CN108597898A - A kind of preparation method of cobalt sulfide zinc nano material - Google Patents

A kind of preparation method of cobalt sulfide zinc nano material Download PDF

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Publication number
CN108597898A
CN108597898A CN201810316955.6A CN201810316955A CN108597898A CN 108597898 A CN108597898 A CN 108597898A CN 201810316955 A CN201810316955 A CN 201810316955A CN 108597898 A CN108597898 A CN 108597898A
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cobalt
zinc
presoma
nano
cobalt sulfide
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陶凯
韩雪
韩磊
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Ningbo University
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Ningbo University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The present invention provides a kind of preparation methods of cobalt sulfide zinc nano material.This method reacts to form metal-organic framework material as nanometer presoma with organic ligand using zinc salt, cobalt salt, and vulcanization reaction then is occurred for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material;In presoma forming process, base material is added, forerunner's precursor reactant of laminated structure is set to generate in the substrate surface, effectively reduce being stacked between presoma, to contribute to vulcanization reaction fully to occur, so that the skeleton structure of nanometer persursor material is kept good, to considerably increase the surface area of cobalt sulfide Zinc material, chemical property is improved when being applied advantageous as electrode material.

Description

A kind of preparation method of cobalt sulfide zinc nano material
Technical field
The present invention relates to technical field of nano material, and in particular to a kind of preparation method of cobalt sulfide zinc nano material.
Background technology
Electric chemical super capacitor abbreviation ultracapacitor is a kind of a kind of storage between traditional capacitor and battery Energy device, is a green technology for being combined the energy with environmental protection, and due to short with the charging time, power-performance is high, cycle Stability is good, and service life is long, and pollution-free, the excellent specific properties such as economic and environment-friendly, and duration can not only be provided in application The energy, moreover it is possible to play the role of environmental protection, therefore, received significant attention in recent years, and had a wide range of applications field, logical The fields such as letter, electric power, electronic product, new-energy automobile are with a wide range of applications.
As a kind of important semiconductor-transition bimetallic sulfide, cobalt sulfide zinc shows excellent electrochemistry Can, it is widely used in electro-catalysis and ultracapacitor field, is a kind of ideal electrode material.Therefore, cobalt sulfide zinc material is improved The chemical property of material is of great significance to electro-catalysis and ultracapacitor field.
Invention content
The technical purpose of the present invention is to provide a kind of preparation method of cobalt sulfide zinc nano material, is made using this method Cobalt sulfide zinc can improve chemical property.
In order to achieve the above technical purposes, the present inventor, which uses, forms transition metal ions and organic ligand with organic Then vulcanization reaction shape is occurred for persursor material and sulphur-containing substance by the metal-organic framework material of skeleton as persursor material It at the method for hollow transient metal sulfide, finds during preparing presoma, if block materials are added as base Bottom, then nanometer forerunner precursor reactant generate in the substrate surface, can effectively avoid being stacked between nanometer persursor material, To contribute to vulcanization reaction fully to occur, the skeleton structure of nano material is made to keep good.
That is, the technical scheme is that:A kind of preparation method of cobalt sulfide zinc nano material, includes the following steps:
(1) zinc salt, cobalt salt and organic ligand, reaction is used to form metal-organic framework material as nanometer presoma;
(2) vulcanization reaction is occurred into for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material;
It is characterized in that:In the reaction process of the step (1), block materials are added as substrate, nano-sheet forerunner Body is generated in the substrate surface.
The base material does not react with zinc salt, cobalt salt and organic ligand, and material is unlimited, including nickel, carbon Deng.In order to improve the surface area of substrate, preferably there is cavernous base material, such as nickel foam, carbon cloth, carbon paper, carbon nanometer Pipe, graphene.
As a kind of realization method, in the step (1), takes a certain amount of zinc salt to be dissolved in the first solvent with cobalt salt and formed Organic ligand is dissolved in the second solvent and forms the second solution by the first solution;First solution is uniformly mixed to be formed with the second solution Mixed solution is added base material, reacts to form a nanometer presoma.Preferably, in mixed solution, zinc salt and cobalt salt, The molar ratio of organic ligand and solvent is 1:(3-8):(0.5-6).Wherein, preferably, the molar ratio of zinc salt and cobalt salt is 1: (0.2-5), further preferably 1:(0.5-3).
The zinc salt is unlimited, including one or more of zinc acetate, zinc nitrate, zinc chloride etc..
