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Research Article

Bonding VSe2 ultrafine nanocrystals on graphene toward advanced lithium-sulfur batteries

Wenzhi Tian1, Baojuan Xi1, Yu Gu1, Qiang Fu1, Zhenyu Feng1, Jinkui Feng2, Shenglin Xiong1( )
Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, and State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China
Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, China
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Abstract

Lithium-sulfur batteries have been attracting considerable research attention due to their high energy densities and low costs. However, one of their main challenges is the undesired shuttling of polysulfides, causing rapid capacity degradation. Herein, we report the first example of sulfiphilic VSe2 ultrafine nanocrystals immobilized on nitrogen-doped graphene to modify the battery separator for alleviating the shuttling problem. VSe2 nanocrystals provide numerous active sites for chemisorption of polysulfides as well as benefit the nucleation and growth of Li2S. Furthermore, the kinetic reactions are accelerated which is confirmed by higher exchange current density and higher lithium ion diffusion coefficient. And the first-principles calculations further show that the exposed sulfiphilic planes of VSe2 boost the redox of Li2S. When used as separators within the lithium sulfur batteries, the cell indicates greatly enhanced electrochemical performances with excellent long cycling stability and exceptional rate capability up to 8 C. Moreover, it delivers a higher areal capacity of 4.04 mAh·cm-2 as well as superior cycling stability with sulfur areal loading up to 6.1 mg·cm-2. The present strategy can encourage us in engineering novel multifunctional separators for energy-storage devices.

Keywords

sulfiphilic VSe2lithium-sulfur batteriesnucleation and growth of Li2Spolysulfide electrocatalysisshuttle effect

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References

[1]
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.
Crossref Google Scholar
[2]
Zhang, G.; Zhang, Z. W.; Peng, H. J.; Huang, J. Q.; Zhang, Q. A toolbox for lithium-sulfur battery research: Methods and protocols. Small Methods 2017, 1, 1700134.
Crossref Google Scholar
[3]
Hao, G. P.; Tang, C.; Zhang, E.; Zhai, P. Y.; Yin, J.; Zhu, W. C.; Zhang, Q.; Kaskel, S. Thermal exfoliation of layered metal-organic frameworks into ultrahydrophilic graphene stacks and their applications in Li-S batteries. Adv. Mater. 2017, 29, 1702829.
Crossref Google Scholar
[4]
Pan, H. L.; Chen, J. Z.; Cao, R. G.; Murugesan, V.; Rajput, N. N.; Han, K. S.; Persson, K.; Estevez, L.; Engelhard, M. H.; Zhang, J. G. et al. Non-encapsulation approach for high-performance Li-S batteries through controlled nucleation and growth. Nat. Energy 2017, 2, 813-820.
Crossref Google Scholar
[5]
Liu, D. H.; Zhang, C.; Zhou, G. M.; Lv, W.; Ling, G. W.; Zhi, L. J.; Yang, Q. H. Catalytic effects in lithium-sulfur batteries: Promoted sulfur transformation and reduced shuttle effect. Adv. Sci. 2018, 5, 1700270.
Crossref Google Scholar
[6]
Li, G. R.; Lei, W.; Luo, D.; Deng, Y. P.; Wang, D.; Chen. Z. W. 3D porous carbon sheets with multidirectional ion pathways for fast and durable lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1702381.
Crossref Google Scholar
[7]
Zhou, Y. Y.; Hu, G. J.; Zhang, W. K., Li, Q. W.; Zhao, Z. G.; Zhao, Y.; Li, F.; Geng, F. X. Cationic two-dimensional sheets for an ultralight electrostatic polysulfide trap toward high-performance lithium-sulfur batteries. Energy Storage Mater. 2017, 9, 39-46.
Crossref Google Scholar
[8]
Liu, W.; Jiang, J. B.; Yang, K. R.; Mi, Y. Y.; Kumaravadivel, P.; Zhong, Y. R.; Fan, Q.; Weng, Z.; Wu, Z. S.; Cha, J. J. et al. Ultrathin dendrimer-graphene oxide composite film for stable cycling lithium- sulfur batteries. Proc. Natl. Acad. Sci. USA 2017, 114, 3578-3583.
