CN110563049A - cobalt zinc sulfide nano material and preparation method and application thereof - Google Patents
cobalt zinc sulfide nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a cobalt zinc sulfide nano material and a preparation method and application thereof, belonging to the field of nano composite material preparation. The cobalt zinc sulfide nano material provided by the invention is in a bead curtain shape, the length of the cobalt zinc sulfide nano material is 15-18 mu m, the width of the cobalt zinc sulfide nano material is 2.5-3.1 mu m, and the diameter of beaded spherical particles in the cobalt zinc sulfide nano material is 360-400 nm. The cobalt zinc sulfide nano material provided by the invention has the characteristics of regular and ordered bead curtain-shaped appearance and large specific surface, a large number of active sites are exposed, and the electrochemical cycle stability of the material is improved.
Description
Technical Field
The invention belongs to the field of preparation of nano composite materials, and particularly relates to a cobalt zinc sulfide nano material and a preparation method and application thereof.
Background
Super capacitors, which are one of the representatives of the products derived from energy storage technology, have been widely studied because of their advantages of fast charge and discharge, high power density, and long life.
The electrode is a key component for constructing a high-efficiency device, and the composition and microstructure of the electrode material have a remarkable influence on the performance of the energy storage device. Currently, various types of electrode materials are widely reported, including transition metal oxides and metal sulfides. Compared with metal oxides, metal sulfides have higher conductivity and excellent rate capability. Bimetallic sulfides have richer redox sites and higher electronic conductivity than monometallic sulfides, and these electrochemical advantages mainly benefit from a perfect combination of material compositions. In addition, the morphology and microstructure of the material become key factors for improving the performance of the energy storage device. The metal sulfide electrode material has various shapes, such as a microstructure of a line shape, a sheet shape, a spherical shape, a flower shape and the like.
Patent CN108597898A provides a method for preparing cobalt zinc sulfide nano material, in which zinc salt, cobalt salt and organic ligand are reacted to form a metal organic framework material as a nano precursor, and then the precursor and a sulfur-containing substance are subjected to a vulcanization reaction to form a hollow cobalt zinc sulfide nano material.
Disclosure of Invention
In view of the above, the invention provides a cobalt zinc sulfide nano material, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a cobalt zinc sulfide nano material, which is in a bead curtain shape, wherein the length of the cobalt zinc sulfide nano material is 15-18 mu m, the width of the cobalt zinc sulfide nano material is 2.5-3.1 mu m, and the diameter of beaded spherical particles in the cobalt zinc sulfide nano material is 360-400 nm.
The invention also provides a preparation method of the cobalt zinc sulfide nano material in the technical scheme, which comprises the following steps:
mixing soluble zinc salt, soluble cobalt salt, a pH auxiliary agent, water and three-dimensional foam nickel to perform a first hydrothermal reaction to obtain a zinc-cobalt-oxygen precursor;
And mixing the zinc-cobalt-oxygen precursor with a vulcanizing agent to perform a second hydrothermal reaction to obtain the cobalt-zinc sulfide nano material.
Preferably, the pH adjuvant is a mixture of ammonium fluoride and hexamethylenetetramine.
Preferably, the molar ratio of ammonium fluoride to hexamethylenetetramine is 1: 2.
Preferably, the vulcanizing agent is added in the form of a vulcanizing agent solution, and the molar concentration of the vulcanizing agent solution is 10-60 mmol/L.
Preferably, the temperature of the first hydrothermal reaction is 140-200 ℃ and the time is 8-14 h.
Preferably, the temperature of the second hydrothermal reaction is 140 ℃ and the time is 6-12 h.
Preferably, the molar volume ratio of the soluble zinc salt to water is 5-30 mmol:1L of the compound.
Preferably, the molar ratio of the soluble zinc salt to the soluble cobalt salt is 1: 2.
The invention also provides the application of the cobalt zinc sulfide nano material prepared by the technical scheme or the preparation method in the technical scheme in the fields of lithium batteries, electrode materials of super capacitors and new electrocatalytic energy.
