CN111463026B - Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof - Google Patents
Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a nickel-cobalt-sulfur/carbon nano tube composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing a mixed solution containing carbon nano tubes, nickel salt, cobalt salt and a precipitator; performing first microwave heating treatment on the mixed solution, then adding a sulfur source, and performing second microwave heating treatment to generate the nickel-cobalt-sulfur/carbon nano tube composite material; wherein the carbon nano tube is provided with electronegative groups, and the precipitator is hydrolyzed to generate hydroxide ions in the heating process of the mixed solution. The preparation method can effectively avoid the agglomeration between nickel-cobalt-sulfur nano particles, and meanwhile, the carbon nano tube has excellent conductivity and mechanical stability, and the carbon nano tube is compounded with nickel-cobalt-sulfur to obtain excellent electrochemical performance; the microwave heating synthesis is beneficial to explosive nucleation, can generate a large number of defects, leads to more active site exposure, and further improves the electrochemical performance of the nickel-cobalt-sulfur/carbon nanotube composite material.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nickel-cobalt-sulfur/carbon nano tube composite material as well as a preparation method and application thereof.
Background
With the increasing energy crisis and environmental pollution, there is a great need to develop and utilize new energy and corresponding energy storage devices, and supercapacitors are favored by researchers due to their advantages of high power density, fast charge and discharge speed, long cycle life, safety, and no maintenance. The performance of the supercapacitor is greatly dependent on the performance of the electrode material, namely spinel-structured nickel cobalt sulfide (NiCo)2S4，CoNi2S4) When the conductive nickel-cobalt composite material is used as an electrode material, the conductivity is higher than that of a nickel-cobalt double metal oxide, single-component nickel sulfide and cobalt sulfide by more than 2 orders of magnitude; in addition, nickel-cobalt-sulfur can provide more abundant redox reaction than corresponding single-component sulfide, so that the nickel-cobalt-sulfur has wide application prospect in the field of electrochemistry. However, in the practical application process, nickel-cobalt-sulfur has the defects of low specific surface area, easy agglomeration and poor structural stability in the charging and discharging processes, thereby resulting in low rate performance and cycle stability.
At present, the synthesis of the nickel-cobalt-sulfur compound is generally carried out by a water/solvent thermal method, an electrodeposition method, a self-assembly method, a template method and the like. Although the prepared material can present more excellent performance, the method has the defects of long reaction time, rigorous synthesis conditions, complicated method or low yield and the like.
Therefore, the prior art is in need of improvement
Disclosure of Invention
The invention aims to provide a nickel-cobalt-sulfur/carbon nanotube composite material and a preparation method and application thereof, and aims to solve the technical problems that the existing nickel-cobalt-sulfur material is easy to agglomerate and poor in stability, so that the electrochemical performance is not ideal.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a nickel-cobalt-sulfur/carbon nano tube composite material, which comprises the following steps:
preparing a mixed solution containing carbon nano tubes, nickel salt, cobalt salt and a precipitator;
performing first microwave heating treatment on the mixed solution, then adding a sulfur source, and performing second microwave heating treatment to generate the nickel-cobalt-sulfur/carbon nano tube composite material;
wherein the carbon nano tube is provided with electronegative groups, and the precipitator is heated and hydrolyzed in the mixed solution to generate hydroxide ions.
The invention provides a preparation method of a nickel-cobalt-sulfur/carbon nano tube composite material, which comprises the step of carrying out first microwave heating treatment on a mixed solution containing carbon nano tubes, nickel salt, cobalt salt and a precipitator, wherein the carbon nano tubes have electronegative groups, and metal cations (Ni) in the mixed solution2+、Co2+) Will combine with electronegative group on the carbon nanotube through the electrostatic adsorption, thus form the nucleation site, the precipitant is hydrolyzed in mixed solution in the microwave heating process and produces hydroxyl ion, hydroxyl ion reacts with metal cation of the nucleation site on the carbon nanotube to produce the precursor; and carrying out microwave heating reaction on the subsequently added sulfur source and the precursor so as to carry out heterogeneous nucleation on the carbon nano tube to grow nickel-cobalt-sulfur nano particles and generate the nickel-cobalt-sulfur/carbon nano tube composite material. According to the preparation method, the nickel-cobalt-sulfur nano particles are anchored on the surface of the carbon nano tube, so that agglomeration among the nickel-cobalt-sulfur nano particles can be effectively avoided, meanwhile, the carbon nano tube has excellent conductivity and mechanical stability, the nickel-cobalt-sulfur nano particles and the nickel-cobalt-sulfur nano particles are compounded to fully exert respective advantages of the nickel-cobalt-sulfur nano particles and the nickel-cobalt-sulfur nano particles, and excellent electrochemical performance is obtained; in addition, the preparation method adopts microwave heating synthesis, which is beneficial to explosive nucleation, can generate a large number of defects, leads to more active sites to be exposed, and further improves the electrochemical performance of the nickel-cobalt-sulfur/carbon nanotube composite material; and the reaction time is short, the operation is simple, and the popularization is easy.
