CN110033956A - A kind of electrode material and preparation method thereof, supercapacitor - Google Patents
A kind of electrode material and preparation method thereof, supercapacitor Download PDFInfo
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- CN110033956A CN110033956A CN201910414978.5A CN201910414978A CN110033956A CN 110033956 A CN110033956 A CN 110033956A CN 201910414978 A CN201910414978 A CN 201910414978A CN 110033956 A CN110033956 A CN 110033956A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of electrode materials and preparation method thereof, supercapacitor, described matrix includes metal organic frame and the carbon nanotube that is formed on the metal organic frame, described matrix passes through selenization, matrix is set to obtain the effect for keeping presoma pattern, to make electrode material that there is excellent electrochemical capacitance performance and good cyclical stability, it can continue to keep excellent circulation conservation rate in electrode cycle use.
Description
Technical field
The present invention relates to electronic component technology fields more particularly to a kind of electrode material and preparation method thereof, super capacitor
Device.
Background technique
The energy is material base for the survival of mankind, the mainly fossil energy of people's consumption.Due to fossil fuel
Supply limited, and the consumption of the energy is very fast, is not only easy to pollute the environment, and the contradiction of shortage of resources becomes increasingly conspicuous, sternly
The development of society is constrained again.The development and utilization ratio that sustainable new energy is continuously improved seems ever more important.
New-energy capacitance is a kind of novel green energy resource, has the advantages that voltage is high, the service life is long, energy density is big.Newly
Energy capacitor includes electrode.Most of commercialized electrode material is mainly the carbon material of bigger serface at present, but its
Energy density is lower, how to improve the research hotspot that electrode performance is current electrode field.
Summary of the invention
The present invention provides a kind of electrode material and preparation method thereof, supercapacitor, has electrode material excellent super
Capacitive property and good cyclical stability.
One aspect of the present invention provides a kind of electrode material, including matrix, and described matrix includes metal organic frame and formation
Carbon nanotube on the metal organic frame, described matrix pass through selenization.
In one embodiment, the metal organic frame is ZIF-67 skeleton.
Another aspect of the present invention provides a kind of preparation method of electrode material, comprising: by carbon nano tube dispersion liquid and metal
Organic dispersions form mixed liquor；The mixed liquor is dried, matrix is formed；In the case where protecting atmosphere to described matrix selenizing
Processing, obtains electrode material.
In one embodiment, it is described by carbon nano tube dispersion liquid and metal organic dispersions formed mixed liquor it
Before, further includes: carbon nanotube is mixed with polyvinylpyrrolidone, forms carbon nano tube dispersion liquid in a solvent；By six water nitre
Acidic cobalt solution and the mixing of 2-methylimidazole solution, form metal organic dispersions.
In one embodiment, the solvent is methanol.
In one embodiment, described to mix cobalt nitrate hexahydrate solution and 2-methylimidazole solution, forming metal has
Machine dispersion liquid, comprising: cobalt nitrate hexahydrate dissolution is uniformly dispersed in methyl alcohol, forms the cobalt nitrate hexahydrate solution；By 2- first
The dissolution of base imidazoles is uniformly dispersed in methyl alcohol, forms the 2-methylimidazole solution；Institute is added in the 2-methylimidazole solution
State cobalt nitrate hexahydrate solution, the empurpled metal organic dispersions of shape.
In one embodiment, described that the mixed liquor is dried, form matrix, comprising: to the mixed liquor
It starts the cleaning processing, the mixed liquor after being cleaned；Mixed liquor after the cleaning is subjected to centrifugal treating, obtains filter residue；It will
The filter residue carries out vacuum drying treatment, obtains described matrix.
In one embodiment, described that the mixed liquor is started the cleaning processing, the mixed liquor after being cleaned, packet
It includes: the mixed liquor being subjected to centrifugal treating, obtains sediment；In methyl alcohol by sediment dissolution, the cleaning is obtained
Mixed liquor afterwards；The cleaning treatment is at least twice.
