Designing advanced sandwiched 2D NC/MoSe2@N-doped carbon arrays as new anode materials for efficient sodium storage
Graphical abstract
A novel 2D hierarchical sandwich-liked MoSe2 core/shell nanosheet array is designed and fabricated for use in sodium-ion batteries. The NC/MoSe2@NC delivers a reversible capacity of 669 mAh g−1 at 0.2 A g−1 over 150 cycles for SIB, and the sodium full cell displays a high energy density of 186.2 Wh kg−1 at a power density of 121.2 W kg−1.
Introduction
With the prompt development of modern society and growing demand for clean and renewable energy storage systems, it is pressing to explore high-energy density electrode materials to meet the urgent requirements in energy storage fields [1,2]. Over the past decade, sodium-ion batteries (SIBs) are widely investigated as a strong potential candidate to substitute lithium-ion technologies for its low price, abundant sodium resource, and suitable redox potential [3], [4], [5]. Nevertheless, compared with radius of Li+ ions, the larger inherent radius of Na+ ions may result in sluggish electrochemical dynamics and severe volume change of electrode materials leading to a lower specific capacity and poorer cycle stability [6,7]. Thus, most of the commercial electrode materials suitable for LIBs cannot be directly used by SIBs. Construction high-performance SIBs remains one of significant challenges for finding suitable electrode materials.
Transition metal dichalcogenides (TMDs), have drawn significant studies in electrochemical energy storage fields for the unique layered structures, suitable physicochemical properties and high theoretical specific capacity [8], [9], [10], [11]. Among various TMDs materials, MoS2 has been widely studied as a attractive anode material in LIBs. Nevertheless, owing to the small interlayer spacing (0.62 nm) and a low intrinsic conductivity, the MoS2 was employed as the anode material in SIBs which exhibits much lower capacity and poorer cyclic performance [12,13]. By contrast, MoSe2 possesses a higher theoretical capacity, a larger interlayer spacing (0.64 nm) as well as superior intrinsic conductivity, making it one of the potential anode materials for application in SIBs [14,15]. But the practical application of MoSe2 for SIBs is hampered by fast capacity decay owing to the large volume changes and obvious agglomeration during long charging/discharging process. In addition, its low intrinsic electrical conductivity results in the poor rate capability [16]. Multiple strategies have been undertaken to address these issues, among which modifying nanostructure of electrode materials is widely investigated. For instance, reducing the size of MoSe2 can dramatically decrease the Na+ diffusion distance, and improve the contacts of electrolyte with active materials thus enhancing the rate capability [14,16]. Additionally, expanding the interlayer spacing of MoSe2 enhances sodium ions storage properties by reducing the Na+ diffusion energy barrier, thereby improving the electrochemical kinetics of Na+ [13,17]. Furthermore, to enhance the cycling stability of MoSe2, an effective strategy is to incorporate MoSe2 with the conductive carbon material, which effectively improves the conductivity, alleviates the volume expansion, as well as restrains the structure collapse of electrode materials. Despite these advantages of hybrid MoSe2/carbon configuration, the structural stability of electrode material also exists another challenge during the repeated intense sodiation/desodiation especially in long-term cycling under high current density. In addition, the active materials without conductive protective layer will directly contact with electrolyte to generate of an irreversible solid electrolyte interphase (SEI) layer. When the excessive SEI film accumulation on the surface of electrode materials that cause severe volume expansion, it may lead to a crack of the frangible SEI layer giving rise to rapid capacity decay. Designing a conductive carbon layer on electrode material is regarded one of effective strategies for increasing electron transfer, preserving the structural integrity and enhancing the cyclic stability [18], [19], [20].
As an important member of crystalline materials, metal organic frameworks (MOFs) fabricated by organic ligands and metal nodes, have drawn considerable attention owing to their tunable porous structures and ordered open tunnel. In recent years, MOFs have been regarded as an ideal precursor to fabricate porous carbonaceous materials, which hold great promise as low-cost and efficient electrode materials for application in energy storage field [21]. However, the most of MOFs derived carbonaceous materials are powder samples, thus requiring additional amount of binder and conductive additive to construct compact film. The introduced binder not only weakens the electron transfer, but also increases the interfacial resistance as well as reduces the utilization of active materials [22,23]. To address this issue, constructing self-supporting electrode on the current collector is an effective strategy.
