As a potential substitute for commercial lithium ion batteries (LIBs), sodium ion batteries (NIBs) have attracted increasing interest during the last decade. However, compared to the LIBs, the sluggish kinetics of sodium ion diffusion in NIBs due to its larger ionic radius results in deteriorated electrochemical performances, which hinders the future development and application of NIBs. Therefore, exploring anode materials that exhibit a novel kinetic mechanism is desired. Recently, extremely rapid kinetics has been realized by introducing the pseudocapacitance effect into battery systems; this effect generally refers to faradaic charge-transfer reactions, including surface or near-surface redox reactions, and fast bulk ion intercalation. To obtain a pseudocapacitance effect in battery systems, the critical step involves the rational design of a two-dimensional structure with a high conductivity. In this regard, the bimetallic sulfide thiospinel NiCo2S4 stands out by virtue of its high conductivity (1.25 × 106 S·m-1) at room temperature, which is at least two orders of magnitude higher than that of the oxide counterpart (NiCo2O4). Herein, NiCo2S4 hexagonal nanosheets with a large lateral dimension of ~2 μm and thickness ~30 nm have been successfully synthesized through coprecipitation followed by a vapor sulfidation method. As the anode material in NIBs, the NiCo2S4 nanosheets deliver a reversible capacity of 387 mAh·g-1 after 60 cycles at a current density of 1000 mA·g-1. Additionally, the NiCo2S4 nanosheets exhibit high reversible capacities of 542, 398, 347, 300, and 217 mAh·g-1 at the current densities 200, 400, 800, 1000, and 2000 mA·g-1, respectively. Ex situ X-ray diffraction analysis has been employed to reveal that the sodium ion storage process is a result of a combined Na+ intercalation and conversion reaction between Na+ and NiCo2S4. Further quantitative analysis of the kinetics has verified the extrinsic pseudocapacitance mechanism of the Na+ storage process, in which the capacitive contribution enlarges as the current density increases. The observed capacitive contribution of NiCo2S4 electrode is as high as 71% at a scan rate of 0.4 mV·s-1. This is closely attributed to the modified thin-sheet structure of NiCo2S4 and hybridization with graphene that account for the superior high-rate performance with long-term cyclability. These intriguing results shed light on a new strategy for the structural design of electrode materials for advanced NIBs. Moreover, this vapor transformation route can be extended to the preparation of other transition metal disulfides with high electrochemical activities, such as FeCo2S4, ZnCo2S4, CuCo2S4, etc.
Received: 11 January 2018
Published: 24 January 2018
Fig 1 (a) XRD pattern of 2D NiCo2S4 hexagonal nanosheets and high-resolution XPS spectra of (b) Ni 2p, (c) Co 2p, and (d) S 2p of as-obtained NiCo2S4 nanosheets sample.
Fig 2 (a, b) SEM images and (c) AFM image of 2D NiCo2S4 hexagonal nanosheets.
Fig 3 TEM image (a); SADE (b) and HR-TEM image (c) of 2D NiCo2S4 hexagonal nanosheets.
Fig 4 (a) First four CVs of NiCo2S4 hexagonal nanosheets; (b) The off-line XRD pattern of the NiCo2S4 electrode of different charging/discharging states; (c) First five charge/discharge profiles of NiCo2S4 hexagonal nanosheets; (d) Cycling performance of NiCo2S4 and NiCo2S4; (e) Rate performance of NiCo2S4 and NiCo2S4.
Fig 5 (a) CVs of NiCo2S4 hexagonal nanosheets at various scan rates from 0.1 to 0.4 mV•s-1; (b)Corresponding lgi vs lgv plots at each redox peak (peak current: i, scan rate: v); (c) CV curve with the pseudocapacitive contribution shown by the blue region at a scan rate of 0.4 mV•s-1; (d) bar chart exhibiting the contribution ratio of pseudocapacitive contribution (blue) at various scan rates.
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