Electrochemical performance of ZIF-derived Co3SnC0.7/Co3Sn2@NC with heterostructure as anode material for sodium-ion batteries
Introduction
The rapid development of information technology has brought a wide variety of electronic products to our life, and most products need batteries to provide energy. In particular, portable electronic products, such as mobile phones, laptops, tablets, mobile power supplies, etc. have high requirements for battery capacity and endurance. In addition, promoting the use of electric vehicles is also an important way to achieve low-carbon economy. Lithium ion battery is one of the main means to realize the above requirements. These devices demand lithium resources so much that lithium resources become more and more scarce and expensive. Therefore, looking for new energy storage materials that can replace lithium has become one of the development trends of material construction [1]. As the same main group element of lithium, sodium has a similar energy storage mechanism with lithium. The experience and technology accumulated in the development of lithium ion batteries can be used for reference. In addition, due to the abundant reserves, low price and convenient extraction of sodium resources, sodium ion battery is generally considered to be the most potential and competitive secondary battery to replace lithium-ion battery for energy storage system [2,3]. However, because the radius of sodium ion (0.102 nm) is greater than that of lithium ion (0.076 nm), many negative electrode materials with excellent lithium storage performance, including graphite negative electrode materials commonly used in commercial lithium-ion batteries, have very slow sodium storage kinetics and are not competent to be used as negative electrode materials for sodium ion batteries, which seriously hinders the development and application of sodium ion batteries [4,5]. Therefore, new anode materials for sodium-ion batteries need to be explored.
Among various SIB anode materials, tin and tin based materials have attracted extensive attention because of their higher capacity and lower voltage platform due to their electrochemical alloying with sodium [6,7]. However, owing to the large volume expansion in the process of sodiation/desodiation, tin based materials are usually used as anode materials of SIB after hybridization with carbon materials [8]. Thangavelu Palaniselvam loaded Sn onto nitrogen doped graphite nanosheets by ball milling and heat treatment to prepare SnNGnP with first charge/discharge specific capacity of 394/517 mAh·g−1 [9]. Nitrogen-doped graphite nanosheets increased the conductivity of the material, and the defect structure provided additional sodium storage performance. Construction of nano alloys is another method to alleviate the volume expansion of tin based materials. Using SnO2/Co3O4 as the precursor, Huang prepared SnCo@C anode material by hybridization with carbon [10]. After 120 cycles at a current density of 100 mA·g−1, SnCo@C still maintained a reversible specific capacity of 276.2 mAh·g−1. In recent years, Metal Organic Frameworks and their derivatives have been used in battery materials for their high porosity and large surface area [11,12]. Sn@3D-NPC was prepared by directly annealing MOFs to obtain three-dimensional nanoporous carbon skeleton, and further formed Sn nanoparticles in the pores or cavities of porous carbon by hydrothermal method, showing excellent electrochemical properties as lithium anode. The carbon converted from ZIF-67 provides a good electron and ion transfer path as the electrode material substrate, and can be used as a skeleton to disperse active material particles, so as to improve the cycle performance and rate performance of the battery [13].
In this work, heterostructured Co3SnC0.7/Co3Sn2@NC has been obtained by pyrolysis of ZIF-67 coated hollow CoSn(OH)6 precursor. The hollow CoSn(OH)6 precursor provides favorable conditions for the formation of non-uniform grain boundaries and the assembly of secondary particles in the subsequent heat treatment. Different amounts of ZIF-67 coatings can be obtained by controlling Co2+ concentration, and then the phase composition of electrode materials can be adjusted through the subsequent calcination process. The heterostructure and nitrogen-containing carbon coating derived from ZIF-67 are beneficial to the transmission of electrons and sodium ions. Co3SnC0.7/Co3Sn2@NC sample shows excellent sodium storage properties with the first discharge/charge specific capacity of 767/421 mAh·g−1 at a current density of 100 mA·g−1 and reversible specific capacity of 300 mAh·g−1 after 100 cycles. This work provides a method to prepare electrode materials with heterogeneous interface using hollow precursors and control the composition of electrode active materials by controlling the amount of ZIF-67 coating, which provides an important strategy for accurately designing the structure and composition of energy materials.
Section snippets
Materials preparation
Hollow precursor CoSn(OH)6, which was obtained by a typical synthesis [14,15], was dispersed in dimethylimidazole solution. Co(NO3)2 and dimethylimidazole were added to the solvent in a molar ratio of 1:4 and stirred evenly. Then the two solutions were mixed, stirred for 1 h, filtered and washed, and vacuum dried at 80 °C. Subsequently, the dried materials were put into a tube furnace at 700 °C for 2 h in an Ar atmosphere with a heating rate of 3 °C min−1 to obtain the final samples. The
Results and discussion
Co3SnC0.7/Co3Sn2@NC was synthesized by the combination of co-precipitation and heat treatment, and the specific process is shown in Fig. 1. Firstly, hollow CoSn(OH)6 was prepared in aqueous solution, and then CoSn(OH)6 and ZIF-67 intermediate products were prepared by co-precipitation method. In this process, the hollow precursor was uniformly coated by ZIF-67. Finally, the target product was obtained by thermal annealing at 700 °C under Ar for 2 h.
XRD technology was used to detect the
Conclusions
In summary, MOF-derived Co3SnC0.7/Co3Sn2@NC composites with heterostructure were successfully prepared by simple co-precipitation and subsequent calcination in ZIF-67 solution using hollow CoSn(OH)6 as precursor. As the anode of SIBs, Co3SnC0.7/Co3Sn2@NC composites show high specific capacity and good cycle stability. EIS results exhibit that the material has very low resistance, and obvious pseudo capacitance behavior has been detected by CV test. Good electrochemical performance benefits from
CRediT authorship contribution statement
Jing Kang: Methodology, Investigation, Writing – original draft. Lijuan Zhang: Conceptualization, Writing – review & editing, Supervision. Xiayan Wang: Resources, Supervision.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (No. 21936001), the Beijing Outstanding Young Scientist Program (BJJWZYJH01201910005017).
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