In this paper, we reported the rational design and fabrication of MoSe2 nanosheets on the MOFs derived N-doped carbon flake arrays (NC) by the hydrothermal process. Particularly, MoSe2 nanosheets were uniformly and vertically distributed on the thin and porous NC arrays construction of a 2D hierarchical nanostructure, which improves the electrical conductivity of hybrid material and effectively protects MoSe2 nanosheets from agglomeration and restacking. Furthermore, the carbon protective layer can improve structural stability and electrochemical properties. Meanwhile, the strong interfacial interactions between MoSe2 nanosheets and porous NC arrays accelerate the electron transfer and enhance Na+ ions adsorption/diffusion kinetic. In addition, the obtained NC/MoSe2@NC array is directly grown on carbon cloth as free-standing electrodes avoiding additional amount of binder and conductive additive which increases the utilization of active materials. We assessed the performance of NC/MoSe2@NC arrays as self-supporting anode materials for SIBs, which achieves 632 mAh g−1 reversible capacity at 0.2 A g−1, and actual capacity of 421 mAh g−1 by deducting the contributed capacity of carbon cloth substrates. Furthermore, the composite material also delivers excellent long cycling stability (348 mAh g−1 at 1 A g−1 over 1000 cycles), and good rate capabilities. Moreover, the density function theory (DFT) calculations further investigate the sodium ions storage behavior of NC/MoSe2@NC electrode materials. The incorporation of carbon enhances the conductivity of MoSe2 as well as the adsorption/diffusion kinetics of Na+, leading to significantly boost electrochemical properties of MoSe2 for SIBs.
Section snippets
Synthesis of Zn/Co-MOFs arrays
In a typical synthesis, zinc nitrate hexahydrate (0.017 mol) and cobalt nitrate hexahydrate (0.034 mol) were dissolved in 40 mL deionized water. 2-methylimidazole (0.4 mol) was dissolved in 40 mL deionized water. Then 2-methylimidazole solution was quickly poured into zinc/cobalt nitrate hexahydrate solution, and a piece (3 cm × 2.8 cm) of carbon cloth was placed into the mixture solution. After aging for 4 h, the carbon cloth was rinsed by distilled water for three times, then dried at 60°C
Results and discussion
The schematic diagram for the preparation process of NC/MoSe2@NC nanosheets arrays is presented in Fig. 1. First, the self-supporting porous N-doped carbon (NC) nanosheets arrays are derived from Zn/Co MOFs precursors via a facile solution process followed by high temperature pyrolysis treatments and acid etching process. Subsequently, the surface of NC arrays are uniformly wrapped by ultrathin MoSe2 nanosheets through a facile hydrothermal reaction to form MoSe2@NC core/shell nanosheets
Conclusion
In summary, the self-supporting sandwiched NC/MoSe2@NC core/shell arrays electrode was designed and fabricated on carbon cloth via facile hydrothermal and thermal treatment. The MoSe2 is encapsulated via strong interfacial interaction into 2D carbon frameworks which are composed of MOFs derived N-doped carbon flake arrays inner-layer and a carbon protective layer. Such assemblage can alleviate the volume expansion, as well as prevent agglomeration and improve durable structural stability.
CRediT authorship contribution statement
Xuan Luo: Investigation, Writing – original draft. Xiangpeng Kong: Methodology. Peng He: Supervision. Jian Shao: Investigation. Kang Li: Investigation. Weiwei Zhao: Supervision.
Declaration of Competing Interest
No conflict of interest exits in the submission of this manuscript, and manuscript is approved by all authors for publication.
Acknowledgements
This work was supported by the Natural Science Foundation of China No. 52073075 and Shenzhen Science and Technology Program (Grant No. KQTD20170809110344233).
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These authors contributed equally to this work.