z.; Nie, H. G.; Gu, C. C.; Hua, W. X.; Xu, X. J.; Chen, X. A.; Chen, Y.; Huang, S. M. A lightweight multifunctional interlayer of sulfur-nitrogen dual-doped graphene for ultrafast, long-life lithium-sulfur batteries. J. Mater. Chem. A 2016, 4, 15343–15352.
DOI Google Scholar
16

Ghazi, Z. A.; He, X.; Khattak, A. M.; Khan, N. A.; Liang, B.; Iqbal, A.; Wang, J. X.; Sin, H.; Li, L. S.; Tang, Z. Y. MoS2/Celgard separator as efficient polysulfide barrier for long-life lithium-sulfur batteries. Adv. Mater. 2017, 29, 1606817.
DOI Google Scholar
17

Li, F.; Kaiser, M. R.; Ma, J. M.; Guo, Z. P.; Liu, H. K.; Wang, J. Z. Free- standing sulfur-polypyrrole cathode in conjunction with polypyrrole-coated separator for flexible Li-S batteries. Energy Storage Mater. 2018, 13, 312–322.
DOI Google Scholar
18

Li, J.; Huang, Y. D.; Zhang, S.; Jia, W.; Wang, X. C.; Guo, Y.; Jia, D. Z.; Wang, L. S. Decoration of silica nanoparticles on polypropylene separator for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2017, 9, 7499–7504.
DOI Google Scholar
19

Song, J. J.; Su, D. W.; Xie, X. Q.; Guo, X.; Bao, W. Z.; Shao, G. J.; Wang, G. X. Immobilizing polysulfides with MXene-functionalized separators for stable lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 29427–29433.
DOI Google Scholar
20

Balach, J.; Singh, H. K.; Gomoll, S.; Jaumann, T.; Klose, M.; Oswald, S.; Richter, M.; Eckert, J.; Giebeler, L. Synergistically enhanced polysulfide chemisorption using a flexible hybrid separator with N and S dual-doped mesoporous carbon coating for advanced lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 14586–14595.
DOI Google Scholar
21

Su, D. W.; Cortie, M.; Fan, H. B.; Wang, G. X. Prussian blue nanocubes with an open framework structure coated with PEDOT as high-capacity cathodes for lithium-sulfur batteries. Adv. Mater. 2017, 29, 1700587.
DOI Google Scholar
22

Zhang, J.; Yang, C. P.; Yin, Y. X.; Wan, L. J.; Guo, Y. G. Sulfur encapsulated in graphitic carbon nanocages for high-rate and long-cycle lithium-sulfur batteries. Adv. Mater. 2016, 28, 9539–9544.
DOI Google Scholar
23

Jin, F. Y.; Xiao, S.; Lu, L. J.; Wang, Y. Efficient activation of high-loading sulfur by small CNTs confined inside a large CNT for high-capacity and high-rate lithium-sulfur batteries. Nano Lett. 2016, 16, 440–447.
DOI Google Scholar
24

Wang, Y.; Kong, D. Z.; Shi, W. H.; Liu, B.; Sim, G. J.; Ge, Q.; Yang, H. Y. Ice templated free-standing hierarchically WS2/CNT-rGO aerogel for high-performance rechargeable lithium and sodium ion batteries. Adv. Energy Mater. 2016, 6, 1601057.
DOI Google Scholar
25

Su, Y. S.; Manthiram, A. A new approach to improve cycle performance of rechargeable lithium-sulfur batteries by inserting a free-standing MWCNT interlayer. Chem. Commun. 2012, 48, 8817–8819.
DOI Google Scholar
26

Pang, Y.; Wei, J. S.; Wang, Y. G.; Xia, Y. Y. Synergetic protective effect of the ultralight MWCNTs/NCQDs modified separator for highly stable lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1702288.
DOI Google Scholar
27

Su, D. W.; Cortie, M.; Wang, G. X. Fabrication of N-doped graphene- carbon nanotube hybrids from prussian blue for lithium-sulfur batteries. Adv. Energy Mater. 2017, 7, 1602014.
DOI Google Scholar
28

