CN113299486A - Selenium nickel cobalt/carbon composite material and preparation method and application thereof - Google Patents
Selenium nickel cobalt/carbon composite material and preparation method and application thereof Download PDFInfo
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- CN113299486A CN113299486A CN202110520990.1A CN202110520990A CN113299486A CN 113299486 A CN113299486 A CN 113299486A CN 202110520990 A CN202110520990 A CN 202110520990A CN 113299486 A CN113299486 A CN 113299486A
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention belongs to the technical field of material synthesis and electrochemistry, and discloses a selenized nickel-cobalt/carbon composite material and a preparation method and application thereof. The preparation method of the nickel cobalt selenide/carbon composite material is simple and easy to implement, and the composite material has higher specific capacitance and better cycle stability when being used for the electrode of the super capacitor.
Description
Technical Field
The invention belongs to the technical field of material synthesis and electrochemistry, and particularly relates to a nickel-cobalt selenide/carbon composite material, and a preparation method and application thereof.
Background
The environmental and energy crisis is aggravated by the excessive consumption of fossil energy, the traditional fossil energy can be replaced by renewable energy such as solar energy, wind energy and the like, and a series of energy storage devices are researched and developed by scientific researchers. As a novel energy storage device, the super capacitor has the advantages of fast charge and discharge capacity, long cycle life and high rate performance, and is widely concerned. According to the difference of energy storage principle, the super capacitor can be divided into two categories: one is an electric double layer capacitor, which usually adopts a carbon material with a large specific surface area as an electrode material and stores charges by utilizing an electric double layer generated at an electrode/electrolyte interface; the other type is a pseudo capacitor, transition metal oxides, hydroxides and conductive polymers are usually adopted as electrode materials, and the electrode materials are subjected to rapid oxidation-reduction reaction on the surface of the electrode and absorption and desorption of ions in the material for energy storage.
ZIFs series metal organic framework materials are crystal materials with zeolite-like topological structures formed by coordination of divalent zinc, cobalt and other transition metals and imidazolyl organic ligands in a self-assembly mode, and besides excellent performances such as large specific surface area and rich pore size distribution, the crystal materials are often selected as precursors or template materials to prepare derivative materials with specific structures. ZIF-67 using transition metal cobalt ion as metal ion and dimethyl imidazole as ligand is widely concerned by researchers because of its stable structure and simple synthesis method. Derivative materials such as porous carbon, metal oxide, metal sulfide and the like prepared by taking the porous carbon, the metal oxide, the metal sulfide and the like as templates show excellent performance in the fields of energy storage, catalysis, biomedicine and the like.
Selenium, oxygen, and sulfur are located in the sixth main group and have similar chemical properties. Selenium has a lower electronegativity than the other two elements, so selenides have a higher electrochemical activity in reactions than metal oxides/sulfides, while much less research work has been done on transition metal selenides than oxides, sulfides. In addition, in the existing reports related to the transition metal selenide, the electrode material is easy to collapse in structure during the charge and discharge processes, and then the stability of the electrode material is affected.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a nickel selenide cobalt/carbon composite material and a preparation method and application thereof. Selenium element has higher conductivity, the nickel cobalt-layered double hydroxide is selenized, the electrochemical performance of the obtained nickel cobalt selenide is obviously improved, glucose is used as a carbon source, and a carbon layer is wrapped on the surface of the nickel cobalt selenide, so that the stability of the nickel cobalt selenide is effectively improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a nickel cobalt selenide/carbon composite material is prepared by selenizing nickel cobalt-layered double hydroxide derived from a metal organic framework ZIF-67 to obtain nickel cobalt selenide, and then performing carbon coating by using glucose as a carbon source.
The invention also provides a preparation method of the selenium nickel cobalt/carbon composite material, which comprises the following steps:
preparing a metal organic framework ZIF-67 by adopting cobalt nitrate hexahydrate and 2-methylimidazole, mixing an ethanol solution of the metal organic framework ZIF-67 and an ethanol solution of nickel nitrate hexahydrate, magnetically stirring, carrying out centrifugal separation to obtain a nickel cobalt-layered double hydroxide, selenizing the nickel cobalt-layered double hydroxide to obtain nickel cobalt selenide, carrying out hydrothermal reaction on the nickel cobalt selenide in a glucose solution, and calcining a hydrothermal product to obtain the nickel cobalt selenide/carbon composite material.