The invention provides a cobalt zinc sulfide nano material, which is in a bead curtain shape, wherein the length of the cobalt zinc sulfide nano material is 15-18 mu m, the width of the cobalt zinc sulfide nano material is 2.5-3.1 mu m, and the diameter of beaded spherical particles in the cobalt zinc sulfide nano material is 360-400 nm. The cobalt zinc sulfide nano material provided by the invention has the characteristics of regular and ordered bead curtain-shaped appearance and large specific surface, a large number of active sites are exposed, and the electrochemical performance and the electrochemical cycle stability of the material are improved. The results of the examples show that when the cobalt zinc sulfide nano material prepared by the invention is used as a super capacitor electrode material, the specific capacitance can still be kept between 86.9 and 92.87 percent after 5000 times of cyclic charge and discharge under the condition that the current density is 5A/g, and the cobalt zinc sulfide nano material has good electrochemical stability.
Furthermore, the preparation method provided by the invention has the advantages of simple process, good reproducibility, environmental protection, safety, accordance with the requirement of environmental protection, low cost of used raw materials and wide source. The method takes three-dimensional foam nickel as a substrate material, so that the surface of the cobalt zinc sulfide grows uniformly and regularly, agglomeration is not easy to occur, and the conductivity of the material is improved; the pH auxiliary agent has the function of adjusting the structure orientation, and in the first hydrothermal reaction process, the pH auxiliary agent adsorbs the crystal face of the generated zinc-cobalt-oxygen precursor, so that the growth direction of the zinc-cobalt-oxygen precursor can be controlled; in the second reaction process, the vulcanizing agent and the generated zinc-cobalt-oxygen precursor generate ion exchange reaction, so that the secondary growth of low-index crystal faces in the zinc-cobalt-oxygen precursor is promoted, a large number of active sites on the crystal faces are exposed, and the electrochemical cycle stability of the cobalt-zinc sulfide nano material is improved.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an XRD pattern of a zinc cobalt oxide precursor and a cobalt zinc sulfide nanomaterial prepared in example 1;
FIG. 2 is SEM images of the zinc-cobalt-oxygen precursor prepared in example 1 under different magnifications, wherein a is a SEM image under a 6000-magnification lens, an embedded image in a is a SEM image under an 800-magnification lens, and b is a SEM image under a 50000-magnification lens;
Fig. 3 is SEM images of cobalt zinc sulfide nanomaterial prepared in example 1 under different magnification, wherein a is SEM image under 1200 magnification, b is SEM image under 2500 magnification, c is SEM image under 10000 magnification, and d is SEM image under 2000 magnification;
FIG. 4 is a TEM image of the cobalt zinc sulfide nanomaterial prepared in example 1;
FIG. 5 is SEM images of the zinc-cobalt-oxygen precursor prepared in example 2 under different magnifications, wherein a is a SEM image under a 5000-magnification microscope, an embedded image in a is a SEM image under an 800-magnification microscope, and b is a SEM image under a 20000-magnification microscope;
fig. 6 is SEM images of the zinc-cobalt-oxygen precursor prepared in example 3 under different magnification, wherein a is SEM image under 1000 magnification, b is SEM image under 2000 magnification, c is SEM image under 10000 magnification, and d is SEM image under 40000 magnification, and it can be seen from the images that the micro-morphology of the prepared zinc-cobalt-oxygen precursor nano material is in a nano flower shape composed of nano sheets;
FIG. 7 is SEM images of the porous cobalt zinc sulfide nano-material prepared in example 4 under different magnifications, wherein a is an SEM image under a 1000-magnification lens, b is an SEM image under a 4000-magnification lens, c is an SEM image under an 13000-magnification lens, and d is an SEM image under an 25000-magnification lens;
Fig. 8 is SEM images of the porous cobalt zinc sulfide nanomaterial prepared in example 5 under different magnifications, wherein a is a SEM image under a 1000-fold mirror, b is a SEM image under a 7000-fold mirror, c is a SEM image under a 30000-fold mirror, and d is a SEM image under a 100000-fold mirror;
Fig. 9 is a graph of the cycling stability life test of the cobalt zinc sulfide nanomaterials prepared in examples 1, 4 and 5.
Detailed Description
The invention provides a cobalt zinc sulfide nano material, which is in a bead curtain shape, wherein the length of the cobalt zinc sulfide nano material is 15-18 mu m, the width of the cobalt zinc sulfide nano material is 2.5-3.1 mu m, and the diameter of beaded spherical particles in the cobalt zinc sulfide nano material is 360-400 nm, and is further preferably 375 nm. The cobalt zinc sulfide nano material provided by the invention has the characteristics of regular and ordered bead curtain-shaped appearance and large specific surface, a large number of active sites are exposed, and the electrochemical performance and the electrochemical cycle stability of the material are improved.