The invention also provides a nickel-cobalt-sulfur/carbon nanotube composite material, which comprises a carbon nanotube and nickel-cobalt-sulfur nanoparticles growing on the carbon nanotube, wherein the nickel-cobalt-sulfur/carbon nanotube composite material is obtained by the preparation method of the nickel-cobalt-sulfur/carbon nanotube composite material.
The nickel-cobalt-sulfur/carbon nano tube composite material provided by the invention is obtained by the special preparation method, not only can improve the dispersibility of nickel-cobalt-sulfur nano particles, but also has better conductivity and stability, so that the nickel-cobalt-sulfur/carbon nano tube composite material has better electrochemical performance; when used as the positive electrode material of the super capacitor, the material has the characteristics of high specific capacity, excellent rate capability and cycle performance, and has good application prospect.
Finally, the invention provides the nickel-cobalt-sulfur/carbon nanotube composite material and the application of the nickel-cobalt-sulfur/carbon nanotube composite material obtained by the preparation method of the invention as a super capacitor anode material.
Drawings
FIG. 1 is an XRD spectrum of a nickel cobalt sulfide/CNTs composite material of example 4 of the present invention and a comparative nickel cobalt sulfide;
FIG. 2 is an SEM image of the nickel cobalt sulfide/CNTs composite material of example 4 of the present invention and the comparative example nickel cobalt sulfide;
FIG. 3 is a cyclic voltammogram of the nickel cobalt sulfide/CNTs composite of example 4 of the present invention;
FIG. 4 is a graph showing the charge and discharge curves of the nickel cobalt sulfide/CNTs composite material of example 4 of the present invention and the comparative example nickel cobalt sulfide;
FIG. 5 is a multiplying power curve of the nickel-cobalt-sulfur/CNTs composite material of the embodiment 4 and the comparative example nickel-cobalt-sulfur when the current density is 1-15A/g;
FIG. 6 is a graph of the cycle performance of the nickel-cobalt-sulfur/CNTs// AC asymmetric supercapacitor assembled by using the nickel-cobalt-sulfur/CNTs composite material as the positive electrode and Activated Carbon (AC) as the negative electrode in example 4 of the present invention, at a current density of 5A/g.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In one aspect, an embodiment of the present invention provides a method for preparing a nickel-cobalt-sulfur/carbon nanotube composite material, including the following steps:
s01: preparing a mixed solution containing carbon nano tubes, nickel salt, cobalt salt and a precipitator;
s02: performing first microwave heating treatment on the mixed solution, then adding a sulfur source, and performing second microwave heating treatment to generate the nickel-cobalt-sulfur/carbon nano tube composite material;
wherein the carbon nano tube is provided with electronegative groups, and the precipitator is heated and hydrolyzed in the mixed solution to generate hydroxide ions.
