4.6 Article

Porous NiS2 nanosheets anchored on reduced graphene oxide as high-rate and long-life anode materials for sodium-ion batteries

Journal

ELECTROCHIMICA ACTA
Volume 462, Issue -, Pages -

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2023.142705

Keywords

Two dimensional; Nickel sulfides; Ni(OH)(OCH3); reduced graphene oxide; Anode; Sodium-ion battery

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In this study, graphene oxide is utilized as a platform for the synthesis of Ni(OH)(OCH3) and subsequent conversion to NiS2 on reduced graphene oxide (rGO) nanosheets. The resulting NiS2@rGO composite exhibits a 2D porous structure, providing abundant active sites for charge storage and facilitating ion/electron transport. Additionally, rGO nanosheets suppress the shuttle effect of polysulfides and enhance electrical conductivity. The NiS2@rGO electrode demonstrates exceptional rate capability and a long lifespan in an ether-based electrolyte. However, its performance is poor in an ester-based electrolyte. The unique hierarchical structure of the NiS2@rGO composite makes it a promising candidate for anode materials in sodium-ion batteries. The work also suggests a novel M(OH)(OCH3)@rGO intermediate for the synthesis of transition-metal oxides/sulfides@rGO composites for energy storage and catalysis applications.
In this work, graphene oxide is used as a substrate for the nucleation and growth of Ni(OH)(OCH3) during solvothermal synthesis. As a result, 2D Ni(OH)(OCH3) nanosheets are vertically anchored on 2D reduced graphene oxide (rGO) nanosheets, forming a Ni(OH)(OCH3)@rGO composite. Afterward, a NiS2@rGO hybrid is created by sulfurizing the Ni(OH)(OCH3)@rGO intermediate, which presents the same morphology as the intermediate but a porous structure of NiS2 nanosheets. The characteristic 2D porous structure of NiS2 nanosheets offers abundant active sites for charge storage, accelerates ion/electron transport, and buffers volume expansion. Meanwhile, rGO nanosheets can suppress the shuttle of polysulfides while also enhancing electrical conductivity. These factors in conjunction with the thin and robust ether-derived SEI are favorable to mechanical stability and rapid sodiation kinetics in the NiS2@rGO electrode in the ether-based electrolyte, thereby endowing it with exceptional rate capability (324 mA h g(-1) at 5 A g(-1)) and a long lifespan (378 mA h g(-1) over 1800 cycles at 1 A g(-1)). However, in the ester-based electrolyte, NiS2@rGO shows poor rate capability and cyclability. The kinetic analysis unveils the mechanism underlying the different electrochemical behavior in NiS2@rGO in the two electrolytes. More importantly, the NiS2@rGO electrode outperforms most NiS2-based materials reported in terms of rate and cycling performance owing to its unique hierarchical structure, making it a viable contender for anode materials in sodium-ion batteries. We also propose a novel M(OH)(OCH3)@rGO intermediate for the fabrication of transition-metal oxides/sulfides@rGO composites for energy storage and catalysis.

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