The invention also provides a preparation method of the cobalt zinc sulfide nano material in the technical scheme, which comprises the following steps:
Mixing soluble zinc salt, soluble cobalt salt, a pH auxiliary agent, water and three-dimensional foam nickel to perform a first hydrothermal reaction to obtain a zinc-cobalt-oxygen precursor;
And mixing the zinc-cobalt-oxygen precursor with a vulcanizing agent to perform a second hydrothermal reaction to obtain the cobalt-zinc sulfide nano material.
In the present invention, the starting materials used are not specifically described as being commercially available products which are conventional in the art.
According to the invention, soluble zinc salt, soluble cobalt salt, a pH auxiliary agent, water and three-dimensional foam nickel are mixed for a first hydrothermal reaction to obtain a zinc-cobalt-oxygen precursor.
in the present invention, the soluble zinc salt preferably comprises ZnCl2、Zn(NO3)2or Zn (CH)3COO)2The molar volume ratio of the soluble zinc salt to water is preferably 5-30 mmol:1L, and more preferably 15mmol: 1L. In the present invention, the soluble cobalt salt is preferably CoCl2、Co(NO3)2Or C4H6O4·Co·4H2o, the molar ratio of the soluble zinc salt to the soluble cobalt salt is preferably 1: 2.
In the invention, the molar concentration of the pH auxiliary agent is preferably 20-360 mmol, the pH auxiliary agent is preferably a mixture of ammonium fluoride and hexamethylenetetramine, the molar ratio of the ammonium fluoride to the hexamethylenetetramine is preferably 1:2, and the molar ratio of the soluble zinc salt to the ammonium fluoride is preferably 1: 2-4. The invention adopts pH auxiliary agent with specific concentration to adjust the structure orientation of the product, and in the first hydrothermal reaction process, the OH formed by the hydrolysis of ammonium fluoride and hexamethylenetetramine-With zinc cobaltthe ions form a ligand-zinc-cobalt precursor, which can inhibit the transverse growth of the special crystal face of the precursor, promote the vertical growth or horizontal growth of the precursor and form a nano-belt with a certain transverse-longitudinal ratio.
in the present invention, the water is preferably distilled water.
In the present invention, the volume of the three-dimensional nickel foam is preferably 0.1cm × 1cm × 5cm, and is preferably purchased from the source battery company of the shinny area force of taiyuan city. The invention adopts the three-dimensional foam nickel as the substrate, so that the zinc-cobalt-oxygen precursor grows uniformly and regularly on the surface of the zinc-cobalt-oxygen precursor, agglomeration is not easy to occur, the three-dimensional foam nickel has a three-dimensional structure, full contact between electrolyte and an active material is facilitated, and meanwhile, a foam nickel framework provides a channel for electron conduction and improves the conductivity of the material.
According to the invention, the three-dimensional foam nickel is preferably washed and dried in sequence, and then mixed with soluble zinc salt, soluble cobalt salt, pH auxiliary agent and water. In the present invention, the washing is preferably performed in the order of a dilute hydrochloric acid solution having a concentration of 20 wt%, acetone and distilled water. The specific operation of the cleaning is not particularly limited in the present invention, and a cleaning method known to those skilled in the art may be used. The drying operation is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
According to the invention, soluble zinc salt, soluble cobalt salt, pH auxiliary agent and water are preferably subjected to first mixing, and then are subjected to second mixing with the three-dimensional foamed nickel. In the invention, the first mixing is preferably carried out under ultrasonic conditions, and the ultrasonic time is preferably 5-10 min. The conditions of the ultrasound are not particularly limited in the present invention, and the ultrasound conditions known to those skilled in the art may be used. In the present invention, the first mixing means is preferably magnetic stirring. The magnetic stirring condition is not specially limited, and the mixed materials can be uniformly mixed. In the present invention, the second mixing is preferably performed in a reaction kettle, the mixing is preferably performed by stirring, and the stirring manner in the present invention is not particularly limited, and may be performed by a stirring manner known to those skilled in the art.