According to the preparation method of the nickel-cobalt-sulfur/carbon nano tube composite material provided by the embodiment of the invention, the mixed solution containing the carbon nano tube, the nickel salt, the cobalt salt and the precipitator is subjected to the first microwave heating treatment, and the carbon nano tube has electronegative groups, so that metal cations (Ni) in the mixed solution2+、Co2+) Will combine with electronegative group on the carbon nanotube through the electrostatic adsorption, thus form the nucleation site, hydrolyze in mixed solution in the microwave heating process precipitating agent and make the solution produce hydroxide ion, hydroxide ion and metal cation of nucleation site on the carbon nanotube react and produce the precursor; and carrying out microwave heating reaction on the subsequently added sulfur source and the precursor so as to carry out heterogeneous nucleation on the carbon nano tube to grow nickel-cobalt-sulfur nano particles and generate the nickel-cobalt-sulfur/carbon nano tube composite material. The preparation method anchors the nickel-cobalt-sulfur nanoparticles on the surface of the carbon nanotube, so that agglomeration between the nickel-cobalt-sulfur nanoparticles can be effectively avoided, the carbon nanotube has excellent electrical conductivity and mechanical stability, the nickel-cobalt-sulfur nanoparticles are compounded with the nickel-cobalt-sulfur nanoparticles, respective advantages of the nickel-cobalt-sulfur nanoparticles and the nickel-cobalt-sulfur nanoparticles can be fully exerted, and excellent electricity can be obtainedChemical properties; in addition, the preparation method adopts microwave heating synthesis, which is beneficial to explosive nucleation, can generate a large number of defects, leads to more active sites to be exposed, and further improves the electrochemical performance of the nickel-cobalt-sulfur/carbon nanotube composite material; and the reaction time is short, the operation is simple, and the popularization is easy.
The pure nickel cobalt sulfur has low specific surface area and is easy to agglomerate, so that the electrochemical performance is unstable. The invention provides a method for compounding functionalized Carbon Nanotubes (CNTs) with nickel cobalt sulfur, wherein the functionalized CNTs are CNTs with electronegative groups on the surface, the electronegative groups comprise one or more of carboxyl and hydroxyl, such as carboxylated CNTs and hydroxylated CNTs, and due to the fact that a large number of electronegative groups exist on the CNTs, a nickel cobalt hydroxide can be induced to nucleate and grow on the surface of the CNTs, the agglomeration of nickel cobalt sulfide in a vulcanization process can be effectively weakened by the existence of the CNTs, and the surface nucleation work of nickel cobalt sulfur on the CNTs is relatively small, so that the nucleation growth of nickel cobalt sulfur is easier. Therefore, the preparation method realizes the advantage complementation between the nickel and the cobalt, and achieves the purpose of improving the electrochemical properties, such as high specific capacity, excellent rate capability and cycle performance, of the nickel-cobalt-sulfur/carbon nanotube composite material (namely the nickel-cobalt-sulfur/CNTs composite material).
According to the embodiment of the invention, the nickel-cobalt-sulfur/CNTs composite material can be synthesized by induction heating under normal pressure through a microwave heating method, the preparation of the nickel-cobalt-sulfur/CNTs composite material through the microwave heating method is simple and efficient, the heating is uniform, the time is greatly reduced (from ten hours to several minutes in the prior art), and the method has the advantages of high reaction efficiency, mild synthesis conditions, small temperature gradient, less pollutants, high yield and the like, so that the method is green and energy-saving, has the potential of industrial amplification, and is easy for large-scale preparation and synthesis of the nickel-cobalt-sulfur/CNTs composite material with high multiplying power and high cycle stability.
In the step S01, the step of preparing the mixed solution containing the carbon nanotube, the nickel salt, the cobalt salt, and the precipitant includes: dispersing the carbon nano tube in a mixed solvent of water and alcohol, and then adding nickel salt, cobalt salt and a precipitator for dissolution. Wherein, in the mixed solvent of water and alcohol, the alcohol is selected from one or more of ethanol and glycol. The alcohol can reduce the dielectric constant of the solution, thereby changing the interaction force between the solute and the solvent and reducing the crystal nucleation barrier. Such a mixed solvent is more advantageous for nucleation on the carbon nanotubes. Further, in the mixed solvent of water and alcohol, the volume ratio of water to alcohol is 2.5: 1.
wherein the electronegative groups on the carbon nanotubes comprise one or more of carboxyl and hydroxyl; specifically, hydroxylated carbon nanotubes or carboxylated carbon nanotubes, and combinations thereof. The cobalt salt comprises one or more of cobalt nitrate, cobalt acetate and cobalt chloride; the nickel salt comprises one or more of nickel nitrate, nickel acetate and nickel chloride; the precipitant comprises one or more of hexamethylenetetramine and urea.