Further, the method comprises the following steps:
weighing cobalt nitrate hexahydrate and 2-methylimidazole, respectively dissolving the cobalt nitrate hexahydrate and the 2-methylimidazole in absolute methanol, carrying out ultrasonic treatment until the solution is clear and transparent, mixing the two solutions, carrying out ultrasonic dispersion after purple precipitation occurs, uniformly mixing the two solutions, carrying out self-assembly at room temperature, finishing the reaction, washing a solid substance obtained after centrifugal separation for several times by using absolute ethyl alcohol, and drying the solid substance to obtain a metal organic framework ZIF-67;
weighing nickel nitrate hexahydrate and a metal organic framework ZIF-67, respectively dissolving the nickel nitrate hexahydrate and the metal organic framework ZIF-67 in absolute ethyl alcohol, then quickly adding an ethanol solution of the nickel nitrate hexahydrate into an ethanol solution of the ZIF-67, carrying out magnetic stirring, after the reaction is finished, washing a solid substance obtained after centrifugal separation for several times by using absolute ethyl alcohol, and drying to obtain nickel-cobalt-layered double hydroxide;
selenium powder and nickel cobalt-layered double hydroxide are mixed and stirred uniformly and then are placed in a quartz container, and selenization treatment is carried out in a tube furnace under the argon atmosphere to obtain nickel cobalt selenide;
immersing nickel cobalt selenide in a glucose solution, ultrasonically dispersing uniformly, transferring to a reaction kettle for hydrothermal reaction, washing a solid substance obtained after centrifugal separation with deionized water and absolute ethyl alcohol for several times, drying to obtain a hydrothermal product, and calcining the hydrothermal product in a tubular furnace under the condition of argon to obtain the nickel cobalt selenide/carbon composite material.
Further, the mass ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole is 0.4-1.2; the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1-2 g: 60-100 mL; the mass-volume ratio of the 2-methylimidazole to the absolute ethyl alcohol is 1-2 g: 60-100 mL; the self-assembly time is 12-36 h; the drying temperature of the reaction product of the cobalt nitrate hexahydrate and the 2-methylimidazole is 50-100 ℃, and the drying time is 10-20 hours.
Further, the mass ratio of the nickel nitrate hexahydrate to the ZIF-67 is 1.8-2.2; the mass volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol is 20-40 g: 1-3L; the ratio of ZIF-67 to absolute ethyl alcohol is 5-10 g: 1-2L; the reaction temperature of nickel nitrate hexahydrate and ZIF-67 is 60-120 ℃, and the reaction time is 20-40 min; the drying temperature of the nickel nitrate hexahydrate and the ZIF-67 product is 50-100 ℃, and the drying time is 10-20 hours.
Further, the mass ratio of the selenium powder to the nickel-cobalt-layered double hydroxide is 2-6: 1-3; the selenizing temperature in the tube furnace is 300-400 ℃, and the selenizing time is 1-2 hours.
Further, the mass volume ratio of the nickel cobalt selenide, the glucose and the solvent water is 5-15 mg: 30-50 mg: 8-12 mL;
the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 8-12 h;
the drying temperature of the hydrothermal product is 50-100 ℃, and the drying time is 10-20 h;
the calcining temperature in the tubular furnace is 400-500 ℃, and the calcining time is 1-3 h.
The invention also provides a selenized nickel-cobalt/carbon composite material, which is prepared by coating the nickel-cobalt selenide prepared after selenizing the nickel-cobalt-layered double hydroxide derived from ZIF-67 with a carbon layer.
The invention also provides a preparation method of the nickel cobalt selenide/carbon composite material, which comprises the following steps:
step a, preparing a metal organic framework ZIF-67: weighing cobalt nitrate hexahydrate and 2-methylimidazole, respectively dissolving in anhydrous methanol, performing ultrasonic treatment until the solution is clear and transparent, quickly mixing the two solutions to obtain purple precipitate, performing ultrasonic dispersion to uniformly mix the two solutions, and performing self-assembly at room temperature. And (3) after the reaction is finished, washing the solid substance obtained after the centrifugal separation for a plurality of times by using absolute ethyl alcohol, and drying to obtain the metal organic framework ZIF-67.
Step b, preparing nickel cobalt-layered double hydroxide: weighing nickel nitrate hexahydrate and the metal organic framework ZIF-67 prepared in the step a, respectively dissolving the nickel nitrate hexahydrate and the metal organic framework ZIF-67 in absolute ethyl alcohol, then quickly adding the ethanol solution of the nickel nitrate hexahydrate into the ethanol solution of the ZIF-67 for magnetic stirring, after the reaction is finished, washing the solid matter obtained after centrifugal separation with absolute ethyl alcohol for several times, and drying to obtain the nickel-cobalt-layered double hydroxide.