in the invention, the first hydrothermal reaction is preferably carried out in an oven, the temperature of the first hydrothermal reaction is preferably 140-200 ℃, more preferably 180 ℃, and the time is preferably 8-14 h, more preferably 12 h. The first hydrothermal reaction is carried out at a specific temperature, so that the transverse growth of a special crystal face of a precursor can be inhibited, the vertical growth or the horizontal growth of the special crystal face of the precursor is promoted, and a nanobelt with a certain transverse-longitudinal ratio is formed; if the temperature is too low, nanoneedles or nanowires are formed, and if the temperature is too high, nanosheets or flowers are formed. In the invention, the thickness of the nanobelt is preferably 48.8-78.5 nm. In the present invention, the aspect ratio is preferably 3.9 to 6.
After the first hydrothermal reaction is finished, the obtained first hydrothermal product is preferably sequentially cooled, washed and dried to obtain the zinc-cobalt-oxygen precursor. In the present invention, the cooling method is preferably natural cooling at room temperature. In the present invention, the washing is preferably performed in ethanol and deionized water in this order, and the number of washing is independently preferably 3. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the invention, the drying is preferably carried out under a vacuum condition, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 12-24 h. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
After obtaining the zinc-cobalt-oxygen precursor, mixing the zinc-cobalt-oxygen precursor with a vulcanizing agent to perform a second hydrothermal reaction to obtain the cobalt-zinc sulfide nano material.
In the present invention, the vulcanizing agent is preferably thioacetamide or sodium sulfide. In the invention, the mass of the zinc-cobalt-oxygen precursor is preferably 3-7 mg, and more preferably 4 mg. In the invention, the vulcanizing agent is preferably added in the form of a vulcanizing agent solution, and the molar concentration of the vulcanizing agent solution is preferably 10-60 mmol/L, and more preferably 60 mmol/L. According to the invention, a vulcanizing agent solution with a specific concentration is adopted to carry out vulcanization etching on the nanobelt prepared by the first hydrothermal reaction to form fine particles, the fine particles grow for the second time in the second hydrothermal reaction and are converged to form porous bead balls, and finally, a bead curtain-shaped cobalt zinc sulfide nano material in ordered arrangement is formed, so that the active sites of the electrochemical reaction are enlarged.
In the invention, the temperature of the second hydrothermal reaction is preferably 140 ℃, and the time is preferably 6-12 h, and more preferably 8 h. The method is used for carrying out a second hydrothermal reaction under a specific temperature condition, and can promote the divalent sulfur ions and the anions of the zinc-cobalt-oxygen precursor to carry out an ion exchange reaction, form a strong coordination bond, secondarily grow low-index crystal faces, expose the crystal faces to the maximum extent, and finally form the orderly-arranged bead curtain-shaped porous cobalt-zinc sulfide nano material.
After the second hydrothermal reaction is finished, the obtained second hydrothermal product is preferably sequentially cooled, washed and dried to obtain the cobalt zinc sulfide nano material. In the present invention, the cooling method is preferably natural cooling at room temperature. In the present invention, the washing is preferably performed in ethanol and deionized water in this order, and the number of washing is independently preferably 3. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the invention, the drying is preferably carried out under a vacuum condition, the drying temperature is preferably 60-80 ℃, and the drying time is preferably 12-24 h. The drying method is not particularly limited in the present invention, and a drying method known to those skilled in the art may be used.
The invention also provides the application of the cobalt zinc sulfide nano material prepared by the technical scheme or the cobalt zinc sulfide nano material prepared by the preparation method in the fields of lithium batteries, supercapacitors and electrocatalysis new energy.
The cobalt-zinc sulfide nano material provided by the present invention, the preparation method and the application thereof are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Taking commercial three-dimensional foam nickel, cutting the commercial three-dimensional foam nickel into strips with the dimensions of 1cm multiplied by 5cm multiplied by 0.3cm, cleaning the strips by using 20 wt% of dilute hydrochloric acid solution, acetone and distilled water, and drying the strips overnight for later use;
(2) Reacting ZnCl2And Co (NO)3)2Adding into distilled water to form mixed solution; wherein, ZnCl is contained in the mixed solution2has a molar concentration of 15mmol/L, Co (NO)3)2The three-dimensional foam nickel is added, and simultaneously a mixture of ammonium fluoride and hexamethylenetetramine as pH aids is added, wherein the molar concentration of the ammonium fluoride is 45mmol/L, the molar concentration of the hexamethylenetetramine is 90mmol/L, and the mixture is uniformly mixed under magnetic stirring after ultrasonic treatment for 5 min. And transferring the solution into a reaction kettle with a polytetrafluoroethylene substrate, sealing, placing in an oven, carrying out hydrothermal reaction at the reaction temperature of 180 ℃ for 12 hours, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the nano-belt-shaped zinc-cobalt-oxygen precursor nano-material.