Further, in the mixed solution, the molar concentration ratio of the nickel salt, the cobalt salt and the precipitant is x: (3. about. x): (16-32); wherein x is more than 0.5 and less than 2.5. The mixed solution prepared according to the proportion is Ni as nickel cobalt sulfur nano-particles produced subsequentlyxCo3-xS4Like nanoparticles.
In the step S02, the first microwave heating process includes: heating and reacting for 5 min-4 h under 200-600W; the first microwave heating can generate a precursor of the nickel-cobalt double hydroxide/CNTs composite material, and the precipitator can be decomposed in the heating process to enable the solution to generate hydroxide ions (OH)-) With metal ions (Ni)2+、Co2+) Reacting to generate a precursor, namely a precursor of the nickel-cobalt double hydroxide/CNTs composite material. Under the above conditions, the effect of the microwave heating condition is better. Further, the generated precursor may be subjected to solid-liquid separation, for example, by heating with a microwave, cooling to room temperature, and subjecting the obtained product to centrifugal washing.
Further, the second microwave heating process includes: heating and reacting for 5 min-4 h under 200-600W. And (3) carrying out second microwave heating to carry out vulcanization treatment, wherein the added sulfur source reacts with the precursor, so that nickel-cobalt-sulfur nano particles are generated on the carbon nano tube, and the nickel-cobalt-sulfur/CNTs composite material is obtained. The effect of the microwave heating condition is better. The particle size of the generated nickel-cobalt-sulfur nanoparticles can be 10-50 nm.
Wherein the sulfur source comprises one or more of thioacetamide and sodium sulfide. The sulfur source can be added in liquid state, such as thioacetamide solution or sodium sulfide solution, and when the sulfur source is added in solution, the molar concentration of the sulfur source is 0.3-0.6 mol/L. The mass ratio of the carbon nano tube to the nickel-cobalt-sulfur nano particles in the generated composite material is 1-20: and 100, adding a sulfur source to perform a vulcanization reaction.
Further, the method also comprises a step of solid-liquid separation after the second microwave heating treatment. Namely, the solid nickel cobalt sulfur/CNTs composite material is obtained after the solvent is removed. The specific steps can be that the second microwave is heated and then naturally cooled, the obtained product is centrifugally cleaned and dried at constant temperature in vacuum, and the nickel-cobalt-sulfur/CNTs composite material is obtained.
In one embodiment, the nickel cobalt sulfur/CNTs composite is prepared by the steps comprising:
(1) weighing a proper amount of CNTs (such as carboxylated CNTs) powder with negative electric groups, adding a proper amount of deionized water into a beaker, placing the beaker into an ultrasonic dispersion instrument for ultrasonic dispersion for 20-60 min, uniformly stirring, adding a certain amount of absolute ethanol into the beaker for mixing, then adding nickel salt, cobalt salt and a precipitator (such as hexamethylenetetramine), and continuously stirring to prepare a mixed solution;
(2) transferring the mixed solution prepared in the step (1) into a reaction container, placing the reaction container into a microwave synthesis instrument, reacting for 5 min-4 h under 200-600W, cooling to room temperature, and centrifugally cleaning the obtained product to obtain a precursor;
(3) and (3) transferring the precursor prepared in the step (2) to a beaker, adding deionized water, uniformly stirring, then adding a proper amount of sulfur source (such as thioacetamide) into the beaker, and continuously and uniformly stirring. And transferring the solution into a reaction vessel, placing the reaction vessel into a microwave synthesis instrument, reacting for 10 min-4 h at 200-600W, naturally cooling, centrifugally cleaning the obtained product, and drying at constant temperature in vacuum to obtain the nickel-cobalt-sulfur/CNT composite material.
The reaction vessel may be a conical flask, a round-bottomed flask, a two-necked flask or a three-necked flask.
On the other hand, the embodiment of the invention also provides a nickel-cobalt-sulfur/carbon nanotube composite material, the nickel-cobalt-sulfur/carbon nanotube composite material comprises a carbon nanotube and nickel-cobalt-sulfur nanoparticles growing on the carbon nanotube, and the nickel-cobalt-sulfur/carbon nanotube composite material is obtained by the preparation method of the nickel-cobalt-sulfur/carbon nanotube composite material.