Liang, J.; Yin, L. C.; Tang, X. N.; Yang, H. C.; Yan, W. S.; Song, L.; Cheng, H. M.; Li, F. Kinetically enhanced electrochemical redox of polysulfides on polymeric carbon nitrides for improved lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2016, 8, 25193–25201.
DOI Google Scholar
29

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
30

Zhao, M. Q.; Liu, X. F.; Zhang, Q.; Tian, G. L.; Huang, J. Q.; Zhu, W. C.; Wei, F. Graphene/single-walled carbon nanotube hybrids: One-step catalytic growth and applications for high-rate Li-S batteries. ACS Nano 2012, 6, 10759–10769.
DOI Google Scholar
31

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
32

Su, L. W.; Zhou, Z.; Shen, P. W. Ni/C hierarchical nanostructures with Ni nanoparticles highly dispersed in N-containing carbon nanosheets: Origin of Li storage capacity. J. Phys. Chem. C 2012, 116, 23974–23980.
DOI Google Scholar
33

Yoo, J.; Cho, S. J.; Jung, G. Y.; Kim, S. H.; Choi, K. H.; Kim, J. H.; Lee, C. K.; Kwak, S. K.; Lee, S. Y. COF-net on CNT-net as a molecularly designed, hierarchical porous chemical trap for polysulfides in lithium-sulfur batteries. Nano Lett. 2016, 16, 3292–3300.
DOI Google Scholar
34

Xu, J. Q.; Zhou, K.; Chen, F.; Chen, W.; Wei, X. F.; Liu, X. W.; Liu, J. H. Natural integrated carbon architecture for rechargeable lithium–sulfur batteries. ACS Sustain. Chem. Eng. 2016, 4, 666–670.
DOI Google Scholar
35

Yang, J. Q.; Zhou, X. L.; Wu, D. H.; Zhao, X. D.; Zhou, Z. S-doped N-rich carbon nanosheets with expanded interlayer distance as anode materials for sodium-ion batteries. Adv. Mater. 2017, 29, 1604108.
DOI Google Scholar
36

Yuan, X. Q.; Wu, L. S.; He, X. L.; Zeinu, K.; Huang, L.; Zhu, X. L.; Hou, H. J.; Liu, B. C.; Hu, J. P.; Yang, J. K. Separator modified with N, S co-doped mesoporous carbon using egg shell as template for high performance lithium-sulfur batteries. Chem. Eng. J. 2017, 320, 178–188.
DOI Google Scholar
37

Zhang, W. L.; Xu, C.; Ma, C. Q.; Li, G. X.; Wang, Y. Z.; Zhang, K. Y.; Li, F.; Liu, C.; Cheng, H. M.; Du, Y. W. et al. Nitrogen-superdoped 3D graphene networks for high-performance supercapacitors. Adv. Mater. 2017, 29, 1701677.
DOI Google Scholar
38

Anantharaj, S.; Karthick, K.; Venkatesh, M.; Simha, T. V. S. V.; Salunke, A. S.; Ma, L.; Liang, H.; Kundu, S. Enhancing electrocatalytic total water splitting at few layer Pt-NiFe layered double hydroxide interfaces. Nano Energy 2017, 39, 30–43.
DOI Google Scholar
39

Chen, G. P.; Song, X.; Wang, S. Q.; Wang, Y.; Gao, T.; Ding, L. X.; Wang, H. H. A multifunctional separator modified with cobalt and nitrogen co-doped porous carbon nanofibers for Li-S batteries. J. Membr. Sci. 2018, 548, 247–253.
DOI Google Scholar
40

Song, X.; Wang, S. Q.; Chen, G. P.; Gao, T.; Bao, Y.; Ding, L. X.; Wang, H. H. Fe-N-doped carbon nanofiber and graphene modified separator for lithium-sulfur batteries. Chem. Eng. J. 2018, 333, 564–571.
DOI Google Scholar
41

