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(Nis2 and Nise2) Decorated with Graphene for Efficient Supercapac

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(Nis2 and Nise2) Decorated with Graphene for Efficient Supercapac RSC Advances View Article Online PAPER View Journal | View Issue Controllable synthesis of hollow spherical nickel chalcogenide (NiS and NiSe ) decorated with Cite this: RSC Adv.,2021,11,11786 2 2 graphene for efficient supercapacitor electrodes† Min Lu,*a Ming-yuan Sun,a Xiao-hui Guan, a Xue-mei Chen*a and Guang-Sheng Wang *b New carbon-loaded nickel chalcogenide electrode materials (NiS2/GO and NiSe2/rGO) have been synthesized through an easy-to-operate process: NiSe2 was obtained based on NiS2 hollow spheres, and was successfully synthesized with L-cysteine assistance under the hydrothermal method at 120 C. GO of different mass fraction was added together with L-cysteine. The electrochemical performance of NiS2/ GO and NiSe2/rGO has been greatly improved because the formation of a carbon-loaded layer effectively increased the specific surface area and reduced the charge transport resistance. Compared with pure NiS2 and NiSe2, NiS2/GO and NiSe2/rGO presented much better specific capacitance (1020 F À1 À1 À1 Creative Commons Attribution-NonCommercial 3.0 Unported Licence. g and 722 F g respectively at a current density of 1 A g ) and more superior rate capability (when Received 22nd December 2020 À À À the current density was raised to 5 A g 1 the specific capacitance remained at 569 F g 1 and 302 F g 1). Accepted 9th March 2021 This work highlights the advantages of nickel compounds through a very simple experimental method, DOI: 10.1039/d0ra10659c and contributes to providing a good reference for preparation of superior supercapacitor materials with rsc.li/rsc-advances high performance. 1 Introduction and cycle stability of energy storage device and further improve the properties. This article is licensed under a With the decline of fossil energy, there has been a positive As we all know, electrode materials, as the core component exploitation of alternative energy sources and high efficiency of the device, play a decisive role in the development and energy storage devices.1,2 Supercapacitors (SCs),3,4 also called commercial application of supercapacitors. Moreover, their composition, morphology and structure have a crucial impact Open Access Article. Published on 23 March 2021. Downloaded 9/26/2021 2:34:47 PM. ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. As new on the electrochemical performance of the materials in the – energy storage components, SCs are different from traditional design of electrode materials.12 14 Nanostructured transition capacitors and batteries because of their advantages, including metal chalcogenide, as electrode materials, are considered to be high power density, high specic capacity, quick charge and inorganic functional materials with application prospects due discharge, long cycle life and high safety capacity.5–9 Therefore, to the charge storage through Faraday reaction of metal ions.15 SCs have a good application prospect in the elds of high-power Nevertheless, a series of single nanomaterials with different and high-energy power supply, clean energy, smart grid, trans- compositions and morphologies, have mostly been explored at portation, wireless communication, aerospace, military, elec- the research level as pseudo capacitors (PCs) electrode materials tronic equipment and so on. However, the relatively low energy in labs rather than at the industrial level for practical applica- density of supercapacitors seriously limits their commercial tion, due to their rapid degradation and low capacity retention application.10,11 At present, research teams at home and abroad in high reversible ion adsorption or rapid redox reactions.16 For mainly develop new electrode materials, electrolytes and instance, Pang etc. prepared nickel oxide nanostructures with asymmetric super capacitors to maintain high power density different lengths and NiO nanowires with the longest length À have the largest specic capacitance of 180 F g 1.17 Sun etc. prepared NiS2 nanospheres via a facile one-step poly- vinylpyrrolidone assisted method which delivers a high revers- À1 aSchool of Chemical Engineering, Northeast Electric Power University, Jilin 132000, P. ible specic capacity of 692 mA h g .18 Mondal etc. produced R. China porous NiCo2O4 hollow spheres which showed specic capacity bKey Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry À1 19 as high as 183 C g . Li etc. prepared graphene/NiS2 composite of Education, School of Chemistry, Beihang University, Beijing 100191, P. R. China. through a template-free solvothermal reaction using graphene E-mail: [email protected] À1 † Electronic supplementary information (ESI) available. See DOI: oxide shows a great value of 478.1 F g at a current density of À1 20 10.1039/d0ra10659c 0.5 A g . However, it is noteworthy that the hollow spheres 11786 | RSC Adv.,2021,11, 11786–11792 © 