In one embodiment, electrode material is obtained to described matrix selenization in the case where protecting atmosphere, comprising:
Under vacuum condition, selenium powder and the filter residue are made annealing treatment, electrode material is obtained；Or, under atmosphere of inert gases, to selenium
Powder and the filter residue are made annealing treatment, and electrode material is obtained.
Another aspect of the present invention provides a kind of supercapacitor, including electrode material described in above embodiment.
A kind of electrode material provided by the invention and preparation method thereof, supercapacitor, by carbon nanotube and metal
Organic frame is compounded to form matrix, while carrying out selenization to the matrix after compound, obtains matrix by selenization
The effect of presoma pattern is kept, thus make electrode material that there is excellent electrochemical capacitance performance and good cyclical stability,
It can continue to keep excellent circulation conservation rate in electrode cycle use.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 the electrode obtained material of the embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 the electrode obtained material of the embodiment of the present invention；
Fig. 3 is 3 the electrode obtained material working electrode of the embodiment of the present invention in the different cyclic voltammograms swept under speed；
Fig. 4 is constant current charge-discharge of the 3 the electrode obtained material working electrode of the embodiment of the present invention under different current densities
Figure；
Fig. 5 is the cycle performance figure of 3 the electrode obtained material of the embodiment of the present invention.
Specific embodiment
To keep the purpose of the present invention, feature, advantage more obvious and understandable, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, and not all embodiments.Based on the embodiments of the present invention, those skilled in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
On the one hand the embodiment of the present invention provides a kind of electrode material, including matrix, matrix includes metal organic frame and shape
At the carbon nanotube on metal organic frame, matrix passes through selenization.
Electrode material provided in an embodiment of the present invention, by being compounded to form base to carbon nanotube and metal organic frame
Body, while selenization is carried out to the matrix after compound, the effect of matrix acquisition holding presoma pattern is made by selenization,
To make electrode material that there is excellent electrochemical capacitance performance and good cyclical stability.
Specifically, carbon nanotube has many abnormal mechanics, electricity and chemical property as monodimension nanometer material, it can
Conductive material is made.And metal organic frame is to be self-assembly of by organic ligand and metal ion or cluster by coordinate bond
The hybrid inorganic-organic materials with molecule inner pore.In metal organic frame, organic ligand and metal ion or cluster
Arrangement have apparent directionality, different frame pore structures can be formed, to show different absorption properties, light
Learn property, electromagnetic property.It has high porosity, low-density, bigger serface, duct rule, aperture is adjustable and topological
The advantages that structure diversity and Scalability.As conducting polymer, the network structure of metal organic frame is flourishing, receiving from
Son amount is big, and energy density and power density are big.And transition metal oxide and hydroxide storage charge are different from carbon material,
By surface faraday's redox reaction, there is the energy density higher than carbon material, and its structure can be transition metal
Ion provides well-proportioned dispersion liquid, there is good application prospect in electrochemistry.
By carbon nanotube in conjunction with metal organic frame, the pore structure that metal organic frame has is received compared to by carbon
Mitron is directly incorporated in planar substrates, and carbon nanotube is incorporated on metal organic frame, can be provided for carbon nanotube compared with
The carbon nanotube of more specific surface areas, introducing is connected with each other, and so that electrode material is had more or active site, to mention
Its high chemical property.Further, since metal organic frame can form different frame pore structures, the present invention
Electrode material obtained by embodiment can be the arbitrarily shape as made from metal organic frame, such as blocky, rodlike, film
Shape, therefore the embodiment of the present invention is not defined the concrete shape of electrode material, and any required shape can be made according to demand
Shape.
Further, the embodiment of the present invention also carries out selenizing to by matrix of the carbon nanotube in conjunction with metal organic frame
Reason, by selenization, selenium can be wrapped in around matrix to form matrix and protect, thus it enables that matrix, which obtains, keeps presoma
The effect of pattern, thus enable electrode material it is continuous and stable have excellent electrochemical capacitance performance.