The nickel-cobalt-sulfur/carbon nanotube composite material provided by the embodiment of the invention is obtained by the specific preparation method of the embodiment of the invention, and comprises the carbon nanotube and the nickel-cobalt-sulfur nanoparticles growing on the carbon nanotube, wherein the nickel-cobalt-sulfur nanoparticles are anchored on the surface of the CNTs in the structure, so that the agglomeration among the nanoparticles can be effectively avoided, the dispersibility of the nickel-cobalt-sulfur nanoparticles is improved, and the excellent electrochemical performance is favorably exhibited; meanwhile, the CNTs have excellent conductivity and mechanical stability, and can fully exert respective advantages of the CNTs and the nickel, cobalt and sulfur by compounding the CNTs with nickel, cobalt and sulfur, so that excellent electrochemical performance is obtained; compared with the traditional hydrothermal method, the nickel-cobalt-sulfur/carbon nanotube composite material prepared by the microwave method has the advantages that the reaction time is greatly shortened, the microwave heating speed is high in the reaction process, explosive nucleation is facilitated, a large number of defects are generated, more active sites are exposed, and better electrochemical performance is facilitated; therefore, when the composite material is used as a super capacitor anode material, the composite material has the characteristics of high specific capacity, excellent rate capability and cycle performance, and has good application prospect.
In one embodiment, the mass ratio of the carbon nanotubes to the nickel-cobalt-sulfur nanoparticles is 1-20: 100, respectively; within the proportion range, the electrochemical performance of the obtained nickel-cobalt-sulfur/carbon nano tube composite material is better. Furthermore, the particle size of the nickel-cobalt-sulfur nano particles is 10-50 nm.
In one embodiment, the nickel cobalt sulfur nanoparticles are NixCo3-xS4Quasi-nano particles, wherein x is more than 1 and less than 3. In particular, specific nickel cobalt sulfur compounds, such as NiCo, can be obtained by adjusting the molar ratio of nickel cobalt ions2S4/CoNi2S4And (c) a compound such as a quaternary ammonium compound.
Finally, an embodiment of the present invention further provides an application of the nickel-cobalt-sulfur/carbon nanotube composite material according to the embodiment of the present invention or the nickel-cobalt-sulfur/carbon nanotube composite material obtained by the preparation method according to the embodiment of the present invention as a super capacitor positive electrode material.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of a nickel-cobalt-sulfur/CNTs composite material comprises the following steps:
(1) weighing 0.04g of carboxylated CNTs powder, adding the weighed carboxylated CNTs powder into a 100mL beaker, adding 50mL of deionized water into the beaker, placing the beaker into an ultrasonic dispersion instrument for ultrasonic dispersion for 20min, uniformly stirring, adding 20mL of absolute ethyl alcohol into the beaker for mixing, adding 1.164g of nickel nitrate hexahydrate, 2.328g of cobalt nitrate hexahydrate and 2.8g of hexamethylenetetramine, and continuously stirring for 10min to obtain a mixed solution.
(2) And (2) transferring the mixed solution prepared in the step (1) into a reaction vessel with the volume of 250mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 20min under 200W, cooling to room temperature, centrifugally cleaning the obtained product, washing for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol to obtain the precursor.
(3) And (3) adding the precursor prepared in the step (2) into a 100mL beaker, adding 70mL deionized water into the beaker, uniformly stirring until the solid is dispersed, then adding 1.2g thioacetamide into the beaker, and continuing stirring for 10 min. And transferring the solution into a reaction vessel with the volume of 250mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 20min under 200W, cooling to room temperature, centrifugally cleaning the obtained product, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at constant temperature in vacuum for 12h to obtain the nickel-cobalt-sulfur/CNTs composite material.
Example 2
A preparation method of a nickel-cobalt-sulfur/CNTs composite material comprises the following steps:
(1) weighing 0.08g of hydroxylated CNTs powder, adding the powder into a 100mL beaker, adding 50mL of deionized water into the beaker, placing the beaker into an ultrasonic dispersion instrument for ultrasonic dispersion for 20min, uniformly stirring, adding 20mL of absolute ethyl alcohol into the beaker for mixing, adding 1.164g of nickel nitrate hexahydrate, 2.328g of cobalt nitrate hexahydrate and 2.8g of hexamethylenetetramine, and continuously stirring for 10min to obtain a mixed solution.
