Metallic and polar Co9S8 inlaid carbon hollow nanopolyhedra as efficient polysulfide mediator for lithium−sulfur batteries

doi:10.1016/j.nanoen.2017.05.064

Nano Energy

Volume 38, August 2017, Pages 239-248

https://doi.org/10.1016/j.nanoen.2017.05.064 Get rights and content

Highlights

•
Metallic and polar Co₉S₈ nanocrystals inlaid carbon (Co₉S₈/C) hollow nanopolyhedra as sulfur host have been prepared.
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The Co₉S₈/C hollow nanopolyhedra can ensure the loading mass and buffer the volume expansion of sulfur during cycling.
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The Co₉S₈/C shell offers synergetic spatial confinement and chemical binding to prevent the shutting effect.

Abstract

Lithium−sulfur (Li−S) batteries are promising to replace current commercial Li−ion batteries due to the high energy density. Despite this, the poor cyclic stability induced by the shuttle effect of electrolyte-soluble intermediate polysulfides is one of the great obstacles for the application of Li−S batteries. To overcome this issue, here we report a self-template synthesis of metallic and polar Co₉S₈ nanocrystals inlaid carbon (Co₉S₈/C) hollow nanopolyhedra as an efficient sulfur host material. The Co₉S₈/C hollow nanopolyhedra with large inner space can ensure the loading mass of sulfur and buffer the volume expansion of Li₂S_x species during cycling; while the metallic and polar Co₉S₈/C shell offers synergetic spatial confinement and chemical binding to immobilize polysulfides and prevent the shutting effect. The Co₉S₈/C-S composite cathode exhibits high capacity and long cycle life with a low capacity decay of 0.041% per cycle over 1000 cycles at 2.0 C. When the areal sulfur content is as high as 3.0 mg cm^–2, the Co₉S₈/C-S cathode still maintains high cycling stability.

Graphical abstract

Section snippets

Results and discussion

The synthetic process of Co₉S₈/C nanopolyhedra and Co₉S₈/C-S composite is schematically shown in Fig. 1a. Firstly, monodispersed zeolitic imidazole framework-67 (ZIF-67) precursor nanopolyhedra were prepared via a reported precipitation method [46]. After subsequent sulfidation by thioacetamide (TAA) and annealing at 350 °C in N₂ atmosphere, Co₉S₈/C hollow nanopolyhedra were successfully obtained. Finally, sulfur was filled in Co₉S₈/C hollow nanopolyhedra via a melt-diffusion process to obtain Co

Conclusions

In summary, we have designed and synthesized a novel hollow Co₉S₈/C nanopolyhedra as an efficient sulfur host for Li-S batteries. This nanostructure can efficiently prevent polysulfide shuttling by the combined chemical binding of polar Co₉S₈ nanocrystals and the spatial entrapment of carbon shells. Meanwhile, the strong interaction of Co₉S₈ with Li₂S_x species also can improve the redox reaction kinetics. In result, the Co₉S₈/C-S electrode exhibited a high specific capacity and a long cycling

Preparation of ZIF-67 precursor nanopolyhedra

Typically, 3.2 mmol of Co(NO₃)₂·6H₂O and 9.6 mmol of 2-methylimidazole were respectively dissolved in 40 mL methanol and then mixed together rapidly under vigorously stirring. The mixture was incubated at room temperature for 24 h. The precipitate was collected by repeatedly washing with ethanol for 3 times and then dried overnight.

Synthesis of Co₉S₈/C hollow nanopolyhedra

Firstly, 60 mg of ZIF-67 precursor nanopolyhedra was dispersed into 30 mL ethanol. Then, 90 mg of thioacetamide was added into the above solution and continuously stirred

Acknowledgements

This work was supported by National Materials Genome Project (2016YFB0700600), National 973 Basic Research Program (2015CB659300), National Natural Science Foundation of China (21403105, 21573108), China Postdoctoral Science Foundation (2015M580413, 2015M581769), Natural Science Foundation for Young Scholars of Jiangsu Province (BK20150583, BK20160647), Fundamental Research Funds for the Central Universities and a project funded by the Priority Academic Program Development (PAPD) of Jiangsu

Dr. Tao Chen received his Ph.D. degree in Chemical Engineering and Technology under supervision of Prof. Jiajun Fu from Nanjing University of Science and Technology in June 2015. He is currently a postdoctoral researcher in the group of Prof. Zhong Jin and Prof. Jie Liu at Nanjing University. His current research focuses on the design and synthesis of nanostructured electrode materials for rechargeable batteries.