Crossref Google Scholar
[9]
Mikhaylik, Y. V.; Akridge, J. R. Polysulfide shuttle study in the Li/S battery system. J. Electrochem. Soc. 2004, 151, A1969-A1976.
Crossref Google Scholar
[10]
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.
Crossref Google Scholar
[11]
Zhang, J. H.; Huang, M.; Xi, B. J.; Mi, K.; Yuan, A. H.; Xiong, S. L. Systematic study of effect on enhancing specific capacity and electrochemical behaviors of lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1701330.
Crossref Google Scholar
[12]
Lu, H. Y.; Zhang, C.; Zhang, Y. F.; Huang, Y. P.; Liu M. K.; Liu, T. X. Simultaneous growth of carbon nanotubes on inner/outer surfaces of porous polyhedra: Advanced sulfur hosts for lithium-sulfur batteries. Nano Res. 2018, 11, 6155-6166.
Crossref Google Scholar
[13]
Mi, K.; Jiang, Y.; Feng, J. K.; Qian, Y. T.; Xiong, S. L. Hierarchical carbon nanotubes with a thick microporous wall and inner channel as efficient scaffolds for lithium-sulfur batteries. Adv. Funct. Mater. 2016, 26, 1571-1579.
Crossref Google Scholar
[14]
Qie, L.; Manthiram, A. A facile layer-by-layer approach for high-areal- capacity sulfur cathodes. Adv. Mater. 2015, 27, 1694-1700.
Crossref Google Scholar
[15]
Zhang, C. F.; Wu, H. B.; Yuan, C. Z.; Guo, Z. P.; Lou, X. W. Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries. Angew. Chem., Int. Ed. 2012, 51, 9592-9595.
Crossref Google Scholar
[16]
Jayaprakash, N.; Shen, J.; Moganty, S. S.; Corona, A.; Archer, L. A. Porous hollow carbon@sulfur composites for high-power lithium- sulfur batteries. Angew. Chem., Int. Ed. 2011, 50, 5904-5908.
Crossref Google Scholar
[17]
Zheng, G. Y.; Zhang, Q. F.; Cha, J. J.; Yang, Y.; Li, W. Y.; Seh, Z. W.; Cui, Y. Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. Nano Lett. 2013, 13, 1265-1270.
Crossref Google Scholar
[18]
Li, Z.; Zhang, J. T.; Lu, Y.; Lou, X. W. A pyrolyzed polyacrylonitrile/ selenium disulfide composite cathode with remarkable lithium and sodium storage performances. Sci. Adv. 2018, 4, eaat1687.
Crossref Google Scholar
[19]
Fu, Y. Z.; Manthiram, A. Orthorhombic bipyramidal sulfur coated with polypyrrole nanolayers as a cathode material for lithium-sulfur batteries. J. Phys. Chem. C 2012, 116, 8910-8915.
Crossref Google Scholar
[20]
Zhou, W. D.; Yu, Y. C.; Chen, H.; DiSalvo, F. J.; Abruña, H. D. Yolk-shell structure of polyaniline-coated sulfur for lithium-sulfur batteries. J. Am. Chem. Soc. 2013, 135, 16736-16743.
Crossref Google Scholar
[21]
Li, Z.; Zhang, J. T.; Lou, X. W. Hollow carbon nanofibers filled with MnO2 nanosheets as efficient sulfur hosts for lithium-sulfur batteries. Angew. Chem., Int. Ed. 2015, 54, 12886-12890.
Crossref Google Scholar
[22]
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.
Crossref Google Scholar
[23]
Li, Z.; Guan, B. Y.; Zhang, J. T.; Lou, X. W. A compact nanoconfined sulfur cathode for high-performance lithium-sulfur batteries. Joule 2017, 1, 576-587.
Crossref Google Scholar
[24]
Lin, C.; Qu. L. B.; Li, J. T.; Cai, Z. Y.; Liu, H. Y.; He, P.; Xu, X.; Mai, L. Q. Porous nitrogen-doped carbon/MnO coaxial nanotubes as an efficient sulfur host for lithium sulfur batteries. Nano Res. 2019, 12, 205-210.