Step c, preparing nickel cobalt selenide: and c, mixing selenium powder with the nickel cobalt-layered double hydroxide prepared in the step b according to a certain proportion, uniformly stirring, placing in a quartz container, and carrying out selenylation treatment in a tube furnace under the argon atmosphere to obtain a selenylation product, namely the selenylation nickel cobalt.
Step d, preparing the selenized nickel-cobalt/carbon composite material: and c, immersing the nickel cobalt selenide prepared in the step c in a glucose solution, ultrasonically dispersing uniformly, transferring to a reaction kettle for hydrothermal reaction, washing the solid matter obtained after centrifugal separation with deionized water and absolute ethyl alcohol for several times, drying to obtain a hydrothermal product, and calcining the hydrothermal product in a tubular furnace under the condition of argon to obtain the nickel cobalt selenide/carbon composite material.
In some embodiments, in the step a, the mass ratio of the added cobalt nitrate hexahydrate to the 2-methylimidazole is 0.4-1.2, preferably 0.9, the self-assembly time is 12-36 hours, the drying temperature is 50-100 ℃, and the drying time is 10-20 hours.
In the step a, the mass of the added cobalt nitrate hexahydrate is 1-2 g, the mass of the 2-methylimidazole is 1-2 g, and the volume of the anhydrous methanol is 60-100 mL.
In the step b, the mass ratio of the added nickel nitrate hexahydrate to the ZIF-67 is 1.8-2.2, and preferably 2. Further, in the step b, the reaction temperature is 60-120 ℃, the reaction time is 20-40 min, the drying temperature is 50-100 ℃, and the drying time is 10-20 h.
In the step b, the mass of the added nickel nitrate hexahydrate is 100-200 mg, the mass of the ZIF-67 is 50-100 mg, the volume of absolute ethyl alcohol used for dissolving the ZIF-67 is 10-20 mL, and the volume of absolute ethyl alcohol used for dissolving the nickel nitrate hexahydrate is 5-15 mL.
In the step c, the mass ratio of the added selenium powder to the nickel cobalt-layered double hydroxide is 2, the selenizing temperature in the tube furnace is 300-400 ℃, and the selenizing time is 1-2 hours.
In the step c, the mass of the selenium powder is 100-300 mg, and the mass of the nickel cobalt-layered double hydroxide is 50-150 mg.
In the step d, the mass ratio of the nickel selenide cobalt to the glucose is 0.2-0.3, preferably 0.25, the hydrothermal reaction temperature is 160-200 ℃, the hydrothermal reaction time is 8-12 hours, the drying temperature is 50-100 ℃, and the drying time is 10-20 hours.
In the step d, the calcining temperature in the tubular furnace is 400-500 ℃, the calcining time is 1-3 hours, the mass of the nickel selenide cobalt is 25-75 mg, the mass of the glucose is 150-250 mg, and the volume of the solvent water for the hydrothermal reaction is 40-60 mL.
A selenium nickel cobalt/carbon composite material is prepared by the preparation method of the selenium nickel cobalt/carbon composite material.
The invention also provides application of the nickel selenide cobalt/carbon composite material in a super capacitor electrode material.
In some embodiments, the application comprises: dispersing the nickel cobalt selenide/carbon composite material in ultrapure water to obtain a dispersion liquid, transferring the dispersion liquid, dripping the dispersion liquid on the surface of the glassy carbon electrode, and drying under an infrared lamp to obtain the nickel cobalt selenide/carbon composite material modified glassy carbon electrode.
Further, the application further comprises: the method is characterized in that a nickel-cobalt selenide/carbon composite material modified glassy carbon electrode is used as a working electrode, a saturated calomel electrode is used as an auxiliary electrode, a platinum sheet electrode is used as a counter electrode, 2mol/L KOH is used as electrolyte, and the nickel-cobalt selenide/carbon composite material is subjected to constant current charge and discharge testing and circulation stability testing through an electrochemical workstation.
In some embodiments, the concentration of the dispersion is 1-5 mg/mL, the voltage range of the constant current charge and discharge test is-0.1-0.4V, and the current density of the cycle stability test is 5-15A/g.
Advantageous effects
The invention provides a selenizing nickel cobalt/carbon composite material and a preparation method and application thereof, wherein the nickel cobalt-layered double hydroxide derived from ZIF-67 is selenized, and the porous structure is favorable for the transmission of electrons and electrolyte ions at an electrode/electrolyte interface. And then the carbon layer is wrapped on the surface of the nickel cobalt selenide, so that the stability of the nickel cobalt selenide composite material is effectively improved. Has the following advantages: the preparation method is simple and easy to implement, and the prepared composite material has higher specific capacitance and better cycle stability when being used for the electrode of the super capacitor.