It should be noted that the embodiment of the present invention is not defined the number of plies of carbon nanotube, single-layered carbon nanotube can be
Pipe or multilayer carbon nanotube, are not also defined the structure of carbon nanotube, can be armchair carbon nanotubes, sawtooth shaped carbon
Nanotube and Chiral carbon nanotube；The wall defects of carbon nanotube are not limited also, can be and improve carbon nanotube and contain
Defect carbon nanotube.In addition to this, there are also the thickness of carbon nanotube and area, the embodiment of the present invention is equally not limited.
On this basis, metal organic frame of the invention refer mainly to generation passed through by organic ligand and metal ion or cluster
The hybrid inorganic-organic materials with molecule inner pore that coordinate bond is self-assembly of.Organic ligand and metal ion therein
Respectively or it can comprehensively consider and selected according to actual needs.Since the arrangement of organic ligand and metal ion or cluster has
There is apparent directionality, selects organic ligand and metal ion that can form different frame pore structures according to demand, thus
Different absorption properties, optical property, electromagnetic property etc. are shown to meet production requirement.As ZIF series, MOF series and
MIL series etc..
Specifically, in embodiments of the present invention, metal organic frame is ZIF-67 skeleton.ZIF-67 framework material has just
The pattern of dodecahedron has the characteristics that simple synthetic method, porosity, large specific surface area and flexible structure are controllable.With
ZIF-67 skeleton can provide more specific surface areas as metal organic frame for carbon nanotube, that is, provide more activity
Site is conducive to be mass produced simultaneously as synthetic method is simple.
The metal organic frame of the embodiment of the present invention can also be ferrous metals organic frame (Fe-MOFs), ferrous metals
Organic frame has good property and Chemical Diversity.One characteristic feature of ferrous metals organic framework materials is that its is highly dense
The unsaturated ferrous metal center of degree can form stronger iron-oxygen key with the oxygen atom in organic ligand.Therefore, most of iron
Base Metal organic framework materials show preferable stability in organic solvent and water phase.Such as with some traditional porous materials
Zeolite is compared, and ferrous metals organic framework materials have better potentiality in various applications.For example, ferrous metals flexible have
Machine frame frame material can efficiently control its pore size and internal holes environment, to accelerate the entrance of guest molecule, that is, promote this
The entrance of the carbon nanotube molecule of inventive embodiments.Meanwhile ferro element abundant content in nature and hypotoxicity also promote
The development of ferrous metals organic framework materials.
On the other hand the embodiment of the present invention provides a kind of preparation method of electrode material, comprising: firstly, by carbon nanotube point
Dispersion liquid and metal organic dispersions form mixed liquor；Then, mixed liquor is dried, forms matrix；It is right in the case where protecting atmosphere
Matrix selenization, obtains electrode material.
The embodiment of the present invention also provides the preparation method for manufacturing the above embodiment of the present invention electrode material, by by carbon
Nanotube dispersion liquid and the dispersion of metal organic dispersions, both make to be sufficiently mixed contact, to form mixed liquor, then by mixed liquor
After drying, matrix grain is formed, after carrying out selenization to matrix, selenium material is wrapped in matrix grain outer surface, to matrix crystalline substance
Particle shape makes matrix obtain the effect for keeping presoma pattern at protection.So operation, step is simple, and technique is convenient, is conducive to throw
Enter large-scale production, beneficial to production.The obtained electrode material passes through the complex to carbon nanotube and metal organic frame
Selenization is carried out at matrix, while to the matrix after compound, matrix is obtained by selenization and keeps presoma pattern
Effect, to make electrode material that there is excellent electrochemical capacitance performance and good cyclical stability.