(3) and adding the 4mg of zinc-cobalt oxide precursor into a thioacetamide solution for hydrothermal reaction, wherein the concentration of thioacetamide is 60mmol/L, reacting for 8 hours at 140 ℃, taking out, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and vacuum-drying for 12 hours at 60 ℃ to obtain the bead curtain-shaped porous cobalt-zinc sulfide nano material.
After the zinc-cobalt-oxygen precursor prepared in the embodiment is used as an electrode material of a supercapacitor and is circularly charged and discharged for 5000 times at a current density of 5A/g, an electrochemical result is tested, and the specific capacitance is 92.87%.
Fig. 1 is an XRD chart of the zinc-cobalt-oxygen precursor and the cobalt-zinc sulfide nanomaterial prepared in example 1, and it can be seen from the XRD chart that the positions and relative intensities of the diffraction peaks are respectively matched with JPCDS cards (32-1468) and JPCDS cards (47-1456), indicating that the products are respectively the zinc-cobalt-oxygen precursor nanomaterial and the cobalt-zinc sulfide nanomaterial.
FIG. 2 is SEM images of the zinc-cobalt-oxygen precursor prepared in example 1 under different power mirrors, wherein a is an SEM image under a 6000 power mirror, an embedded image in the image a is an SEM image under an 800 power mirror, and b is an SEM image under a 50000 power mirror, and it can be seen from the images that the micro-morphology of the prepared zinc-cobalt-oxygen precursor nano-material is in an orderly nano-belt shape, the length of the nano-belt is 13-15 μm, the width of the nano-belt is 2.5-3.3 μm, and the thickness of the nano-belt is 48.8-78.5 nm.
FIG. 3 is SEM images of the cobalt zinc sulfide nano-material prepared in example 1 under different power mirrors, wherein a is a 1200 power SEM image, b is a 2500 power SEM image, c is a 10000 power SEM image, and d is a 20000 power SEM image, and it can be seen from the images that the micro-morphology of the prepared cobalt zinc sulfide nano-material is in an ordered and regular bead curtain shape, the length of the bead curtain shape is 15-18 μm, the width of the bead curtain shape is 2.8-3.3 μm, and the diameter of the bead spherical particles is 370-400 nm.
FIG. 4 is a TEM image of the cobalt-zinc sulfide nanomaterial prepared in example 1, and it can be seen from the TEM image that the beads have a porous structure, which is favorable for wetting with electrolyte and improving its electrochemical performance, and the diameter of the spherical beads is 375nm, which is consistent with the measurement result in FIG. 3.
Example 2
In this example, the zinc cobalt oxide precursor was prepared in the same manner as in example 1, except that the first hydrothermal reaction temperature was 140 ℃.
fig. 5 is SEM images of the zinc cobalt oxide precursor prepared in example 2 under different magnification, wherein a is SEM image under 5000 magnification, an embedded image in a is SEM image under 800 magnification, b is SEM image under 20000 magnification, and it can be seen from the images that the micro-morphology of the prepared zinc cobalt oxide precursor nano-material is nanowire or nanowire-shaped.
After the zinc-cobalt-oxygen precursor prepared in the embodiment is used as an electrode material of a supercapacitor and is circularly charged and discharged for 5000 times at a current density of 5A/g, an electrochemical result is tested, and the specific capacitance is 63.5%.
Example 3
In this example, the zinc-cobalt-oxygen precursor was prepared in the same manner as in example 1, except that the first hydrothermal reaction temperature was 200 ℃.
Fig. 6 is SEM images of the zinc-cobalt-oxygen precursor prepared in example 3 under different magnification, where a is a SEM image under 1000 magnification, b is a SEM image under 2000 magnification, c is a SEM image under 10000 magnification, and d is a SEM image under 40000 magnification, and it can be seen from the SEM images that the micro-morphology of the prepared zinc-cobalt-oxygen precursor nanomaterial is in a nano flower shape composed of nano sheets.