Drawings
Fig. 1 is a scanning electron microscope image of the nickel cobalt selenide/carbon composite prepared in the first embodiment.
Fig. 2 is a transmission electron microscope image of the nickel cobalt selenide/carbon composite prepared in the first embodiment.
Fig. 3 is an X-ray powder diffraction pattern of the nickel cobalt selenide/carbon composite prepared in example one, ZIF-67 in comparative example one, a nickel cobalt-layered double hydroxide in comparative example two, and nickel cobalt selenide in comparative example three.
Fig. 4 is an X-ray photoelectron spectrum of the nickel selenide cobalt/carbon composite prepared in the first example.
Fig. 5 is a plot of cyclic voltammetry for the nickel cobalt selenide/carbon prepared in the first example at different sweep rates.
Fig. 6 is a plot of galvanostatic charge and discharge curves for nickel cobalt selenide/carbon prepared in example one, ZIF-67 in comparative example one, nickel cobalt-layered double hydroxide in comparative example two, and nickel cobalt selenide in comparative example three.
Fig. 7 is a graph of the cycling stability of the nickel cobalt selenide/carbon composite prepared in example one, ZIF-67 in comparative example one, a nickel cobalt-layered double hydroxide in comparative example two, and nickel cobalt selenide in comparative example three.
FIG. 8 is a scanning electron micrograph of ZIF-67 prepared in comparative example one.
Fig. 9 is a scanning electron microscope image of the nickel cobalt-layered double hydroxide prepared in comparative example second.
Fig. 10 is a scanning electron micrograph of nickel cobalt selenide prepared according to comparative example three.
Detailed Description
The present invention will be further described with reference to the following drawings and specific examples, but the present invention is not limited to the following examples.
The first embodiment is as follows:
a preparation method of a nickel-cobalt selenide/carbon composite material for an electrode material of a super capacitor comprises the following steps:
(1) weighing 1.455g of cobalt nitrate hexahydrate (molecular weight of 291.03) and 1.642g of 2-methylimidazole (molecular weight of 82.1), respectively dissolving in 80mL of anhydrous methanol, performing ultrasonic treatment until the solution is clear and transparent, quickly mixing the two solutions to obtain purple precipitate, performing ultrasonic dispersion to uniformly mix the purple precipitate, performing self-assembly for 24 hours at room temperature, washing the solid matter obtained after centrifugal separation with anhydrous ethanol for several times, and drying in an oven at 60 ℃ for 12 hours to obtain the metal organic framework ZIF-67.
(2) Weighing 80mg of metal organic frame ZIF-67 powder in the step (1) and dissolving in 15mL of absolute ethyl alcohol, weighing 160mg of nickel nitrate hexahydrate (molecular weight of 218.63) and dissolving in 10mL of absolute ethyl alcohol, after uniform ultrasonic dispersion, quickly adding the nickel nitrate hexahydrate ethanol solution into the ZIF-67 ethanol solution, continuously stirring for 30min at 90 ℃, washing solid substances obtained after centrifugal separation with absolute ethyl alcohol for several times, and drying in an oven at 60 ℃ for 12h to obtain the nickel-cobalt-layered double hydroxide.
(3) Weighing 0.1g of nickel cobalt-layered double hydroxide powder obtained in the step (2) and 0.2g of selenium powder (molecular weight of 78.96), mixing and stirring uniformly, placing in a quartz container, placing in a tube furnace, and selenizing at 350 ℃ for 90min under argon atmosphere to obtain the nickel cobalt selenide.