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Lianbo Ma received his M.S. degree in Applied Chemistry from Jiangsu University, PR China (2015). He is now pursing his Ph.D. degree under the supervision of Prof. Zhong Jin and Jie Liu in School of Chemistry and Chemical Engineering, Nanjing University, P.R. China. His main interest is the design and fabrication nanomaterials for photoelectric conversion.

Baorui Cheng entered School of Chemistry and Chemical Engineering, Nanjing University in 2013. He majors in chemistry and currently works as an assistant of Dr. Tao Chen in the group of Prof. Zhong Jin. His current research focuses on preparation of MOFs-based functional materials.

Renpeng Chen has graduated from the Northeastern University (China) since 2014. Now, he is pursuing his M.S. degree under the guidance of Prof. Zhong Jin in School of Chemistry and Chemical Engineering at Nanjing University. His research interest is focused on the synthesis of alloy materials for lithium-ion batteries.

Yi Hu received his B.S. degree in Chemistry from Sichuan University in 2014. He is now pursuing his Ph.D. degree under the supervision of Prof. Zhong Jin in School of Chemistry and Chemical Engineering at Nanjing University. His research interests reside in two-dimensional nanomaterials for electrochemical energy storage and photoelectric conversion.

Guoyin Zhu obtained his M.S. degree from Nanjing University of Posts & Telecommunications in 2014. Currently, he is pursuing his Ph.D. degree under the supervision of Prof. Zhong Jin and Jie Liu at Nanjing University. His research is mainly focused on the synthesis of carbonaceous nanomaterials, and their application for energy conversion and storage devices.

Yanrong Wang received her master degree in physical chemistry under the supervision of Professor Yong Hu in College of Chemistry and life sciences at Zhejiang Normal University in 2015. She is now pursuing her Ph.D. degree under the supervision of Prof. Zhong Jin and Jie Liu in School of Chemistry and Chemical Engineering at Nanjing University. Her current research interest is the design of new type of battery.

Dr. Jia Liang received his Ph.D. in the Key Laboratory for Physics and Chemistry of Nanodevices from Peking University in 2015, under the guidance of Prof. Gengmin Zhang. He joined Prof. Jun Lou’s research group in Rice University as a visiting student in 2014. He is currently an assistant researcher in the group directed by Prof. Zhong Jin and Jie Liu at Nanjing University. His main research interest is synthesis of energy nanomaterials and their applications in solar cells, catalyses, and flow batteries.

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CommunicationMetallic and polar Co9S8 inlaid carbon hollow nanopolyhedra as efficient polysulfide mediator for lithium−sulfur batteries

Highlights

Abstract

Graphical abstract

Section snippets

Results and discussion

Conclusions

Preparation of ZIF-67 precursor nanopolyhedra

Synthesis of Co9S8/C hollow nanopolyhedra

Acknowledgements

Energy Storage Mater.

Catal. Today

Chem. Soc. Rev.

Nat. Rev. Mater.

Chem. Soc. Rev.

Nat. Mater.

Adv. Mater.

Adv. Energy Mater.

Angew. Chem. Int. Ed.

Chem. Rev.

Adv. Mater.

Phys. Chem. Chem. Phys.

Adv. Energy Mater.

Nat. Commun.

Adv. Mater.

Nat. Commun.

Nat. Mater.

Adv. Mater.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

ACS Nano

Nat. Commun.

Nat. Commun.

Nano Lett.

Energy Environ. Sci.

Angew. Chem. Int. Ed.

Angew. Chem. Int. Ed.

Adv. Energy Mater.

Adv. Funct. Mater.

Communication
Metallic and polar Co₉S₈ inlaid carbon hollow nanopolyhedra as efficient polysulfide mediator for lithium−sulfur batteries

Synthesis of Co₉S₈/C hollow nanopolyhedra