(2) And (2) transferring the mixed solution prepared in the step (1) into a reaction vessel with the volume of 300mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 20min under 300W, cooling to room temperature, centrifugally cleaning the obtained product, washing for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol to obtain the precursor.
(3) And (3) adding the precursor prepared in the step (2) into a 100mL beaker, adding 70mL deionized water into the beaker, placing the beaker on a magnetic stirrer, uniformly stirring until the solid is dispersed, then adding 1.2g thioacetamide into the beaker, and continuing stirring for 10 min. And transferring the solution into a reaction vessel with the volume of 300mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 3h under 300W, cooling to room temperature, centrifugally cleaning the obtained product, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at constant temperature in vacuum for 12h to obtain the nickel-cobalt-sulfur/CNTs composite electrode material.
Example 3
A preparation method of a nickel-cobalt-sulfur/CNTs composite material comprises the following steps:
(1) weighing 0.12g of carboxylated CNTs powder, adding the weighed carboxylated CNTs powder into a 100mL beaker, adding 50mL of deionized water into the beaker, placing the beaker into an ultrasonic dispersion instrument for ultrasonic dispersion for 20min, uniformly stirring, adding 20mL of absolute ethyl alcohol into the beaker for mixing, then adding 1.19g of nickel chloride hexahydrate, 2.38g of cobalt chloride hexahydrate and 3.5g of hexamethylenetetramine, and continuously stirring for 10min to obtain a mixed solution.
(2) And (2) transferring the mixed solution prepared in the step (1) into a reaction vessel with the volume of 500mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 6min under 600W, cooling to room temperature, centrifugally cleaning the obtained product, washing for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol to obtain the precursor.
(3) And (3) adding the precursor prepared in the step (2) into a 100mL beaker, adding 70mL deionized water into the beaker, placing the beaker on a magnetic stirrer, uniformly stirring until the solid is dispersed, then adding 1.5g thioacetamide into the beaker, and continuing stirring for 10 min. And transferring the solution into a reaction vessel with the volume of 300mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 10min under 600W, cooling to room temperature, centrifugally cleaning the obtained product, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at constant temperature in vacuum for 12h to obtain the nickel-cobalt-sulfur/CNTs composite electrode material.
Example 4
Preparation method of nickel-cobalt-sulfur/CNTs composite material and application of nickel-cobalt-sulfur/CNTs composite material as electrode material of super capacitor
(1) Weighing 0.12g of carboxylated CNTs powder, adding the weighed carboxylated CNTs powder into a 100mL beaker, adding 50mL of deionized water into the beaker, placing the beaker into an ultrasonic dispersion instrument for ultrasonic dispersion for 20min, uniformly stirring, adding 20mL of absolute ethyl alcohol into the beaker for mixing, then adding 1.164g of nickel nitrate hexahydrate, 2.328g of cobalt nitrate hexahydrate and 2.8g of hexamethylenetetramine, and continuously stirring for 10min to obtain a mixed solution.
(2) And (2) transferring the mixed solution prepared in the step (1) into a reaction vessel with the volume of 250mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 20min under 400W, cooling to room temperature, centrifugally cleaning the obtained product, washing for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol to obtain the precursor.
(3) And (3) adding the precursor prepared in the step (2) into a 100mL beaker, adding 70mL deionized water into the beaker, uniformly stirring until the solid is dispersed, then adding 1.2g thioacetamide into the beaker, and continuing stirring for 10 min. And transferring the solution into a reaction vessel with the volume of 250mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 20min under 300W, cooling to room temperature, centrifugally cleaning the obtained product, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at constant temperature in vacuum for 12h to obtain the nickel-cobalt-sulfur/CNTs composite material.
Comparative example
A preparation method of nickel cobalt sulfur comprises the following steps:
(1) 1.164g of nickel nitrate hexahydrate, 2.328g of cobalt nitrate hexahydrate and 2.8g of hexamethylenetetramine are weighed and added into a 100mL beaker, 50mL of deionized water is added into the beaker, and the mixture is uniformly stirred for 20min to be uniformly dispersed, so that a mixed solution is prepared.