After the zinc-cobalt-oxygen precursor prepared by the embodiment is used as an electrode material of a super capacitor and is circularly charged and discharged for 5000 times under the condition that the current density is 5A/g, the electrochemical result is tested, and the specific capacitance is 80.2%.
Example 4
In this example, the preparation method of the porous cobalt zinc sulfide nano material is the same as that of example 1, except that the molar concentration of thioacetamide is 10 mmol/L.
Fig. 7 is SEM images of the porous cobalt zinc sulfide nanomaterial prepared in example 4 under different magnification mirrors, where a is a SEM image under 1000 magnification mirrors, b is a SEM image under 4000 magnification mirrors, c is a SEM image under 13000 magnification mirrors, and d is a SEM image under 25000 magnification mirrors, and it can be seen from the images that the morphology of the prepared porous cobalt zinc sulfide nanomaterial still remains substantially in a shape of a nanobelt, but a few sulfide particles are attached to the surface of the nanobelt.
The porous cobalt zinc sulfide nano material prepared by the embodiment is used as a super capacitor electrode material, and after 5000 times of cyclic charge and discharge under the current density of 5A/g, the electrochemical result is tested, and the specific capacitance is 86.9%.
Example 5
In this example, the preparation method of the porous cobalt zinc sulfide nano material is the same as that of example 1, except that the molar concentration of thioacetamide is 40 mmol/L.
Fig. 8 is SEM images of the porous cobalt zinc sulfide nanomaterial prepared in example 5 under different magnifications, where a is a SEM image under 1000 magnifications, b is a SEM image under 7000 magnifications, c is a SEM image under 30000 magnifications, and d is a SEM image under 100000 magnifications, and it can be seen from the images that the morphology of the prepared porous cobalt zinc sulfide nanomaterial also maintains a nanobelt shape, but the surface of the nanobelt is full of sulfide particles.
The porous cobalt zinc sulfide nano material prepared by the embodiment is used as a super capacitor electrode material, and the specific capacitance is 89.17% by testing the electrochemical result after 5000 times of cyclic charge and discharge under the condition that the current density is 5A/g.
Fig. 9 is a cycle stability life test chart of the cobalt zinc sulfide nano materials prepared in examples 1, 4 and 5, and it can be seen from the chart that the bead curtain-shaped porous cobalt zinc sulfide nano material as the electrode material of the supercapacitor has a specific capacitance of 86.9% -92.87% after 5000 cycles of charge and discharge at a current density of 5A/g.
example 6
(1) Taking commercial three-dimensional foam nickel, cutting the commercial three-dimensional foam nickel into strips with the dimensions of 1cm multiplied by 5cm multiplied by 0.3cm, cleaning the strips by using 20 wt% of dilute hydrochloric acid, acetone and distilled water, and drying the strips overnight for later use;
(2) Adding Zn (NO)3)2and CoCl2Adding into distilled water to form mixed solution; wherein Zn (NO) is contained in the mixed solution3)2Is 5mmol/L in CoCl2the concentration of (A) is 10 mmol/L; and then adding the three-dimensional foamed nickel, and simultaneously adding ammonium fluoride and hexamethylenetetramine as pH aids, wherein the concentration of the ammonium fluoride is 10mmol/L, the concentration of the hexamethylenetetramine is 20mmol/L, and after ultrasonic treatment for 5min, uniformly mixing under magnetic stirring. And transferring the solution into a reaction kettle with a polytetrafluoroethylene substrate, sealing, placing in an oven, carrying out hydrothermal reaction at the reaction temperature of 140 ℃ for 6 hours, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and carrying out vacuum drying at the temperature of 60 ℃ for 24 hours to obtain the nano-strip zinc-cobalt-oxygen precursor nano-material.
(3) And adding the 3mg of zinc-cobalt oxide precursor into a thioacetamide solution for hydrothermal reaction, wherein the concentration of thioacetamide is 10mmol/L, reacting at 140 ℃ for 6 hours, taking out, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and vacuum-drying at 60 ℃ for 12 hours to obtain the bead curtain-shaped porous cobalt-zinc sulfide nano material.