(4) Weighing 0.05g of nickel cobalt selenide powder obtained in the step (3), immersing the powder in 50mL of deionized water containing 0.2g of glucose, ultrasonically dispersing the powder uniformly, transferring the mixed solution into a 100mL high-pressure reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 10 hours. Washing the hydrothermal product with deionized water and absolute ethyl alcohol for several times, drying in a drying oven at 60 ℃ for 12h, finally placing the hydrothermal product in a tube furnace, and calcining at 450 ℃ for 2h in an argon atmosphere to obtain the nickel-cobalt selenide/carbon composite material. As shown in fig. 1, the entire selenized nickel-cobalt/carbon composite material has a three-dimensional structure with rough and wrinkled surface. As shown in fig. 2, the nickel-cobalt selenide/carbon composite material has a distinct carbon layer coating the surface. As shown in fig. 3, which is an X-ray powder diagram of a nickel selenide cobalt/carbon composite material, since nickel selenide and cobalt selenide have diffraction peaks at similar positions, the diffraction peaks occurring at 2 θ of 30.0 °, 33.6 °, 37.0 °, 43.0 °, 50.9 °, 55.7 °, 58.0 ° correspond to the (200), (210), (211), (220), (311), (023) and (321) crystal planes in nickel selenide (JCPDS No.41-1495) and cobalt selenide (JCPDS No. 09-0234). As shown in fig. 4, it can be seen from the X-ray photoelectron spectrum diagram of the nickel selenide cobalt/carbon composite material that elements such as selenium, carbon, cobalt, nickel, etc. are present in the composite material. The cyclic voltammogram of the nickel-cobalt selenide/carbon composite material at different scanning speeds is shown in fig. 5, and the nickel-cobalt selenide/carbon composite material has a pair of obvious redox peaks.
(5) Dispersing the nickel cobalt selenide/carbon composite material in ultrapure water to obtain a dispersion liquid, transferring 10 mu L of the dispersion liquid by using a liquid transfer gun, coating the dispersion liquid on the surface of the glassy carbon electrode, and drying by using an infrared lamp to obtain the nickel cobalt selenide/carbon composite material modified glassy carbon electrode. And then, taking the nickel-cobalt selenide/carbon composite material modified glassy carbon electrode as a working electrode, a saturated calomel electrode as an auxiliary electrode, a platinum sheet electrode as a counter electrode and 2mol/L KOH as electrolyte, and performing constant current charge and discharge test and cycle stability test under the current density of 10A/g on the nickel-cobalt selenide/carbon composite material through an electrochemical workstation at the current density of 1A/g. Fig. 6 is a constant current charge and discharge test chart of the nickel cobalt selenide/carbon composite material, and the nickel cobalt selenide/carbon composite material obtained by calculation according to the formula (a) has a high specific capacitance when the current density is 1A/g, which can reach 1675F/g.
In the formula (a), Cs represents specific capacitance, I represents current, t represents discharge time, m represents the mass of the nickel-cobalt selenide/carbon composite material modified on the glassy carbon electrode, and V represents a potential window.
Fig. 7 is a cycle stability test chart of the nickel-cobalt selenide/carbon composite material, and after 5000 times of charging and discharging, the capacitance retention rate is 88.3%, and the cycle stability is high.
Comparative example one:
a preparation method of a metal organic framework ZIF-67 comprises the following steps:
(1) weighing 1.455g of cobalt nitrate hexahydrate and 1.642g of 2-methylimidazole, respectively dissolving in 80mL of anhydrous methanol, carrying out ultrasonic treatment until the solution is clear and transparent, quickly mixing the two solutions, allowing purple precipitate to appear, carrying out ultrasonic dispersion to uniformly mix the two solutions, carrying out self-assembly for 24h at room temperature, washing the solid matter obtained after centrifugal separation with anhydrous ethanol for several times, and drying in an oven at 60 ℃ for 12h to obtain the metal organic framework ZIF-67. As shown in FIG. 8, ZIF-67 exhibits a regular dodecahedral structure. As shown in FIG. 3, the X-ray powder diffraction pattern of ZIF-67 showed a characteristic diffraction peak of ZIF-67.
(2) And dispersing the obtained ZIF-67 into ultrapure water to obtain 2mg/mL dispersion, transferring 10 mu L of dispersion by using a liquid transfer gun, dripping the dispersion on the surface of a glassy carbon electrode, and drying by using an infrared lamp to obtain the ZIF-67 modified glassy carbon electrode. And then, taking a ZIF-67 modified glassy carbon electrode as a working electrode, a saturated calomel electrode as an auxiliary electrode, a platinum sheet electrode as a counter electrode and 2mol/L KOH as electrolyte, and carrying out constant current charge-discharge test and cycle stability test on the ZIF-67 through an electrochemical workstation. According to the constant current charge-discharge test chart of the ZIF-67 in FIG. 6, the specific capacitance of the ZIF-67 is only 81.4F/g when the current density is 1A/g can be calculated by the formula (a). From the cycle stability test result of the ZIF-67 in fig. 7, it can be seen that the capacity retention rate is 78.3% after 5000 times of charge and discharge.