(2) And (2) transferring the mixed solution prepared in the step (1) into a reaction vessel with the volume of 400mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 1h under 300W, cooling to room temperature, centrifugally cleaning the obtained product, washing for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol to obtain the precursor.
(3) And (3) adding the precursor prepared in the step (2) into a 100mL beaker, adding 70mL deionized water into the beaker, placing the beaker on a magnetic stirrer, uniformly stirring until the solid is dispersed, then adding 1.2g thioacetamide into the beaker, and continuing stirring for 10 min. And transferring the solution into a reaction vessel with the volume of 400mL, placing the reaction vessel into a microwave synthesis instrument, reacting for 2h under 300W, cooling to room temperature, centrifugally cleaning the obtained product, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at constant temperature in vacuum for 12h to obtain pure nickel cobalt sulfur.
Performance testing
The nickel cobalt sulfur/CNTs composite of example 4 and the nickel cobalt sulfur of the comparative example were subjected to relevant characterization and performance tests.
(1) FIG. 1 is an XRD spectrum, and the obtained sample is characterized by XRD to show that the position is consistent with that of a standard card, which shows that the obtained product is a nickel-cobalt-sulfur compound. FIG. 2 is a Scanning Electron Microscope (SEM) representation of the morphology of the product, FIG. 2a is an SEM image of a comparative example of pure nickel cobalt sulfur, and FIG. 2b is an SEM image of the nickel cobalt sulfur/CNTs composite of example 4: fig. 2a shows that the nickel-cobalt-sulfur not complexed with CNTs is mainly composed of nanoparticles and nanosheets, and from its enlarged view it can be seen that the nanosheets are also agglomerated from these nanoparticles. And after the CNTs are added into the graph 2b, the nickel-cobalt-sulfur nano particles are grown on the surfaces of the CNTs, so that the agglomeration of the nano particles is prevented.
(2) The nickel-cobalt-sulfur/CNTs composite of example 4 and the nickel-cobalt-sulfur of the comparative example were used as positive electrode materials, and the following electrochemical performance tests were performed according to the following experimental procedures.
The preparation method of the working electrode comprises the following steps: mixing a nickel-cobalt-sulfur/CNTs composite material or nickel-cobalt-sulfur powder, Ketjen black and PVDF according to a ratio of 8:1:1, using NMP as a solvent to prepare slurry, coating the slurry on a foamed nickel current collector, drying the sample at a constant temperature of 60 ℃ in vacuum for 12h, and then pressing the sample into a sheet under 10 MPa.
The test system adopts a three-electrode test system, the reference electrode is Hg/HgO, the counter electrode is a platinum sheet, and the electrolyte is 3M KOH solution.
FIG. 3 is a cyclic voltammogram obtained for nickel cobalt sulfur/CNTs composite at different scan rates. The abscissa is the relative reference electrode voltage (Potential VS Hg/HgO) and the ordinate is the Current density (Current density): the test result shows that when the scanning rate is increased, the oxidation peak and the reduction peak show good symmetry, which indicates that the prepared nickel-cobalt-sulfur/CNTs composite material has good reversibility. Fig. 4 is a graph of charge and discharge curves of pure nickel-cobalt-sulfur and nickel-cobalt-sulfur/CNTs composite material obtained under different Current densities, with voltage (Potential) on the abscissa and Current density (Current density) on the ordinate: the test result shows that the nickel-cobalt-sulfur/CNTs composite material has the highest specific capacity, and is consistent with the result of the cyclic voltammetry curve. FIG. 5 is a multiplying power curve of the composite material of pure nickel cobalt sulfur and nickel cobalt sulfur/CNTs when the Current density is 1-15A/g, the abscissa is the Current density (Current density), and the ordinate is the Specific capacitance (Specific capacitance): the test result shows that the nickel-cobalt-sulfur/CNTs composite material has the highest specific capacitance and the optimal rate performance. FIG. 6 is a graph of cycle performance obtained after 30000 cycles of current density of 5A/g for a hybrid supercapacitor assembled with a nickel-cobalt-sulfur/CNTs composite material as the positive electrode and activated carbon as the negative electrode; the abscissa is Cycle number (Cycle number), and the ordinate is capacity retention (capacity retention): the test results show that the specific capacity can still maintain 82.5% of the initial capacity after 30000 cycles. The nickel-cobalt-sulfur/CNTs composite material synthesized by microwave has excellent cycle stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the nickel-cobalt-sulfur/carbon nanotube composite material is characterized by comprising the following steps of:
preparing a mixed solution containing carbon nano tubes, nickel salt, cobalt salt and a precipitator;
performing first microwave heating treatment on the mixed solution, then adding a sulfur source, and performing second microwave heating treatment to generate the nickel-cobalt-sulfur/carbon nano tube composite material;
wherein the carbon nano tube is provided with electronegative groups, and the precipitator is heated and hydrolyzed in the mixed solution to generate hydroxide ions; the nickel-cobalt-sulfur/carbon nanotube composite material comprises the carbon nanotube and nickel-cobalt-sulfur nanoparticles heteronucleated and grown on the carbon nanotube.