Specifically, carbon nanotube has many abnormal mechanics, electricity and chemical property as monodimension nanometer material, it can
Conductive material is made.And metal organic frame is to be self-assembly of by organic ligand and metal ion or cluster by coordinate bond
The hybrid inorganic-organic materials with molecule inner pore.In metal organic frame, organic ligand and metal ion or cluster
Arrangement have apparent directionality, different frame pore structures can be formed, to show different absorption properties, light
Learn property, electromagnetic property.It has high porosity, low-density, bigger serface, duct rule, aperture is adjustable and topological
The advantages that structure diversity and Scalability.
By carbon nanotube in conjunction with metal organic frame, the pore structure that metal organic frame has is received compared to by carbon
Mitron is directly incorporated in planar substrates, and carbon nanotube is incorporated on metal organic frame, can be provided for carbon nanotube compared with
The carbon nanotube of more specific surface areas, introducing is connected with each other, and so that electrode material is had more or active site, to mention
Its high chemical property.
In embodiments of the present invention, before carbon nano tube dispersion liquid and metal organic dispersions are formed mixed liquor, also
Include: to mix carbon nanotube with polyvinylpyrrolidone, forms carbon nano tube dispersion liquid in a solvent；Cobalt nitrate hexahydrate is molten
Liquid and the mixing of 2-methylimidazole solution, form metal organic dispersions.
Carbon nanotube is mixed with polyvinylpyrrolidone, is used to prepare carbon nano tube dispersion liquid；By metal organic frame
Cobalt nitrate hexahydrate solution and the mixing of 2-methylimidazole solution, are used to prepare metal organic dispersions.It should be noted that preparing carbon
Nanotube dispersion liquid and the step of prepare metal organic dispersions between and there is no relevances.Carbon nanotube point can first be prepared
Dispersion liquid, after prepare metal organic dispersions, can also first prepare metal organic dispersions, after prepare carbon nano tube dispersion liquid, also
Carbon nano tube dispersion liquid can be prepared and prepare metal organic dispersions while carrying out.
Wherein, the metal organic frame that the embodiment of the present invention is referred to should be carried out according to the specific ingredient of metal organic frame
ZIF-67 material can be made by cobalt nitrate hexahydrate solution and the mixing of 2-methylimidazole solution in selection, when metal organic frame selects
When for other metal organic frames, need replacing cobalt nitrate hexahydrate solution and 2-methylimidazole solution, changed into it is corresponding other
The raw material of metal organic frame, it is e.g., when preparing ferrous metals organic frame, cobalt nitrate hexahydrate solution and 2-methylimidazole is molten
Liquid mixes the mixing for being replaced by iron compound and solution, forms iron-based dispersion liquid；When preparing ZIF-8 skeleton, by six water nitre
Acidic cobalt solution and the mixing of 2-methylimidazole solution are replaced by the mixing of zinc-containing substance and solution.Prepare metal organic dispersions
Concrete operations should change therewith with the variation of metal organic frame.
In embodiments of the present invention, solvent is methanol.By methanol as solvent, carbon nano-tube material can be made to have good
Dispersion effect.
In embodiments of the present invention, cobalt nitrate hexahydrate solution and 2-methylimidazole solution are mixed, forms organic point of metal
Dispersion liquid, comprising: cobalt nitrate hexahydrate dissolution is uniformly dispersed in methyl alcohol, forms cobalt nitrate hexahydrate solution；2-methylimidazole is molten
Solution is uniformly dispersed in methyl alcohol, forms 2-methylimidazole solution；Cobalt nitrate hexahydrate solution is added in 2-methylimidazole solution, is formed
The metal organic dispersions of purple.
Specifically, when metal organic frame is ZIF-67 material, it is same to select alcohol solvent to obtain good dispersion
Effect, meanwhile, it is mixed using cobalt nitrate hexahydrate solution and 2-methylimidazole solution, needs to meet that 2-methylimidazole solution is fast
Speed is added in cobalt nitrate hexahydrate solution, so solution is made to be immediately turned into purple, so that meet metal organic dispersions prepares need
It asks.