Comparative example two:
a preparation method of a nickel cobalt-layered double hydroxide material comprises the following steps:
(1) weighing 1.455g of cobalt nitrate hexahydrate and 1.642g of 2-methylimidazole, respectively dissolving in 80mL of anhydrous methanol, carrying out ultrasonic treatment until the solution is clear and transparent, quickly mixing the two solutions, allowing purple precipitate to appear, carrying out ultrasonic dispersion to uniformly mix the two solutions, carrying out self-assembly for 24h at room temperature, washing the solid matter obtained after centrifugal separation with anhydrous ethanol for several times, and drying in an oven at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) Weighing 80mg of metal organic frame ZIF-67 powder in the step (1) and dissolving in 15mL of absolute ethyl alcohol, weighing 160mg of nickel nitrate hexahydrate and dissolving in 10mL of absolute ethyl alcohol, after uniform ultrasonic dispersion, quickly adding the nickel nitrate hexahydrate ethanol solution into the ZIF-67 ethanol solution, continuously stirring for 30min at 90 ℃, washing solid substances obtained after centrifugal separation with absolute ethyl alcohol for several times, and drying in an oven at 60 ℃ for 12h to obtain the nickel-cobalt-layered double hydroxide. As shown in fig. 9, the nickel-cobalt-layered double hydroxide exhibits a nano-layered structure, and the overall structure remains polyhedral. As shown in fig. 3, the X-ray powder diffraction pattern of the nickel cobalt-layered double hydroxide shows characteristic diffraction peaks of the nickel cobalt-layered double hydroxide, which appear at 2 θ ═ 11.3 °, 22.8 °, 32.8 °, 60.5 ° corresponding to the (003), (006), (012), and (110) crystal planes in the nickel cobalt-layered double hydroxide (JCPDS No. 33-0429).
(3) Dispersing the obtained nickel-cobalt-layered double hydroxide into ultrapure water to obtain 2mg/mL dispersion liquid, transferring 10 mu L of dispersion liquid by using a liquid transfer gun, dripping the dispersion liquid on the surface of a glassy carbon electrode, and drying by using an infrared lamp to obtain the nickel-cobalt-layered double hydroxide modified glassy carbon electrode. Then, a nickel-cobalt-layered double hydroxide modified glassy carbon electrode is used as a working electrode, a saturated calomel electrode is used as an auxiliary electrode, a platinum sheet electrode is used as a counter electrode, 2mol/L KOH is used as electrolyte, and the nickel-cobalt-layered double hydroxide is subjected to constant current charge-discharge testing and cycle stability testing through an electrochemical workstation. According to the constant current charge-discharge test chart of the nickel cobalt-layered double hydroxide in fig. 6, the specific capacitance of the nickel cobalt-layered double hydroxide is 621.8F/g when the current density is 1A/g through the formula (a). As can be seen from the cycle stability test results of the nickel-cobalt-layered double hydroxide in fig. 7, the capacity retention rate is only 51.3% after 5000 times of charging and discharging.
Comparative example three:
a preparation method of a nickel cobalt selenide material comprises the following steps:
(1) weighing 1.455g of cobalt nitrate hexahydrate and 1.642g of 2-methylimidazole, respectively dissolving in 80mL of anhydrous methanol, carrying out ultrasonic treatment until the solution is clear and transparent, quickly mixing the two solutions, allowing purple precipitate to appear, carrying out ultrasonic dispersion to uniformly mix the two solutions, carrying out self-assembly for 24h at room temperature, washing the solid matter obtained after centrifugal separation with anhydrous ethanol for several times, and drying in an oven at 60 ℃ for 12h to obtain the metal organic framework ZIF-67.
(2) Weighing 80mg of metal organic frame ZIF-67 powder in the step (1) and dissolving in 15mL of absolute ethyl alcohol, weighing 160mg of nickel nitrate hexahydrate and dissolving in 10mL of absolute ethyl alcohol, after uniform ultrasonic dispersion, quickly adding the nickel nitrate hexahydrate ethanol solution into the ZIF-67 ethanol solution, continuously stirring for 30min at 90 ℃, washing solid substances obtained after centrifugal separation with absolute ethyl alcohol for several times, and drying in an oven at 60 ℃ for 12h to obtain the nickel-cobalt-layered double hydroxide.