Zeng, P.; Huang, L. W.; Zhang, X. L.; Zhang, R. X.; Wu, L.; Chen, Y. G. Long-life and high-areal-capacity lithium-sulfur batteries realized by a honeycomb-like N, P dual-doped carbon modified separator. Chem. Eng. J. 2018, 349, 327–337.
DOI Google Scholar
42

Chen, X. X.; Ding, X. Y.; Wang, C. S.; Feng, Z. Y.; Xu, L. Q.; Gao, X.; Zhai, Y. J.; Wang, D. B. A multi-shelled CoP nanosphere modified separator for highly efficient Li-S batteries. Nanoscale 2018, 10, 13694–13701.
DOI Google Scholar
43

Ding, H. B.; Zhang, Q. F.; Liu, Z. M.; Wang, J.; Ma, R. F.; Fan, L.; Wang, T.; Zhao, J. G.; Ge, J. M.; Lu, X. L. et al. TiO2 quantum dots decorated multi-walled carbon nanotubes as the multifunctional separator for highly stable lithium sulfur batteries. Electrochim. Acta. 2018, 284, 314–320.
DOI Google Scholar
44

Yang, Y. F.; Zhang, J. P. Highly stable lithium-sulfur batteries based on laponite nanosheet-coated celgard separators. Adv. Energy Mater. 2018, 8, 1801778.
DOI Google Scholar
45

Jiang, K.; Gao, S.; Wang, R. X.; Jiang, M.; Han, J.; Gu, T. T.; Liu, M. Y.; Cheng, S. J.; Wang, K. L. Lithium sulfonate/carboxylate-anchored polyvinyl alcohol separators for lithium sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 18310–18315.
DOI Google Scholar
46

Song, X.; Chen, G. P.; Wang, S. Q.; Huang, Y. P.; Jiang, Z. Y.; Ding, L. X.; Wang, H. H. Self-assembled close-packed MnO2 nanoparticles anchored on a polyethylene separator for lithium-sulfur batteries. ACS Appl. Mater. Interfaces 2018, 10, 26274–26282.
DOI Google Scholar
47

Wu, F.; Zhao, S. Y.; Chen, L.; Lu, Y.; Su, Y. F.; Jia, Y. N.; Bao, L. Y.; Wang, J.; Chen, S.; Chen, R. J. Metal-organic frameworks composites threaded on the CNT knitted separator for suppressing the shuttle effect of lithium sulfur batteries. Energy Storage Mater. 2018, 14, 383–391.
DOI Google Scholar
48

Zhai, P. Y.; Peng, H. J.; Cheng, X. B.; Zhu, L.; Huang, J. Q.; Zhu, W. C.; Zhang, Q. Scaled-up fabrication of porous-graphene-modified separators for high-capacity lithium–sulfur batteries. Energy Storage Mater. 2017, 7, 56–63.
DOI Google Scholar
49

Li, H. P.; Sun, L. C.; Zhang, Y. G.; Tan, T. Z.; Wang, G. K.; Bakenov, Z. Enhanced cycle performance of Li/S battery with the reduced graphene oxide/activated carbon functional interlayer. J. Energy Chem. 2017, 26, 1276–1281.
DOI Google Scholar
50

Huang, J. Q.; Zhuang, T. Z.; Zhang, Q.; Peng, H. J.; Chen, C. M.; Wei, F. Permselective graphene oxide membrane for highly stable and anti-self- discharge lithium-sulfur batteries. ACS Nano 2015, 9, 3002–3011.
DOI Google Scholar
51

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
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Publication history
Copyright
Acknowledgements

Publication history

Received: 12 November 2018
Revised: 21 December 2018
Accepted: 11 January 2019
Published: 25 January 2019
Issue date: April 2019

Copyright

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

Acknowledgements

Acknowledgements

This work was supported by funding from the Postdoctoral Science Foundation of China (No. 2017M611171), the National Natural Science Foundation of China (NSFC) (Nos. 21571170, 21501168, and 51702236), Tianjin Municipal Science and Technology Commission (No. 17JCZDJC38000).

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