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Nano Research 2017, 10(2): 426-436 https://doi.org/10.1007/s12274-016-1303-7
Research Article | Issue | Published: 07 November 2016

Boron-doped microporous nano carbon as cathode material for high-performance Li-S batteries

Show Author's Information Feng Wu1,2,§,  Ji Qian1,§,  Weiping Wu3,  Yusheng Ye1,  Zhiguo Sun1,  Bin Xu4,  Xiaoguang Yang5,  Yuhong Xu6,  Jiatao Zhang7,  Renjie Chen1,2( )
Beijing Key Laboratory of Environmental Science and EngineeringSchool of Material Science and EngineeringBeijing Institute of TechnologyBeijing100081China
Collaborative Innovation Center of Electric Vehicles in BeijingBeijing100081China
School of Computer Science, Mathematics and EngineeringCity, University of London, Northampton Square, LondonEC1V 0HBUK
State Key Laboratory of Chemical Resource EngineeringBeijing Key Laboratory of Electrochemical Process and Technology for MaterialsBeijing University of Chemical TechnologyBeijing100029China
Research and Advanced EngineeringFord Motor CompanyDearbornMI48121USA
Electrified Powertrain EngineeringFord Motor Research and Engineering (Nanjing) Co.Ltd.Nanjing211100China
Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green ApplicationsSchool of Material Science and EngineeringBeijing Institute of TechnologyBeijing100081China

§ These authors contributed equally to this work.

Keywords:
Li-S batteries, boron-doping, microporous carbon, binding energy
Cite this article:
Wu F, Qian J, Wu W, et al. Boron-doped microporous nano carbon as cathode material for high-performance Li-S batteries. Nano Research, 2017, 10(2): 426-436. https://doi.org/10.1007/s12274-016-1303-7
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Abstract Full text Electronic supplementary material About this article

In this study, a boron-doped microporous carbon (BMC)/sulfur nanocomposite is synthesized and applied as a novel cathode material for advanced Li-S batteries. The cell with this cathode exhibits an ultrahigh cycling stability and rate capability. After activation, a capacity of 749.5 mAh/g was obtained on the 54th cycle at a discharge current of 3.2 A/g. After 500 cycles, capacity of 561.8 mAh/g remained (74.96% retention), with only a very small average capacity decay of 0.056%. The excellent reversibility and stability of the novel sulfur cathode can be attributed to the ability of the boron-doped microporous carbon host to both physically confine polysulfides and chemically bind these species on the host surface. Theoretical calculations confirm that boron-doped carbon is capable of significantly stronger interactions with the polysulfide species than undoped carbon, most likely as a result of the lower electronegativity of boron. We believe that this doping strategy can be extended to other metal-air batteries and fuel cells, and that it has promising potential for many different applications.


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Electronic supplementary material
About this article

Boron-doped microporous nano carbon as cathode material for high-performance Li-S batteries

Show Author's information Feng Wu1,2,§, Ji Qian1,§, Weiping Wu3, Yusheng Ye1, Zhiguo Sun1, Bin Xu4, Xiaoguang Yang5, Yuhong Xu6, Jiatao Zhang7, Renjie Chen1,2( )
Beijing Key Laboratory of Environmental Science and EngineeringSchool of Material Science and EngineeringBeijing Institute of TechnologyBeijing100081China
Collaborative Innovation Center of Electric Vehicles in BeijingBeijing100081China
School of Computer Science, Mathematics and EngineeringCity, University of London, Northampton Square, LondonEC1V 0HBUK
State Key Laboratory of Chemical Resource EngineeringBeijing Key Laboratory of Electrochemical Process and Technology for MaterialsBeijing University of Chemical TechnologyBeijing100029China
Research and Advanced EngineeringFord Motor CompanyDearbornMI48121USA
Electrified Powertrain EngineeringFord Motor Research and Engineering (Nanjing) Co.Ltd.Nanjing211100China
Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green ApplicationsSchool of Material Science and EngineeringBeijing Institute of TechnologyBeijing100081China

§ These authors contributed equally to this work.

Abstract

In this study, a boron-doped microporous carbon (BMC)/sulfur nanocomposite is synthesized and applied as a novel cathode material for advanced Li-S batteries. The cell with this cathode exhibits an ultrahigh cycling stability and rate capability. After activation, a capacity of 749.5 mAh/g was obtained on the 54th cycle at a discharge current of 3.2 A/g. After 500 cycles, capacity of 561.8 mAh/g remained (74.96% retention), with only a very small average capacity decay of 0.056%. The excellent reversibility and stability of the novel sulfur cathode can be attributed to the ability of the boron-doped microporous carbon host to both physically confine polysulfides and chemically bind these species on the host surface. Theoretical calculations confirm that boron-doped carbon is capable of significantly stronger interactions with the polysulfide species than undoped carbon, most likely as a result of the lower electronegativity of boron. We believe that this doping strategy can be extended to other metal-air batteries and fuel cells, and that it has promising potential for many different applications.