(3) Weighing 0.1g of nickel cobalt-layered double hydroxide powder obtained in the step (2) and 0.2g of selenium powder, mixing and stirring uniformly, placing in a quartz container, placing in a tube furnace, and selenizing at 350 ℃ for 90min under the argon atmosphere to obtain the selenium nickel cobalt. As shown in fig. 10, nickel-cobalt selenide exhibits a polyhedral structure with a very rough surface. As shown in fig. 3, the X-ray powder diffraction pattern of nickel-cobalt selenide shows that it has a plurality of characteristic diffraction peaks at 2 θ of 30.0 °, 33.6 °, 37.0 °, 43.0 °, 50.9 °, 55.7 °, 58.0 °, corresponding to the (200), (210), (211), (220), (311), (023) and (321) crystal planes of nickel selenide (JCPDS No.41-1495) and cobalt selenide (JCPDS No.09-0234), respectively.
(4) Dispersing the obtained nickel cobalt selenide into ultrapure water to obtain 2mg/mL dispersion liquid, transferring 10 mu L of dispersion liquid by using a liquid transfer gun, dripping the dispersion liquid on the surface of a glassy carbon electrode, and drying by using an infrared lamp to obtain the nickel cobalt selenide modified glassy carbon electrode. And then, taking the nickel-cobalt selenide modified glassy carbon electrode as a working electrode, a saturated calomel electrode as an auxiliary electrode, a platinum sheet electrode as a counter electrode and 2mol/L KOH as electrolyte, and carrying out constant current charge-discharge test and cycle stability test on the nickel-cobalt selenide through an electrochemical workstation. According to the constant current charge-discharge test chart of nickel selenide cobalt in fig. 6, the specific capacitance of the nickel selenide cobalt is 1241.4F/g when the current density is 1A/g through calculation according to the formula (a). As can be seen from the cycle stability test result of nickel selenide cobalt in fig. 7, the capacitance retention rate is only 57.1% after 5000 times of charging and discharging.
As can be seen from the above examples and comparative examples, the nickel-cobalt-layered double hydroxide derived from ZIF-67 was selenized, and the porous structure was favorable for the transport of electrons and electrolyte ions at the electrode/electrolyte interface. And then the carbon layer is wrapped on the surface of the nickel cobalt selenide, so that the stability of the nickel cobalt selenide composite material is effectively improved. The preparation method of the nickel cobalt selenide/carbon composite material is simple and easy to implement, and the composite material has higher specific capacitance and better cycle stability when being used for the electrode of the super capacitor. The embodiment is derived on the basis of a comparative example, the nickel cobalt-layered double hydroxide in the comparative example II is derived from the self-assembled ZIF-67 in the comparative example I, selenization treatment is carried out on the nickel cobalt-layered double hydroxide in the comparative example II to convert the nickel cobalt-layered double hydroxide into nickel cobalt selenide in the comparative example III, and then carbonization treatment is carried out on the nickel cobalt selenide in the comparative example III to obtain the nickel cobalt selenide/carbon composite material in the embodiment. In the embodiment, the selenized nickel-cobalt/carbon composite material has a rich pore channel structure, and is beneficial to the transmission of electrons and electrolyte ions at an electrode/electrolyte interface. The selenium element has higher conductivity, the introduction of the selenium element effectively improves the conductivity of the nickel selenide cobalt/carbon composite material in the embodiment, and the wrapping of the carbon layer inhibits the volume change of the nickel selenide cobalt/carbon composite material in the embodiment in the charging and discharging process, so that the stability of the nickel selenide cobalt/carbon composite material is effectively improved. Therefore, the embodiment has a better technical effect.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. The selenium nickel cobalt/carbon composite material is characterized in that nickel cobalt-layered double hydroxide derived from a metal organic framework ZIF-67 is subjected to selenization treatment to obtain selenium nickel cobalt, and then glucose is used as a carbon source to carry out carbon coating to prepare the selenium nickel cobalt/carbon composite material.
2. The method of preparing a nickel-cobalt-selenide/carbon composite material according to claim 1, comprising the steps of:
preparing a metal organic framework ZIF-67 by adopting cobalt nitrate hexahydrate and 2-methylimidazole, mixing an ethanol solution of the metal organic framework ZIF-67 and an ethanol solution of nickel nitrate hexahydrate, magnetically stirring, carrying out centrifugal separation to obtain a nickel cobalt-layered double hydroxide, selenizing the nickel cobalt-layered double hydroxide to obtain nickel cobalt selenide, carrying out hydrothermal reaction on the nickel cobalt selenide in a glucose solution, and calcining a hydrothermal product to obtain the nickel cobalt selenide/carbon composite material.