The cobalt salt is unlimited, including one kind or more in cobalt acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt carbonate etc. Kind.
The organic ligand is unlimited, including in 2-methylimidazole, benzimidazole, 2- nitroimidazoles, terephthalic acid (TPA) etc. It is one or more.
First solvent is unlimited, including water and organic solvent, and the organic solvent is unlimited, including methanol, ethyl alcohol, It is one or more in DMF, DMA etc..
Second solvent is unlimited, including water and organic solvent, and the organic solvent is unlimited, including methanol, ethyl alcohol, It is one or more in DMF, DMA etc..
Preferably, in the step (1), reaction time 3h-24h.
In the step (1), structure, thickness are preferably 250-300nm to presoma in the form of sheets.
Realization effect as one preferred, presoma nanometer sheet are vertically generated in substrate surface, form array arrangement, from And being stacked between avoiding nanometer persursor material to greatest extent, contribute to vulcanization reaction fully to occur, makes a nanometer material The skeleton structure of material keeps good.
As a kind of realization method, in the step (2), presoma is put into the organic solvent containing sulphur source, into Row hydro-thermal reaction obtains the hollow nanometer cobalt sulfide Zinc material positioned at substrate surface.
In the step (2), sulphur source is unlimited, including one or more in thioacetamide, vulcanized sodium, thiocarbamide etc..
In the step (2), organic solvent is unlimited, including one or more in methanol, ethyl alcohol, DMF, DMA etc..
In the step (2), preferably, a concentration of 0.003-0.04g/mL of sulphur-containing solution.
Preferably, in the step (2), the temperature of hydro-thermal reaction is 100-200 DEG C.
Preferably, in the step (2), the time of hydro-thermal reaction is in 3h-10h.
Compared with prior art, the present invention forms the metal with organic backbone using transition metal ions and organic ligand During organic framework materials are as presoma, base material is added, forerunner's precursor reactant of flaky nanometer structure is made to generate The substrate surface, has the advantages that:
(1) presoma of laminated structure is generated in the substrate surface, is effectively reduced between two-dimensional sheet nanometer presoma Be stacked with, contribute to vulcanization reaction fully to occur, obtain the cobalt sulfide Zinc material of hollow nano-chip arrays structure, make nanometer The skeleton structure of persursor material keeps good, to considerably increase the surface area of cobalt sulfide Zinc material.This is conducive to vulcanize Increase with effective contact area of electrolyte solution when cobalt Zinc material is applied as electrode material, shortens ion transmission path, carry The rate of high electronics transfer improves specific capacitance, to improve chemical property.
(2) preferably, when selecting conductive substrates, which can be directly used as electrode basement, work as to reduce The addition of non-conductivity adhesive when cobalt sulfide Zinc material is applied as electrode material can substantially reduce resistance, improve conductive Property.
(3) preparation method of the invention is simple, and the cobalt sulfide Zinc material of hollow nano-chip arrays structure obtained is with excellent Different chemical property shows good redox peaks, and has efficient charge and discharge when being applied as electrode material Process, excellent specific capacitance performance and good cyclical stability, wherein electrochemical cycle stability can be protected after recycling 1000 times It holds 75% or more, therefore has a good application prospect in supercapacitor technologies field.
Description of the drawings
Fig. 1 is that step (2) is obtained using nickel foam as the scanning electron microscope (SEM) photograph of the presoma of substrate in the embodiment of the present invention 1;
Fig. 2 is the partial enlarged view in Fig. 1;
Fig. 3 is that step (3) is obtained using nickel foam as the scanning of the cobalt sulfide Zinc material of substrate electricity in the embodiment of the present invention 1 Mirror figure;
Fig. 4 is that the embodiment of the present invention 1 is obtained to be made by the zinc sulphide cobalt material of substrate and comparative example 1 of nickel foam The XRD diagram of the zinc sulphide cobalt material obtained;
Fig. 5 is that the cobalt sulfide Zinc material of hollow nano-chip arrays structure made from the embodiment of the present invention 1 is electrolysed in 1M KOH Chemical property figure in matter solution;Wherein, figure a is the cyclic voltammetry curve figure swept in difference under speed;It is that different electric currents are close to scheme b The lower chrono amperometry figure of degree;It is specific capacitance performance map to scheme c, and figure d is cyclical stability;
Fig. 6 is the scanning electron microscope (SEM) photograph of presoma made from step (2) in comparative example 1;
Fig. 7 is the scanning electron microscope (SEM) photograph of cobalt sulfide Zinc material made from step (3) in comparative example 1.