Keywords: Li-S batteries, boron-doping, microporous carbon, binding energy

References(33)

1

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

Bruce, P. G.; Freunberger, S. A.; Hardwick, L. J.; Tarascon, J. M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 2012, 11, 19–29.
DOI Google Scholar
3

Manthiram, A.; Fu, Y. Z.; Su, Y. S. Challenges and prospects of lithium–sulfur batteries. Acc. Chem. Res. 2013, 46, 1125–1134.
DOI Google Scholar
4

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
5

Yang, Y.; Zheng, G. Y.; Cui, Y. Nanostructured sulfur cathodes. Chem. Soc. Rev. 2013, 42, 3018–3032.
DOI Google Scholar
6

Liu, M. N.; Ye, F. M.; Li, W. F.; Li, H. F.; Zhang, Y. G. Chemical routes toward long-lasting lithium/sulfur cells. Nano Res. 2016, 9, 94–116.
DOI Google Scholar
7

Zhou, G. M.; Wang, D. -W.; Li, F.; Hou, P. -X.; Yin, L. C.; Liu, C.; Lu, G. Q.; Gentle, I. R.; Cheng, H. -M. A flexible nanostructured sulphur–carbon nanotube cathode with high rate performance for Li-S batteries. Energy Environ. Sci. 2012, 5, 8901–8906.
DOI Google Scholar
8

Sun, L.; Li, M. Y.; Jiang, Y.; Kong, W. B.; Jiang, K. L.; Wang, J. P.; Fan, S. S. Sulfur nanocrystals confined in carbon nanotube network as a binder-free electrode for high-performance lithium sulfur batteries. Nano Lett. 2014, 14, 4044–4049.
DOI Google Scholar
9

Xu, G. Y.; Yuan, J. R.; Tao, X. Y.; Ding, B.; Dou, H.; Yan, X. H.; Xiao, Y.; Zhang, X. G. Absorption mechanism of carbon-nanotube paper-titanium dioxide as a multifunctional barrier material for lithium-sulfur batteries. Nano Res. 2015, 8, 3066–3074.
DOI Google Scholar
10

Wu, F.; Qian, J.; Chen, R. J.; Zhao, T.; Xu, R.; Ye, Y. S.; Li, W. H.; Li, L.; Lu, J.; Amine, K. Sulfur cathode based on layered carbon matrix for high-performance Li–S batteries. Nano Energy 2015, 12, 742–749.
DOI Google Scholar
11

Wang, Z. Y.; Dong, Y. F.; Li, H. J.; Zhao, Z. B.; Wu, H. B.; Hao, C.; Liu, S. H.; Qiu, J. S.; Lou, X. W. Enhancing lithium-sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide. Nat. Commun. 2014, 5, 5002.
DOI Google Scholar
12

Qiu, Y. C.; Li, W. F.; Li, G. Z.; Hou, Y.; Zhou, L. S.; Li, H. F.; Liu, M. N.; Ye, F. M.; Yang, X. W.; Zhang, Y. G. Polyaniline-modified cetyltrimethylammonium bromide- graphene oxide-sulfur nanocomposites with enhanced performance for lithium-sulfur batteries. Nano Res. 2014, 7, 1355–1363.
DOI Google Scholar
13

Sun, H.; Xu, G. L.; Xu, Y. F.; Sun, S. G.; Zhang, X. F.; Qiu, Y. C.; Yang, S. H. A composite material of uniformly dispersed sulfur on reduced graphene oxide: Aqueous one-pot synthesis, characterization and excellent performance as the cathode in rechargeable lithium-sulfur batteries. Nano Res. 2012, 5, 726–738.
DOI Google Scholar
14

Zhang, B.; Qin, X.; Li, G. R.; Gao, X. P. Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres. Energy Environ. Sci. 2010, 3, 1531–1537.
DOI Google Scholar
15

Ding, B.; Yuan, C. Z.; Shen, L. F.; Xu, G. Y.; Nie, P.; Zhang, X. G. Encapsulating sulfur into hierarchically ordered porous carbon as a high-performance cathode for lithium- sulfur batteries. Chem. —Eur. J. 2013, 19, 1013–1019.
DOI Google Scholar
16

Zhang, K.; Zhao, Q.; Tao, Z. L.; Chen, J. Composite of sulfur impregnated in porous hollow carbon spheres as the cathode of Li-S batteries with high performance. Nano Res. 2013, 6, 38–46.
DOI Google Scholar
17