3. The method of preparing a nickel-cobalt-selenide/carbon composite material according to claim 2, comprising the steps of:
weighing cobalt nitrate hexahydrate and 2-methylimidazole, respectively dissolving the cobalt nitrate hexahydrate and the 2-methylimidazole in absolute methanol, carrying out ultrasonic treatment until the solution is clear and transparent, mixing the two solutions, carrying out ultrasonic dispersion after purple precipitation occurs, uniformly mixing the two solutions, carrying out self-assembly at room temperature, finishing the reaction, washing a solid substance obtained after centrifugal separation for several times by using absolute ethyl alcohol, and drying the solid substance to obtain a metal organic framework ZIF-67;
weighing nickel nitrate hexahydrate and a metal organic framework ZIF-67, respectively dissolving the nickel nitrate hexahydrate and the metal organic framework ZIF-67 in absolute ethyl alcohol, then quickly adding an ethanol solution of the nickel nitrate hexahydrate into an ethanol solution of the ZIF-67, carrying out magnetic stirring, after the reaction is finished, washing a solid substance obtained after centrifugal separation for several times by using absolute ethyl alcohol, and drying to obtain nickel-cobalt-layered double hydroxide;
selenium powder and nickel cobalt-layered double hydroxide are mixed and stirred uniformly and then are placed in a quartz container, and selenization treatment is carried out in a tube furnace under the argon atmosphere to obtain nickel cobalt selenide;
immersing nickel cobalt selenide in a glucose solution, ultrasonically dispersing uniformly, transferring to a reaction kettle for hydrothermal reaction, washing a solid substance obtained after centrifugal separation with deionized water and absolute ethyl alcohol for several times, drying to obtain a hydrothermal product, and calcining the hydrothermal product in a tubular furnace under the condition of argon to obtain the nickel cobalt selenide/carbon composite material.
4. The method for preparing a nickel-cobalt selenide/carbon composite material according to claim 3, wherein the mass ratio of cobalt nitrate hexahydrate to 2-methylimidazole is 0.4-1.2; the mass-volume ratio of the cobalt nitrate hexahydrate to the absolute ethyl alcohol is 1-2 g: 60-100 mL; the mass-volume ratio of the 2-methylimidazole to the absolute ethyl alcohol is 1-2 g: 60-100 mL; the self-assembly time is 12-36 h; the drying temperature of the reaction product of the cobalt nitrate hexahydrate and the 2-methylimidazole is 50-100 ℃, and the drying time is 10-20 hours.
5. The method for preparing a nickel-cobalt-selenide/carbon composite material according to claim 3, wherein the mass ratio of nickel nitrate hexahydrate to ZIF-67 is 1.8-2.2; the mass volume ratio of the nickel nitrate hexahydrate to the absolute ethyl alcohol is 20-40 g: 1-3L; the ratio of ZIF-67 to absolute ethyl alcohol is 5-10 g: 1-2L; the reaction temperature of nickel nitrate hexahydrate and ZIF-67 is 60-120 ℃, and the reaction time is 20-40 min; the drying temperature of the nickel nitrate hexahydrate and the ZIF-67 product is 50-100 ℃, and the drying time is 10-20 hours.
6. The method for preparing a nickel-cobalt selenide/carbon composite material according to claim 3, wherein the mass ratio of the selenium powder to the nickel-cobalt layered double hydroxide is 2-6: 1-3; the selenizing temperature in the tube furnace is 300-400 ℃, and the selenizing time is 1-2 hours.
7. The method for preparing a nickel-cobalt selenide/carbon composite material according to claim 3, wherein the mass-to-volume ratio of nickel-cobalt selenide, glucose and solvent water is 5-15 mg: 30-50 mg: 8-12 mL;
the hydrothermal reaction temperature is 160-200 ℃, and the hydrothermal reaction time is 8-12 h;
the drying temperature of the hydrothermal product is 50-100 ℃, and the drying time is 10-20 h;
the calcining temperature in the tubular furnace is 400-500 ℃, and the calcining time is 1-3 h.
8. The use of the nickel-cobalt selenide/carbon composite according to claim 1 in supercapacitor electrode materials.
9. The application of claim 8, wherein the nickel-cobalt selenide/carbon composite material is dispersed in ultrapure water to obtain a dispersion liquid, the dispersion liquid is removed and dropwise coated on the surface of the glassy carbon electrode, and the glassy carbon electrode modified by the nickel-cobalt selenide/carbon composite material is obtained after drying under an infrared lamp.
10. The application of claim 9, wherein the selenized nickel-cobalt/carbon composite material modified glassy carbon electrode is used as a working electrode, the saturated calomel electrode is used as an auxiliary electrode, the platinum sheet electrode is used as a counter electrode, and 2mol/L KOH is used as an electrolyte.
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