Specific implementation mode
Present invention is further described in detail with embodiment below in conjunction with the accompanying drawings, it should be pointed out that reality as described below It applies example to be intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) 0.49gZn (NO are taken3)2·6H2O, 0.24g Co (NO3)2·6H2O is dissolved in 50mL water, takes 1.6g diformazans Base imidazoles is dissolved in 50mL water;Above two solution is mixed, 5min is stirred, obtains presoma reaction solution;Zinc salt and cobalt salt, Organic ligand, water molar ratio be 1:4:2.8, wherein zinc salt, cobalt salt molar ratio be 1:0.5.
(2) clean nickel foam is added in above-mentioned presoma reaction solution, 4h is stood at 25 DEG C;Then, bubble is taken out Foam nickel is washed with water three times, and the presoma for obtaining that nickel foam is substrate for 24 hours is dried in 75 DEG C of vacuum drying chamber.
(3) presoma obtained in above-mentioned steps is added in the ethanol solution containing 0.003g/ml thioacetamides, Obtain reaction solution;Reaction solution is added in ptfe autoclave liner, reacts 4h at 120 DEG C;Nickel foam is taken out, It is washed respectively with water and ethyl alcohol and is placed in 65 DEG C of vacuum drying chamber dry 12h three times, obtain the vulcanization that nickel foam is substrate Cobalt Zinc material.
Nickel foam made from above-mentioned steps (2) is that the scanning electron microscope (SEM) photograph of the presoma of substrate is as shown in Figure 1, 2, step (3) The scanning electron microscope (SEM) photograph of cobalt sulfide zinc nanometer sheet material obtained is as shown in Figure 3.As can be seen that presoma made from step (2) is in Flaky nanometer structure, size uniformity, thickness is in 250-300nm or so, and vertical-growth, in nickel foam, each nanometer sheet is presented Array-like regular array;It is in hollow form after step (3) vulcanization, flaky nanometer structure holding is well.
Fig. 4 is step in cobalt sulfide zinc nanometer sheet material made from step in the present embodiment (3) and following comparative examples 1 (3) XRD diagram of cobalt sulfide zinc made from.In Fig. 4, cobalt sulfide Zinc material obtained is expressed as Zn-Co- in comparative example 1 S-P, wherein P indicate then powder, i.e., no powder presoma obtained in the case of base material is added obtain after over cure The cobalt sulfide zinc powder body material arrived;Cobalt sulfide Zinc material obtained is expressed as Zn-Co-S-NF in embodiment 1, and wherein NF refers to base Bottom nickel foam (Nickel foam) is added made from substrate NF using NF as the presoma of substrate, is then obtained after over cure Using NF as the cobalt sulfide Zinc material of substrate.Figure 4, it is seen that Zn-Co-S-NF and Zn-Co-S-P has apparent diffraction Peak illustrates that the material has good crystallinity.
Cobalt sulfide zinc nano material obtained above is placed in 1M KOH electrolyte solutions, to be saturated calomel as reference Electrode, Pt, as to electrode, form three-electrode system using the cobalt sulfide zinc nano material as working electrode, test the vulcanization The chemical property of cobalt zinc nano material, the results are shown in Figure 4.
In Fig. 5, a figures are the materials sweeps the cyclic voltammetry curves under speed in difference, shows that the cyclic voltammetry curve of closure has Apparent redox peaks show that the material belongs to fake capacitance electrode material.
In Fig. 5, b figures are charging and discharging curve of the material under different current densities.According to specific capacitance calculation formula C= (I* △ t)/(m* △ V), in conjunction with charging and discharging curve figure, the specific capacitance value under different current densities is calculated, as c schemes institute in Fig. 5 Show, is shown in 0.5A g-1When, specific capacitance value is up to 2354.3F g-1Left and right.
In Fig. 5, it is 10A g that d figures, which are the electrode materials in current density,-1When cyclical stability, cycle 1000 times after, The cyclical stability of material is maintained at 83.3% or so.
Show that the nickel foam is that the hollow nano-chip arrays cobalt sulfide Zinc material of substrate can be used as electrode of super capacitor material Material.
Comparative example 1:
The present embodiment is the comparative example of above-described embodiment 1.
