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Nano Research 2020, 13(8): 2289-2298 https://doi.org/10.1007/s12274-020-2848-z
Research Article | Open Access | Issue | Published: 05 August 2020

Phase boundary engineering of metal-organic-framework-derived carbonaceous nickel selenides for sodium-ion batteries

Show Author's Information Shiyao Lu1,4,§,  Hu Wu1,§,  Jingwei Hou2,7,  Limin Liu1,  Jiao Li1,  Chris J. Harris2,  Cheng-Yen Lao2,  Yuzheng Guo5,  Kai Xi2,3( ),  Shujiang Ding1( ),  Guoxin Gao1( ),  Anthony K. Cheetham2,6,  R. Vasant Kumar2
Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, State Key Laboratory of Electrical Insulation and Power Equipment, School of Chemistry, Xi’an Jiaotong University & Shaanxi Quantong Joint Research Institute of New Energy Vehicles Power, Xi’an Jiaotong University, Xi’an 710049, China
Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK
Cambridge Graphene Centre, Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK
Department of Chemistry, City University of Hong Kong, Hong Kong 999077, Hong Kong, China
School of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, China
Materials Research Laboratory, University of California, Santa Barbara, CA 93106, USA
School of Chemical Engineering, University of Queensland, St Lucia, QLD 4072, Australia

§ Shiyao Lu and Hu Wu contributed equally to this work.

Keywords:
sodium ion batteries, carbon nanotube, metal organic frameworks, phase boundary, metal selenides
Topics:
AnodesLattice mismatch Metal ionsMetalsNickel compoundsOrganic frameworks OrganometallicsSelenium compounds
Cite this article:
Lu S, Wu H, Hou J, et al. Phase boundary engineering of metal-organic-framework-derived carbonaceous nickel selenides for sodium-ion batteries. Nano Research, 2020, 13(8): 2289-2298. https://doi.org/10.1007/s12274-020-2848-z
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Abstract Full text Electronic supplementary material About this article

Sodium-ion batteries (SIBs) are promising power sources due to the low cost and abundance of battery-grade sodium resources, while practical SIBs suffer from intrinsically sluggish diffusion kinetics and severe volume changes of electrode materials. Metal-organic framework (MOFs) derived carbonaceous metal compound offer promising applications in electrode materials due to their tailorable composition, nanostructure, chemical and physical properties. Here, we fabricated hierarchical MOF-derived carbonaceous nickel selenides with bi-phase composition for enhanced sodium storage capability. As MOF formation time increases, the pyrolyzed and selenized products gradually transform from a single-phase Ni3Se4 into bi-phase NiSex then single-phase NiSe2, with concomitant morphological evolution from solid spheres into hierarchical urchin-like yolk-shell structures. As SIBs anodes, bi-phase NiSex@C/CNT-10h (10 h of hydrothermal synthesis time) exhibits a high specific capacity of 387.1 mAh/g at 0.1 A/g, long cycling stability of 306.3 mAh/g at a moderately high current density of 1 A/g after 2,000 cycles. Computational simulation further proves the lattice mismatch at the phase boundary facilitates more interstitial space for sodium storage. Our understanding of the phase boundary engineering of transformed MOFs and their morphological evolution is conducive to fabricate novel composites/hybrids for applications in batteries, catalysis, sensors, and environmental remediation.


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Electronic supplementary material
About this article

Phase boundary engineering of metal-organic-framework-derived carbonaceous nickel selenides for sodium-ion batteries

Show Author's information Shiyao Lu1,4,§, Hu Wu1,§, Jingwei Hou2,7, Limin Liu1, Jiao Li1, Chris J. Harris2, Cheng-Yen Lao2, Yuzheng Guo5, Kai Xi2,3( ), Shujiang Ding1( ), Guoxin Gao1( ), Anthony K. Cheetham2,6, R. Vasant Kumar2
Xi'an Key Laboratory of Sustainable Energy Materials Chemistry, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, State Key Laboratory of Electrical Insulation and Power Equipment, School of Chemistry, Xi’an Jiaotong University & Shaanxi Quantong Joint Research Institute of New Energy Vehicles Power, Xi’an Jiaotong University, Xi’an 710049, China
Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS, UK
Cambridge Graphene Centre, Department of Engineering, University of Cambridge, Cambridge CB3 0FA, UK
Department of Chemistry, City University of Hong Kong, Hong Kong 999077, Hong Kong, China
School of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, China
Materials Research Laboratory, University of California, Santa Barbara, CA 93106, USA
School of Chemical Engineering, University of Queensland, St Lucia, QLD 4072, Australia

§ Shiyao Lu and Hu Wu contributed equally to this work.

Abstract

Sodium-ion batteries (SIBs) are promising power sources due to the low cost and abundance of battery-grade sodium resources, while practical SIBs suffer from intrinsically sluggish diffusion kinetics and severe volume changes of electrode materials. Metal-organic framework (MOFs) derived carbonaceous metal compound offer promising applications in electrode materials due to their tailorable composition, nanostructure, chemical and physical properties. Here, we fabricated hierarchical MOF-derived carbonaceous nickel selenides with bi-phase composition for enhanced sodium storage capability. As MOF formation time increases, the pyrolyzed and selenized products gradually transform from a single-phase Ni3Se4 into bi-phase NiSex then single-phase NiSe2, with concomitant morphological evolution from solid spheres into hierarchical urchin-like yolk-shell structures. As SIBs anodes, bi-phase NiSex@C/CNT-10h (10 h of hydrothermal synthesis time) exhibits a high specific capacity of 387.1 mAh/g at 0.1 A/g, long cycling stability of 306.3 mAh/g at a moderately high current density of 1 A/g after 2,000 cycles. Computational simulation further proves the lattice mismatch at the phase boundary facilitates more interstitial space for sodium storage. Our understanding of the phase boundary engineering of transformed MOFs and their morphological evolution is conducive to fabricate novel composites/hybrids for applications in batteries, catalysis, sensors, and environmental remediation.

Keywords: sodium ion batteries, carbon nanotube, metal organic frameworks, phase boundary, metal selenides

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Received: 16 March 2020
Revised: 23 April 2020
Accepted: 30 April 2020
Published: 05 August 2020
Issue date: August 2020

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© The Author(s) 2020

Acknowledgements

This research was supported by the National Natural Science Foundation of China (No. 51773165), Project of National Defense Science and Technology Innovation Special Zone (No. JZ-20171102), Shaanxi Post-doctoral Foundation (No. 2016BSHYDZZ20), Key Laboratory Construction Program of Xi’an Municipal Bureau of Science and Technology (No. 201805056ZD7CG40), Innovation Capability Support Program of Shaanxi (No. 2018PT-28 and 2019PT-05). The numerical calculations in this paper have been done on the supercomputing system in the Supercomputing Center of Wuhan University. A. K. C. thanks the Ras al Khaimah Centre for Advanced Materials for financial support. J. H. thanks the financial support (No. DE190100803). The authors would like to thank the Center for Advancing Materials Performance from the Nanoscale (CAMP-Nano) for allowing the use of field-emission scanning electron microscopy. We also thank Miss Jiao Li at Instrument Analysis Center of Xi’an Jiaotong University for their assistance with TEM mapping analysis.

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