Crossref Google Scholar
[25]
Sun, Q.; Xi, B. J.; Li, J. Y.; Mao, H. Z.; Ma, X. J.; Liang, J. W.; Feng, J. K.; Xiong, S. L. Nitrogen-doped graphene-supported mixed transition-metal oxide porous particles to confine polysulfides for lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1800595.
Crossref Google Scholar
[26]
Chen, L.; Yang, W. W.; Liu, J. G.; Zhou Y. Decorating CoSe2 hollow nanospheres on reduced graphene oxide as advanced sulfur host material for performance enhanced lithium-sulfur batteries. Nano Res. 2019, 12, 2743-2748.
Crossref Google Scholar
[27]
Yuan, Z.; Peng, H. J.; Hou, T. Z.; Huang, J. Q.; Chen, C. M.; Wang, D. W.; Cheng, X. B.; Wei, F.; Zhang, Q. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett. 2016, 16, 519-527.
Crossref Google Scholar
[28]
Ye, C.; Zhang, L.; Guo, C. X.; Li, D. D.; Vasileff, A.; Wang, H. H.; Qiao, S. Z. A 3D hybrid of chemically coupled nickel sulfide and hollow carbon spheres for high performance lithium-sulfur batteries. Adv. Funct. Mater. 2017, 27, 1702524.
Crossref Google Scholar
[29]
Peng, H. J.; Zhang, G.; Chen, X.; Zhang, Z. W.; Xu, W. T.; Huang, J. Q.; Zhang, Q. Enhanced electrochemical kinetics on conductive polar mediators for lithium-sulfur batteries. Angew. Chem., Int. Ed. 2016, 55, 12990-12995.
Crossref Google Scholar
[30]
Zhou, T. H.; Zhao, Y.; Zhou, G. M.; Lv, W.; Sun, P. J.; Kang, F. Y.; Li, B. H.; Yang, Q. H. An in-plane heterostructure of graphene and titanium carbide for efficient polysulfide confinement. Nano Energy 2017, 39, 291-296.
Crossref Google Scholar
[31]
Zhong, Y. R.; Yin, L. C.; He, P.; Liu, W.; Wu, Z. S.; Wang, H. L. Surface chemistry in cobalt phosphide-stabilized lithium-sulfur batteries. J. Am. Chem. Soc. 2018, 140, 1455-1459.
Crossref Google Scholar
[32]
Zhang, J. T.; Hu, H.; Li, Z.; Lou, X. W. Double-shelled nanocages with cobalt hydroxide inner shell and layered double hydroxides outer shell as high-efficiency polysulfide mediator for lithium-sulfur batteries. Angew. Chem., Int. Ed. 2016, 55, 3982-3986.
Crossref Google Scholar
[33]
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.
Crossref Google Scholar
[34]
Zhou, J. W.; Li, R.; Fan, X. X.; Chen, Y. F.; Han, R. D.; Li, W.; Zheng, J.; Wang, B.; Li, X. G. Rational design of a metal-organic framework host for sulfur storage in fast, long-cycle Li-S batteries. Energy Environ. Sci. 2014, 7, 2715-2724.
Crossref Google Scholar
[35]
Liu, J.; Qian, T.; Xu, N.; Wang, M. F.; Zhou, J. Q.; Shen, X. W.; Yan, C. L. Dendrite-free and ultra-high energy lithium sulfur battery enabled by dimethyl polysulfide intermediates. Energy Storage Mater. 2020, 24, 265-271.
Crossref Google Scholar
[36]
Chen, W.; Qian, T.; Xiong, J.; Xu, N.; Liu, J.; Zhou, J. Q.; Shen, X.; Yang, T. Z.; Chen, Y.; Yan, C. L. A new type of multifunctional polar binder: Toward practical application of high energy lithium sulfur batteries. Adv. Mater. 2017, 29, 1605160.
Crossref Google Scholar
[37]
Yuan, H.; Huang, J. Q.; Peng, H. J.; Titirici, M. M.; Xiang, R.; Chen, R. J.; Liu, Q. B.; Zhang, Q. A review of functional binders in lithium-sulfur batteries. Adv. Energy Mater. 2018, 8, 1802107.
Crossref Google Scholar
[38]
Niu, C. Q.; Liu, J.; Qian, T.; Shen, X. W.; Zhou, J. Q.; Yan, C. L. Single lithium-ion channel polymer binder for stabilizing sulfur cathodes. Natl. Sci. Rev. 2020, 7, 315-323.