2021 The Author(s). Published by the Royal Society of Chemistry View Article Online Paper RSC Advances sul des with the large internal space are more likely showing 2.1.2 Preparation of NiS2 and NiS2/GO hollow spheres. All excellent physical and chemical properties such as low density, of the chemicals are analytical grade and used without further ff 36 large e ective area and good mass permeability to have more purication. In a typical synthesis, 1 mmol Ni(NO3)2$6H2O active sites and faster charge transfer ability and further and 1 mmol urea were dissolved in 20 mL of deionized water 21,22 improve the electrochemical properties of materials. with magnetic stirring, then 4 mmol L-cysteine and 50 mL Compared with single nickel chalcogenide, nanocomposites deionized water were added. L-Cysteine is the source of sulfur. can make full use of the synergistic and complementary effects Aer ultrasonic treatment, the homogeneous suspension was among components, which makes them have greater advan- transferred into a 100 mL teon-lined stainless steel autoclave tages in application.23–25 Among them, for the carbon based for solvothermal reaction at 120 C for 24 h. The black precip- transition metal compound composite, the introduction of itates of hollow spherical NiS2 were washed several times with carbon material can improve the overall conductivity of the distilled water and absolute ethanol and dried at 60 C for 12 h ff material on the one hand, and e ectively inhibit the agglom- for further characterization. To obtain NiS2/GO nano- eration of small-size active substances, so that the composite composites, GO of ten percent (10 wt%), een percent has a larger specic surface area, fully contact with the elec- (15 wt%), twenty percent (20 wt%), twenty ve percent (25 wt%) trolyte, thus improving its charge transfer and storage and thirty percent (30 wt%) was added to the above mixed 26,27 capacity. On the other hand, the excellent structure and solvent together with 4 mmol L-cysteine. To distribute GO evenly chemical stability of carbon materials can buffer the volume in the solution, an additional stirring time of 30 minutes was change of materials during charging and discharging, and added. The following processing steps are consistent with the 28–30 improve the cyclic stability of materials. When nickel method used to prepare NiS2. sul des/graphene composites are used as pseudocapacitor 2.1.3 Preparation of NiSe2 and NiSe2/rGO hollow spheres. electrode materials, the graphene can not only provide an The 1 mmol above-prepared hollow spherical NiS2 was stably elastic space to buffer the volume change of the electrode dispersed in 40 mL of deionized water under magnetic stirring. $ Creative Commons Attribution-NonCommercial 3.0 Unported Licence. materials during the repetitive charge/discharge process, but 2 mmol H2SeO3 and 5 mL of N2H4 H2O were added in this also facilitate the faster electron transport, resulting in an solution, and transferred to a 100 mL teon-lined stainless steel enhanced electrochemical performance.31,32 It has been autoclave and heated at 140 C for 24 h, then the solution was demonstrated that the solvothermal synthesized NiS/graphene cooled to room temperature. The products of NiSe2 were ob- 33,34 35 composite and Ni3S2/N-doped graphene composite tained aer washing and drying. In composite preparation, GO exhibited the enhanced electrochemical performances in of one percent (1 wt%), three percent (3 wt%), ve percent comparison with the NiS and Ni3S2. In particular, when (5 wt%) and seven percent (7 wt%) was added to the above $ combined with graphene, the speci c capacitance of NiO mixed solvent together with N2H4 H2O. The following pro- À À À increased from 47.2 F g 1 to 187.53 F g 1 at 10 mV s 1 scan rate. cessing steps are consistent with the method used to prepare This article is licensed under a – And the discharge charge cycling stability of the Ni3S2@N-G NiSe2 except the addition of graphite oxide. and bare Ni3S2 was examined at a current density of À1 – 50 mA g between 0.01 and 3.0 V delivers initial discharge 2.2 Characterization À1 Open Access Article. Published on 23 March 2021. Downloaded 9/26/2021 2:34:47 PM. charge capacities of 1739 and 729 mA h g respectively. The morphology and size of the products were obtained using Herein, in this work, we prepared a series of controllable scanning electron microscopy (SEM) with a JSM-6510A micro- morphology hollow spheres NiS and microspheres NiSe 2 2 scope and by sputtering with gold. The samples were examined composited with graphene by a simple and effective hydro- by X-ray diffraction (XRD-7000), recorded using a Shimadzu X- thermal process by adjusting the graphene oxide concentration, ray powder diffractometer with Cu-Ka radiation (l ¼ 0.15405 and the result composites were characterized by XRD (X-ray nm). X-ray photoelectron spectroscopy (XPS, ESCALAB-250) with diffraction pattern), SEM (scanning electron microscopy), an Al-Ka radiation source were used.
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