Ahn, W.; Kim, K. -B.; Jung, K. -N.; Shin, K. -H.; Jin, C. -S. Synthesis and electrochemical properties of a sulfur-multi walled carbon nanotubes composite as a cathode material for lithium sulfur batteries. J. Power Sources 2012, 202, 394–399.
DOI Google Scholar
18

Chen, J. J.; Zhang, Q.; Shi, Y. N.; Qin, L. L.; Cao, Y.; Zheng, M. S.; Dong, Q. F. A hierarchical architecture S/MWCNT nanomicrosphere with large pores for lithium sulfur batteries. Phys. Chem. Chem. Phys. 2012, 14, 5376– 5382.
DOI Google Scholar
19

Zhao, Y.; Yang, L. J.; Chen, S.; Wang, X. Z.; Ma, Y. W.; Wu, Q.; Jiang, Y. F.; Qian, W. J.; Hu, Z. Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes? J. Am. Chem. Soc. 2013, 135, 1201–1204.
DOI Google Scholar
20

Wang, S. Y.; Zhang, L. P.; Xia, Z. H.; Roy, A.; Chang, D. W.; Baek, J. B.; Dai, L. M. BCN graphene as efficient metal- free electrocatalyst for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2012, 51, 4209–4212.
DOI Google Scholar
21

Kruk, M.; Jaroniec, M. Gas adsorption characterization of ordered organic-inorganic nanocomposite materials. Chem. Mater. 2001, 13, 3169–3183.
DOI Google Scholar
22

Wu, F.; Qian, J.; Chen, R.; Lu, J.; Li, L.; Wu, H.; Chen, J.; Zhao, T.; Ye, Y.; Amine, K. An effective approach to protect lithium anode and improve cycle performance for Li-S batteries. ACS Appl. Mater. Interfaces 2014, 6, 15542–15549.
DOI Google Scholar
23

Chen, R. J.; Zhao, T.; Lu, J.; Wu, F.; Li, L.; Chen, J. Z.; Tan, G. Q.; Ye, Y. S.; Amine, K. Graphene-based three- dimensional hierarchical sandwich-type architecture for high-performance Li/S batteries. Nano Lett. 2013, 13, 4642–4649.
DOI Google Scholar
24

Ferrari, A. C.; Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 2000, 61, 14095–14107.
DOI Google Scholar
25

Katagiri, G.; Ishida, H.; Ishitani, A. Raman spectra of graphite edge planes. Carbon 1988, 26, 565–571.
DOI Google Scholar
26

Ward, A. T. Raman spectroscopy of sulfur, sulfur-selenium, and sulfur-arsenic mixtures. J. Phys. Chem. 1968, 72, 4133–4139.
DOI Google Scholar
27

Moulder, J. F.; Chastain, J.; King, R. C. Handbook of X-ray Photoelectron Spectroscopy; Perkin-Elmer Corporation: Eden Prairie, MN, USA, 1992.
28

Panchakarla, L. S.; Subrahmanyam, K. S.; Saha, S. K.; Govindaraj, A.; Krishnamurthy, H. R.; Waghmare, U. V.; Rao, C. N. R. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 2009, 21, 4726–4730.
Google Scholar
29

Ennaceur, M. M.; Terreault, B. XPS study of the process of oxygen gettering by thin films of PACVD boron. J. Nucl. Mater. 2000, 280, 33–38.
DOI Google Scholar
30

Akridge, J. R.; Mikhaylik, Y. V.; White, N. Li/S fundamental chemistry and application to high-performance rechargeable batteries. Solid State Ionics 2004, 175, 243–245.
DOI Google Scholar
31

Zhang, S. S. Role of LiNO3 in rechargeable lithium/sulfur battery. Electrochim. Acta 2012, 70, 344–348.
DOI Google Scholar
32

Koh, J. Y.; Park, M. S.; Kim, E. H.; Kim, T. J.; Kim, S.; Kim, K. J.; Kim, Y. J.; Jung, Y. Electrochemical reduction mechanism of sulfur particles electrically isolated from carbon cathodes of lithium-sulfur cells. J. Electrochem. Soc. 2014, 161, A2117–A2120.
DOI Google Scholar
33

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
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Publication history
Copyright
Acknowledgements

Publication history

Received: 30 July 2016
Revised: 15 September 2016
Accepted: 27 September 2016
Published: 07 November 2016
Issue date: February 2017

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016

Acknowledgements

Acknowledgements

This work was supported by the National Key Research and Development Program "New Energy Project for Electric Vehicle" (No. 2016YFB0100204), the National Natural Science Foundation of China (No. 21373028), Major achievements Transformation Project for Central University in Beijing, Beijing Science and Technology Project (No. D151100003015001) and the Ford University Research Program (URP) project. W. P. W. acknowledges support from George Daniels Educational Trust.

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