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) identical with step (1) in embodiment 1;
(2) essentially identical with the step (2) in embodiment 1, the difference is that being added without in presoma reaction solution clean Net nickel foam states presoma reaction solution and stands 4h at 25 DEG C, obtains presoma;
(3) identical with step (3) in embodiment 1, since presoma does not have nickel foam as substrate, obtain Cobalt sulfide Zinc material.
The scanning electron microscope (SEM) photograph of presoma made from above-mentioned steps (2) is as shown in fig. 6, hollow cobalt sulfide made from step (3) The scanning electron microscope (SEM) photograph of zinc nanometer sheet is as shown in Figure 7.As can be seen that presoma made from step (2) has complete leaf plate shape, But it is stacked between piece and piece;After step (3) vulcanization, leaf laminated structure is deteriorated completely.
The cobalt sulfide zinc nano material is tested, test method is identical with the method in embodiment 1, the results show that phase With under the conditions of three-electrode system test chemical property be:Current density is in 0.5A g-1When, specific capacitance value is in 355.3F g-1Left and right;Current density is in 10A g-1When chemical property cyclical stability be maintained at 75.8%.
It is compared with above-mentioned comparative example 1, illustrates in embodiment 1, using nickel foam as substrate, the pattern of material is maintained Prodigious benefit.In addition, pattern can not only be kept by substrate of nickel foam, when as electrode material, electrification is also advantageously improved Learn performance.
Embodiment 2:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) it takes 0.49g zinc nitrates, 0.59g cobalt acetates to be dissolved in 10mL methanol, 1.58g methylimidazoles is taken to be dissolved in 5mL In methanol;Above two solution is mixed, 30min is stirred, obtains presoma reaction solution, wherein cobalt salt, organic ligand, solvent Molar ratio be 1:4:5, zinc salt, cobalt salt molar ratio be 1:2.
(2) clean nickel foam is added in above-mentioned presoma reaction solution, is stood for 24 hours at 25 DEG C;Then, bubble is taken out Foam nickel is washed three times with ethyl alcohol, and the presoma for obtaining that nickel foam is substrate for 24 hours is dried in 75 DEG C of vacuum drying chamber.
(3) presoma obtained above is added in the ethanol solution containing 0.039g/mL vulcanized sodium, obtains reacting molten Liquid;Reaction solution is added in ptfe autoclave liner, is placed in baking oven and reacts 5h at 100 DEG C;Nickel foam is taken out, point It is not washed with water and ethyl alcohol and is placed in 80 DEG C of vacuum drying chamber dry 12h three times, obtain the cobalt sulfide that nickel foam is substrate Zinc material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step (3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking;After step (3) vulcanization, nano-sheet knot Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1 Together, the results show that the chemical property of the three-electrode system test under the same terms is:Current density is in 0.5A g-1When, than electricity Capacitance is 1580.5F g-1, cyclical stability is maintained at 80% or so.
Embodiment 3:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) 0.14g zinc chloride, 0.29g Co (NO are taken3)2·6H2O is dissolved in 20mL methanol, takes 1.31g dimethyl miaows Azoles is dissolved in 20mL methanol;Above two solution is mixed, 15min is stirred, obtains presoma reaction solution, wherein zinc salt and cobalt Salt, organic ligand, solvent molar ratio be 1:8:0.99, zinc salt, cobalt salt molar ratio be 1:1.
(2) clean nickel foam is put into above-mentioned reaction solution, is stood at room temperature for 24 hours;Then, nickel foam is taken out, is used Methanol washs the presoma for obtaining that nickel foam is substrate three times.
(3) presoma obtained above is put into the aqueous solution dissolved with 0.04g thiocarbamides, obtains reaction solution;
Reaction solution is added in ptfe autoclave liner, reacts 8h at 150 DEG C in baking oven;Nickel foam is taken out, It is washed respectively with water and ethyl alcohol and is placed in 65 DEG C of vacuum drying chamber dry 20h three times, obtain the vulcanization that nickel foam is substrate Cobalt Zinc material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step (3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking;After step (3) vulcanization, nano-sheet knot Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1 Together, the results show that the chemical property of the three-electrode system test under the same terms is:Current density is in 0.5A g-1When, than electricity Capacitance is in 856.2F g-1Left and right, cyclical stability are maintained at 78.3%.