Crossref Google Scholar
[39]
Zhuang, T. Z.; Huang, J. Q.; Peng, H. J.; He, L. Y.; Cheng, X. B.; Chen, C. M.; Zhang, Q. Rational integration of polypropylene/ graphene oxide/nafion as ternary-layered separator to retard the shuttle of polysulfides for lithium-sulfur batteries. Small 2016, 12, 381-389.
Crossref Google Scholar
[40]
Su, Y. S.; Manthiram, A. Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer. Nat. Commun. 2012, 3, 1166.
Crossref Google Scholar
[41]
Chung, S. H.; Han, P.; Singhal, R.; Kalra, V.; Manthiram, A. Electrochemically stable rechargeable lithium-sulfur batteries with a microporous carbon nanofiber filter for polysulfide. Adv. Energy Mater. 2015, 5, 1500738.
Crossref Google Scholar
[42]
Yao, H. B.; Yan, K.; Li, W. Y.; Zheng, G. Y.; Kong, D. S.; Seh, Z. W.; Narasimhan, V. K.; Liang, Z.; Cui, Y. Improved lithium-sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode-separator interface. Energy Environ. Sci. 2014, 7, 3381-3390.
Crossref Google Scholar
[43]
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.
Crossref Google Scholar
[44]
Hu, Z.; Liu, Q. N.; Chou, S. L.; Dou, S. X. Advances and challenges in metal sulfides/selenides for next-generation rechargeable sodium-ion batteries. Adv. Mater. 2017, 29, 1700606.
Crossref Google Scholar
[45]
Zhu, P.; Zhu, J. D.; Zang, J.; Chen, C.; Lu, Y.; Jiang, M. J.; Yan, C. Y.; Dirican, M.; Selvan, R. K.; Zhang, X. W. A novel bi-functional double-layer rGO-PVDF/PVDF composite nanofiber membrane separator with enhanced thermal stability and effective polysulfide inhibition for high-performance lithium-sulfur batteries. J. Mater. Chem. A 2017, 5, 15096-15104.
Crossref Google Scholar
[46]
Huang, J. Q.; Zhang, Q.; Peng, H. J.; Liu, X. Y.; Qian, W. Z.; Wei, F. Ionic shield for polysulfides towards highly-stable lithium-sulfur batteries. Energy Environ. Sci. 2014, 7, 347-353.
Crossref Google Scholar
[47]
Kong, Y. W.; an, L.; Luo, Y.; Wang, D.; Jiang, K.; Li, Q.; Fan, S.; Wang, J. Ultrathin MnO2/graphene oxide/carbon nanotube interlayer as efficient polysulfide-trapping shield for high-performance Li-S batteries. Adv. Funct. Mater. 2017, 27, 1606663.
Crossref Google Scholar
[48]
Fan, L. L.; Li, M.; Li, X. F.; Xiao, W.; Chen, Z. W.; Lu, J. Interlayer material selection for lithium-sulfur batteries. Joule 2019, 3, 361-386.
Crossref Google Scholar
[49]
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.
Crossref Google Scholar
[50]
Li, W.; Hicks-Garner, J.; Wang, J.; Liu, J.; Gross, A. F.; Sherman, E.; Graetz, J.; Vajo, J. J.; Liu, P. V2O5 polysulfide anion barrier for long-lived Li-S batteries. Chem. Mater. 2014, 26, 3403-3410.
Crossref Google Scholar
[51]
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.
Crossref Google Scholar
[52]
Zhang, Z. P.; Niu, J. J.; Yang, P. F.; Gong, Y.; Ji, Q. Q.; Shi, J. P.; Fang, Q. Y.; Jiang, S. L.; Li, H.; Zhou, X. B. et al. Van der waals epitaxial growth of 2D metallic vanadium diselenide single crystals and their extra-high electrical conductivity. Adv. Mater. 2017, 29, 1702359.
Crossref Google Scholar
[53]
Marcano, D. C.; Kosynkin, D. V.; Berlin, J. M.; Sinitskii, A.; Sun, Z. Z.; Slesarev, A.; Alemany, L. B.; Lu, W.; Tour, J. M. Improved synthesis of graphene oxide. ACS Nano 2010, 4, 4806-4814.