The bead curtain-shaped porous cobalt zinc sulfide nano material prepared by the embodiment is used as a super capacitor electrode material, and after 5000 times of cyclic charge and discharge under the current density of 5A/g, the electrochemical result is tested, and the specific capacitance is 87.41%.
Example 7
(1) Taking commercial three-dimensional foam nickel, cutting the commercial three-dimensional foam nickel into strips with the dimensions of 1cm multiplied by 5cm multiplied by 0.3cm, cleaning the strips by using 20 wt% of dilute hydrochloric acid, acetone and distilled water, and drying the strips overnight for later use;
(2) adding Zn (CH)3COO)2And C4H6O4·Co·4H2Adding O into distilled water to form a mixed solution; wherein Zn (CH) is contained in the mixed solution3COO)2Has a concentration of 30mmol/L, C4H6O4·Co·4H2The concentration of O is 60 mmol/L; and then adding the three-dimensional foamed nickel, and simultaneously adding ammonium fluoride and hexamethylenetetramine as pH aids, wherein the concentration of the ammonium fluoride is 120mmol/L, the concentration of the hexamethylenetetramine is 120mmol/L, and after ultrasonic treatment for 5min, uniformly mixing under magnetic stirring. And transferring the solution into a reaction kettle with a polytetrafluoroethylene substrate, sealing, placing in an oven, carrying out hydrothermal reaction at the reaction temperature of 200 ℃ for 14 hours, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and carrying out vacuum drying at the temperature of 80 ℃ for 12 hours to obtain the nano-strip zinc-cobalt-oxygen precursor nano-material.
(3) and adding the 7mg of zinc-cobalt-oxygen precursor into a sodium sulfide solution for hydrothermal reaction, wherein the concentration of sodium sulfide is 40mmol/L, reacting at 140 ℃ for 12 hours, taking out, cooling to room temperature, washing with ethanol and deionized water for three times respectively, and vacuum-drying at 60 ℃ for 12 hours to obtain the bead curtain-shaped porous cobalt-zinc sulfide nano material.
The bead curtain-shaped porous cobalt zinc sulfide nano material prepared by the embodiment is used as a super capacitor electrode material, and an electrochemical result is tested after 5000 times of cyclic charge and discharge under the condition that the current density is 5A/g, so that the specific capacitance is 89.37%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The cobalt-zinc sulfide nano material is characterized by being in a bead curtain shape, the length of the cobalt-zinc sulfide nano material is 15-18 mu m, the width of the cobalt-zinc sulfide nano material is 2.5-3.1 mu m, and the diameter of beaded spherical particles in the cobalt-zinc sulfide nano material is 360-400 nm.
2. The method for preparing the cobalt-zinc sulfide nano material of claim 1, which is characterized by comprising the following steps of:
Mixing soluble zinc salt, soluble cobalt salt, a pH auxiliary agent, water and three-dimensional foam nickel to perform a first hydrothermal reaction to obtain a zinc-cobalt-oxygen precursor;
And mixing the zinc-cobalt-oxygen precursor with a vulcanizing agent to perform a second hydrothermal reaction to obtain the cobalt-zinc sulfide nano material.
3. The method of claim 2, wherein the pH adjuvant is a mixture of ammonium fluoride and hexamethylenetetramine.
4. The method according to claim 3, wherein the molar ratio of ammonium fluoride to hexamethylenetetramine is 1: 2.
5. the preparation method according to claim 2, wherein the vulcanizing agent is added in the form of a vulcanizing agent solution, and the molar concentration of the vulcanizing agent solution is 10-60 mmol/L.
6. the preparation method according to claim 2, wherein the temperature of the first hydrothermal reaction is 140 to 200 ℃ and the time is 8 to 14 hours.
7. The preparation method according to claim 2, wherein the temperature of the second hydrothermal reaction is 140 ℃ and the time is 6-12 h.
8. The preparation method according to claim 2, wherein the molar volume ratio of the soluble zinc salt to water is 5-30 mmol:1L of the compound.
9. The preparation method according to claim 2, wherein the molar ratio of the soluble zinc salt to the soluble cobalt salt is 1: 2.
10. the cobalt zinc sulfide nano material of claim 1 or the cobalt zinc sulfide nano material prepared by the preparation method of any one of claims 2 to 9 is applied to the fields of lithium batteries, supercapacitors and electrocatalytic new energy.
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