2. The method of claim 1, wherein the step of preparing a mixed solution comprising carbon nanotubes, a nickel salt, a cobalt salt, and a precipitating agent comprises: dispersing the carbon nano tube in a mixed solvent of water and alcohol, and then adding nickel salt, cobalt salt and a precipitating agent for dissolution.
3. The method of claim 2, wherein in the mixed solvent of water and alcohol, the alcohol is selected from one or more of ethanol and ethylene glycol; and/or the presence of a gas in the gas,
in the mixed solvent of water and alcohol, the volume ratio of water to alcohol is 2.5: 1.
4. the method of claim 1, wherein the molar concentration ratio of the nickel salt to the cobalt salt to the precipitant in the mixed solution is x: (3. about. x): (16-32); wherein x is more than 0.5 and less than 2.5.
5. The method of preparing a nickel cobalt sulfur/carbon nanotube composite of claim 1, wherein said first microwave heating treatment comprises: heating and reacting for 5 min-4 h under 200-600W; and/or the presence of a gas in the gas,
the second microwave heating process includes: heating and reacting for 5 min-4 h under 200-600W.
6. The method of claim 1 further comprising a step of solid-liquid separation after the second microwave heating step.
7. The method of any of claims 1 to 6, wherein the electronegative groups on the carbon nanotubes comprise one or more of carboxyl and hydroxyl groups; and/or the presence of a gas in the atmosphere,
the nickel salt comprises one or more of nickel nitrate, nickel acetate and nickel chloride; and/or the presence of a gas in the gas,
the cobalt salt comprises one or more of cobalt nitrate, cobalt acetate and cobalt chloride; and/or the presence of a gas in the gas,
the sulfur source comprises one or more of thioacetamide and sodium sulfide; and/or the presence of a gas in the gas,
the precipitant comprises one or more of hexamethylenetetramine and urea.
8. A nickel cobalt sulfur/carbon nanotube composite material, comprising carbon nanotubes and nickel cobalt sulfur nanoparticles grown on the carbon nanotubes, wherein the nickel cobalt sulfur/carbon nanotube composite material is obtained by the method for preparing a nickel cobalt sulfur/carbon nanotube composite material according to any one of claims 1 to 7.
9. The nickel cobalt sulfur/carbon nanotube composite material of claim 8, wherein the mass ratio of the carbon nanotubes to the nickel cobalt sulfur nanoparticles is 1 to 20: 100, respectively; and/or the presence of a gas in the gas,
the particle size of the nickel-cobalt-sulfur nano particles is 10-50 nm; and/or the presence of a gas in the gas,
the nickel-cobalt-sulfur nano-particles are NixCo3-xS4Quasi-nano particles, wherein x is more than 1 and less than 3.
10. Use of the nickel cobalt sulfur/carbon nanotube composite material obtained by the method for preparing a nickel cobalt sulfur/carbon nanotube composite material according to any one of claims 1 to 7 or the nickel cobalt sulfur/carbon nanotube composite material according to any one of claims 8 to 9 as a positive electrode material for a supercapacitor.
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| CN113643908B (en) * | 2021-06-25 | 2023-03-17 | 浙江工业大学 | One kind (Ni, co) 3 S 4 CNT material and preparation method and application thereof |
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