Crossref Google Scholar
[54]
Ghazi, Z. A.; He, X.; Khattak, A. M.; Khan, N. A.; Liang, B.; Iqbal, Z.; 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.
Crossref Google Scholar
[55]
Kong, L.; Chen, J. X.; Peng, H. J.; Huang, J. Q.; Zhu, W. C.; Jin, Q.; Li, B. Q.; Zhang, X. T.; Zhang, Q. Current-density dependence of Li2S/Li2S2 growth in lithium-sulfur batteries. Energy Environ. Sci. 2019, 12, 2976-2982.
Crossref Google Scholar
[56]
Kresse, G.; Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1996, 54, 11169-11186.
Crossref Google Scholar
[57]
Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953-17979.
Crossref Google Scholar
[58]
Dion, M.; Rydberg, H.; Schröder, E.; Langreth, D. C.; Lundqvist, B. I. Van der Waals density functional for general geometries. Phys. Rev. Lett. 2004, 92, 246401.
Crossref Google Scholar
[59]
Henkelman, G.; Uberuaga, B. P.; Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 2000, 113, 9901-9904.
Crossref Google Scholar
[60]
Yang, C.; Feng, J. R.; Lv, F.; Zhou, J. H.; Lin, C. F.; Wang, K.; Zhang, Y. L.; Yang, Y.; Wang, W.; Li, J. B. et al. Metallic graphene-like VSe2 ultrathin nanosheets: Superior potassium-ion storage and their working mechanism. Adv. Mater. 2018, 30, 1800036.
Crossref Google Scholar
[61]
Yuan, H.; Peng, H. J.; Li, B. Q.; Xie, J.; Kong, L.; Zhao, M.; Chen, X.; Huang, J. Q.; Zhang, Q. Conductive and catalytic triple-phase interfaces enabling uniform nucleation in high-rate lithium-sulfur batteries. Adv. Energy Mater. 2019, 9, 1802768.
Crossref Google Scholar
[62]
Kong, L.; Chen, X.; Li, B. Q.; Peng, H. J.; Huang, J. Q.; Xie, J.; Zhang, Q. A bifunctional perovskite promoter for polysulfide regulation toward stable lithium-sulfur batteries. Adv. Mater. 2018, 30, 1705219.
Crossref Google Scholar
[63]
Fan, F. Y.; Carter, W. C.; Chiang, Y. M. Mechanism and kinetics of Li2S precipitation in lithium-sulfur batteries. Adv. Mater. 2015, 27, 5203-5209.
Crossref Google Scholar
[64]
Zhou, J. B.; Liu, X. J.; Zhu, L. Q.; Zhou, J.; Guan, Y.; Chen, L.; Niu, S. W.; Cai, J. Y.; Sun, D.; Zhu, Y. C. et al. Deciphering the modulation essence of p bands in Co-based compounds on Li-S chemistry. Joule 2018, 2, 2681-2693.
Crossref Google Scholar
[65]
Shi, H. F.; Lv, W.; Zhang, C.; Wang, D. W.; Ling, G. W.; He, Y. B.; Kang, F. Y.; Yang, Q. H. Functional carbons remedy the shuttling of polysulfides in lithium-sulfur batteries: Confining, trapping, blocking, and breaking up. Adv. Funct. Mater. 2018, 28, 1800508.
Crossref Google Scholar
Nano Research
Volume 13 Issue 10,
October 2020
Pages 2673-2682
DOI: 10.1007/s12274-020-2909-3
Cite this article:
Tian W, Xi B, Gu Y, et al. Bonding VSe2 ultrafine nanocrystals on graphene toward advanced lithium-sulfur batteries. Nano Research, 2020, 13(10): 2673-2682. https://doi.org/10.1007/s12274-020-2909-3
Topics:
CalculationsDoping (additives)GrapheneIon batteriesIon exchangeLithiumLithium compoundsNanocrystalsPolysulfidesSelenium compoundsSulfur compoundsVanadium compounds

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Received: 07 April 2020
Revised: 28 May 2020
Accepted: 30 May 2020
Published: 01 July 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
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