Constructing heterostructures in the anode materials of sodium-ion batteries has been regarded as an efficient method to improve the electrochemical sodium storage capability. However, preparing bimetallic chalcogenide heterostructure materials is still challenging. Organic hybrid ternary metal chalcogenides possess two kinds of metal ions in their structures. These materials would be promising precursors to prepare bimetallic chalcogenide heterostructures. However, this concept has never been executed to date. For this purpose, herein, a crystalline organic hybrid ternary selenide [Ni(phen)3]Sn3Se7·1.5H2O (NPTS) has been first selected as a precursor to prepare the bimetallic selenide heterostructure. After the bulk crystals of NPTS were heated at 400 °C, nanosheets of NiSe2/SnSe2@CN (CN = nitrogen-doped carbon) containing both Schottky and NiSe2–SnSe2 junctions were formed. The NiSe2 and SnSe2 nanosheets were stacked layer by layer, and the surface of the NiSe2/SnSe2 nanosheet was coated by a CN layer. Benefiting from the heterointerfaces among NiSe2 nanosheets, SnSe2 nanosheets, and CN layers, NiSe2/SnSe2@CN can provide a capacity of 357.4 mA h g–1 at 1000 mA g–1 after 2700 cycles, much higher than the sole NiSe2 nanoparticles and SnSe2 nanosheets. In addition, the NiSe2/SnSe2@CN electrode also exhibited superior rate performance, as compared with the previously reported NiSe2- or SnSe2-based anode materials. This work proved that pyrolysis of organic hybrid ternary metal selenide could be a promising approach to synthesize bimetallic selenide heterostructure materials for electrochemical sodium storage.
Inorganic metal sulfides have received extensive investigation as anode materials in lithium-ion batteries (LIBs). However, applications of crystalline organic hybrid metal sulfides as anode materials in LIBs are quite rare. In addition, combining the nanoparticles of crystalline organic hybrid metal sulfides with conductive materials is expected to enhance the electrochemical lithium storage performance. Nevertheless, due to the difficulty of harvesting the nanoparticles of crystalline organic hybrid metal sulfides, this approach has never been tried to date. Herein, nanoparticles of a crystalline organic hybrid cadmium antimony sulfide (1,4-DABH2)Cd2Sb2S6 (DCAS) were prepared by a top-down method, including the procedures of solvothermal synthesis, ball milling, and ultrasonic pulverization. Thereafter, the nanoparticles of DCAS with sizes of ∼500 nm were intercalated into graphene oxide nanosheets through a freeze-drying treatment and a DCAS@GO composite was obtained. Compared with the reported Sb2S3- and CdS-based composites, the DCAS@GO composite exhibited superior electrochemical Li+ ion storage performance, including a high capacity of 1075.6 mAh g–1 at 100 mA g–1 and exceptional rate tolerances (646.8 mAh g–1 at 5000 mA g–1). In addition, DCAS@GO can provide a high capacity of 705.6 mAh g–1 after 500 cycles at 1000 mA g–1. Our research offers a viable approach for preparing the nanoparticles of crystalline organic hybrid metal sulfides and proves that intercalating organic hybrid metal sulfide nanoparticles into GO nanosheets can efficiently boost the electrochemical Li+ ion storage performance.
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