Embodiment 4:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) 0.04gZn (COOH) is taken2·2H2O, 0.12g CoCl2·6H2O is dissolved in 40mL methanol, takes 0.08g benzene And imidazoles is dissolved in 40mL methanol;Above two solution is mixed, 60min is stirred, obtains presoma reaction solution, wherein cobalt Salt, organic ligand, solvent molar ratio be 1:4:1.86, zinc salt, cobalt salt molar ratio be 1:2.5.
(2) clean nickel foam is put into above-mentioned reaction solution, stands 10h at room temperature;Then, nickel foam is taken out, is used Methanol, ethyl alcohol wash the presoma for obtaining that nickel foam is substrate three times respectively.
(3) presoma obtained above is put into dissolved with 0.028g/ml Na2In the ethanol solution of S, reaction solution is obtained; Reaction solution is added in ptfe autoclave liner, reacts 8h at 120 DEG C in baking oven;Nickel foam is taken out, uses water respectively It is placed on dry 20h in 65 DEG C of vacuum drying chamber three times with ethyl alcohol washing, obtains the cobalt sulfide Zinc material that nickel foam is substrate.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step (3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking;After step (3) vulcanization, nano-sheet knot Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1 Together, the results show that the chemical property of the three-electrode system test under the same terms is:Current density is in 0.5A g-1When, than electricity Capacitance is in 698.3F g-1Left and right, cyclical stability are maintained at 80%.
Embodiment 5:
In the present embodiment, the preparation method of hollow cobalt sulfide zinc nano material is as follows:
(1) 0.23g anhydrous zinc chlorides, 1.5g Co (NO are taken3)2·6H2O is dissolved in 60mL ethyl alcohol, takes 2.4g dimethyl Imidazoles is dissolved in 20mL ethyl alcohol;Above two solution is mixed, 15min is stirred, obtains presoma reaction solution, wherein cobalt salt, Organic ligand, solvent molar ratio be:1:4.3:1.87, zinc salt, cobalt salt molar ratio be 1:3.
(2) clean nickel foam is put into above-mentioned presoma reaction solution, stands 5h at room temperature;Then, foam is taken out Nickel washs the presoma for obtaining that nickel foam is substrate three times with methanol.
(3) presoma obtained above is put into the aqueous solution dissolved with 0.014g/ml thioacetamides, obtains reacting molten Liquid;Reaction solution is added in ptfe autoclave liner, reacts 8h at 150 DEG C in baking oven;Nickel foam is taken out, is used respectively Water and ethyl alcohol washing are placed on dry 20h in 65 DEG C of vacuum drying chamber three times, obtain the cobalt sulfide zinc material that nickel foam is substrate Material.
Nickel foam made from above-mentioned steps (2) is the scanning electron microscope (SEM) photograph of the presoma of substrate similar to shown in Fig. 1,2, step (3) scanning electron microscope (SEM) photograph of cobalt sulfide zinc made from is similar to Figure 3, shows that presoma obtained is in flaky nanometer structure, and Be grown in nickel foam, each nanometer sheet forms array arrangement, between do not form stacking;After step (3) vulcanization, nano-sheet knot Structure keeps good.
Test the cobalt sulfide zinc nano material that the nickel foam is substrate, test method and the complete phase of method in embodiment 1 Together, the results show that the chemical property of the three-electrode system test under the same terms is:Current density is in 0.5A g-1When, than electricity Capacitance is in 583.4F g-1Left and right, cyclical stability are maintained at 76.2%.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that the above is only For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in the spirit of the present invention, Supplement or similar fashion replacement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of preparation method of cobalt sulfide zinc nano material, includes the following steps:
(1) zinc salt, cobalt salt and organic ligand, reaction is used to form metal-organic framework material as nanometer presoma;
(2) vulcanization reaction is occurred into for the presoma and sulphur-containing substance, forms hollow cobalt sulfide zinc nano material;
It is characterized in that:In the reaction process of the step (1), block materials are added as substrate, the life of nano-sheet presoma At in the substrate surface.
2. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that:The base material includes Nickel and/or carbon.
3. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that:The base material is in more Pore structure.
4. the preparation method of cobalt sulfide zinc nano material as claimed in claim 3, it is characterized in that:The base material is bubble One or several kinds in foam nickel, carbon cloth, carbon paper, carbon nanotube, graphene.
5. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that:The zinc salt includes acetic acid One or more of zinc, zinc nitrate, zinc chloride;
Preferably, the cobalt salt includes one or more in cobalt acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt carbonate;
Preferably, the organic ligand includes in 2-methylimidazole, benzimidazole, 2- nitroimidazoles, terephthalic acid (TPA) It is one or more.
6. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that:It is preceding in the step (1) Drive body structure in the form of sheets, thickness 250-300nm.
7. the preparation method of cobalt sulfide zinc nano material as described in claim 1, it is characterized in that:It is preceding in the step (1) It drives body nanometer sheet vertically to generate in substrate surface, forms array arrangement.
8. the preparation method of the cobalt sulfide zinc nano material as described in any claim in claim 1 to 7, it is characterized in that: It in the step (1), takes a certain amount of zinc salt and cobalt salt to be dissolved in the first solvent and forms the first solution, organic ligand is dissolved in the Two solvents form the second solution;First solution is uniformly mixed to form mixed solution with the second solution, base material is added, is occurred Reaction forms nanometer presoma;
Preferably, in mixed solution, the molar ratio of zinc salt and cobalt salt, organic ligand and solvent is 1:(3-8):(0.5-6);
Preferably, the molar ratio of zinc salt and cobalt salt is 1:(0.2-5), further preferably 1:(0.5-3).
9. the preparation method of the cobalt sulfide zinc nano material as described in any claim in claim 1 to 7, it is characterized in that: In the step (2), presoma is put into the organic solvent containing sulphur source and is reacted;
Preferably, sulphur source includes one or more in thioacetamide, vulcanized sodium, thiocarbamide;
Preferably, organic solvent includes one or more in methanol, ethyl alcohol, DMF, DMA;
Preferably, a concentration of 0.003-0.04g/mL of sulfur-bearing solvent.
10. the preparation method of cobalt sulfide zinc nano material as claimed in claim 9, it is characterized in that:In the step (2), Reaction temperature is 100-200 DEG C;
Preferably, in the step (2), the reaction time is in 3h-10h.
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CN110527107A (en) * 2019-08-27 2019-12-03 深圳大学 A kind of orderly two-dimentional electroconductive molecule monolayer array preparation method and photoelectric device
CN110563049A (en) * 2019-09-30 2019-12-13 淮阴师范学院 cobalt zinc sulfide nano material and preparation method and application thereof
CN110634688A (en) * 2019-08-12 2019-12-31 江苏大学 Preparation method and application of composite film electrode with CoZn-S nano particles inserted in graphene
CN110844899A (en) * 2019-10-28 2020-02-28 广州大学 Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof
CN111524714A (en) * 2020-04-06 2020-08-11 电子科技大学 Preparation method of self-supporting nano array with secondary structure
CN111599606A (en) * 2020-05-07 2020-08-28 宁波大学 Preparation method and application of cobalt oxysulfide porous nanorod material
CN111668503A (en) * 2020-07-20 2020-09-15 山东大学 Bimetal sulfide lithium-air battery positive electrode material and preparation method and application thereof
CN111755695A (en) * 2020-06-30 2020-10-09 陕西科技大学 Folded polyhedral cobalt sulfide electrode material and preparation method thereof
CN112103092A (en) * 2020-07-27 2020-12-18 浙江工业大学 Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof

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CN110527107A (en) * 2019-08-27 2019-12-03 深圳大学 A kind of orderly two-dimentional electroconductive molecule monolayer array preparation method and photoelectric device
CN110563049A (en) * 2019-09-30 2019-12-13 淮阴师范学院 cobalt zinc sulfide nano material and preparation method and application thereof
CN110844899A (en) * 2019-10-28 2020-02-28 广州大学 Carbon nano tube composite cobalt sulfide nano material and preparation method and application thereof
CN111524714A (en) * 2020-04-06 2020-08-11 电子科技大学 Preparation method of self-supporting nano array with secondary structure
CN111599606A (en) * 2020-05-07 2020-08-28 宁波大学 Preparation method and application of cobalt oxysulfide porous nanorod material
CN111755695A (en) * 2020-06-30 2020-10-09 陕西科技大学 Folded polyhedral cobalt sulfide electrode material and preparation method thereof
CN111668503A (en) * 2020-07-20 2020-09-15 山东大学 Bimetal sulfide lithium-air battery positive electrode material and preparation method and application thereof
CN112103092A (en) * 2020-07-27 2020-12-18 浙江工业大学 Metal cation doped cobalt polysulfide/cobalt hydroxide composite material and preparation method and application thereof

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