In embodiments of the present invention, mixed liquor is dried, forms matrix, comprising: mixed liquor is started the cleaning processing,
Mixed liquor after being cleaned；Mixed liquor after cleaning is subjected to centrifugal treating, obtains filter residue；Filter residue is carried out at vacuum drying
Reason, obtains matrix.
The metal organic frame of high-purity in order to obtain needs to start the cleaning processing mixed liquor to remove the original in solution
Material matter, then centrifugal drying is carried out to the mixed liquor for removing raw material, it so can get matrix.Vacuum drying herein is true
Sky is dried, but it is to be appreciated that vacuum imperfect vacuum herein, but meeting general processing equipment can reach
Vacuum degree so that filter residue keeps stable state in the drying process.Similarly, dry so that filter by being passed through inert gas
Slag keeps stable state equally in the drying process and can satisfy the demand of the dry filter residue of the embodiment of the present invention.
In embodiments of the present invention, mixed liquor is started the cleaning processing, the mixed liquor after being cleaned, comprising: will mix
Liquid carries out centrifugal treating, obtains sediment；In methyl alcohol by sediment dissolution, the mixed liquor after being cleaned；Cleaning treatment is extremely
Less twice.
By methanol washed mixture, the same raw material using mixed liquor has the spy of good dispersion in methyl alcohol
Point can sufficiently remove raw material.The embodiment of the present invention is not defined the number of cleaning treatment, can for twice, three
It is secondary, four times, five times it is even more, be in cost consideration, the embodiment of the present invention preferably three times.
In embodiments of the present invention, electrode material is obtained, comprising: in vacuum to matrix selenization in the case where protecting atmosphere
Under the conditions of, selenium powder and the filter residue are made annealing treatment, electrode material is obtained；Or, under atmosphere of inert gases, to selenium powder and
The filter residue is made annealing treatment, and electrode material is obtained.
Protection atmosphere herein refers specifically to, and under the atmosphere that makes selenium powder and filter residue and will not occur redox reaction, such as exists
Under the atmosphere, selenium powder will not be aoxidized, the organic substance in filter residue will not volatilize, metallics maintains original shape state etc..Specifically, protecting
Shield atmosphere can be vacuum condition or inert gas conditions, and vacuum condition imperfect vacuum environment herein only needs general device
The vacuum degree that can be formed, and can satisfy that selenium powder will not aoxidize, the organic substance in filter residue will not volatilize, metallics remains former
The condition of form.Inert gas can be the inert gases such as nitrogen, helium, neon, argon gas, Krypton, xenon or radon gas.
On the other hand the embodiment of the present invention provides a kind of supercapacitor, including the electrode material in above embodiment.
The one kind of supercapacitor as electrochemical energy storage device, the great potential with large-scale application.Simultaneously as
The advantages that its power density with higher, fast charging and discharging and longer shelf-life, allows to be widely used in track friendship
Way system, road traffic, portable equipment and smart grid etc..It should be noted that being applied to Rail Transit System, road is handed over
Supercapacitor in the fields such as logical, portable equipment and smart grid also belongs to the supercapacitor that the embodiment of the present invention is referred to
Protection scope.Outside it, as a kind of electrode material, electrode material can also be applied to the fields such as sensor, battery.
For the purpose, technical solution and its advantage of the above embodiment of the present invention is more clearly understood, below with reference to specific
The embodiment of the present invention is further elaborated in embodiment.
Embodiment 1
A kind of preparation method of electrode material, comprising:
Firstly, 25mg carbon nanotube powder and 150mg polyvinylpyrrolidone are weighed, by carbon nanotube and polyvinyl pyrrole
Alkanone be added in the 21.4mL methanol solution measured in advance simultaneously carry out it is pre-dispersed, to obtain good CNTs dispersion effect.It will
It is labeled as solution 1 and stores for future use.
Then, it weighs 0.361g cobalt nitrate hexahydrate and 0.819g 2-methylimidazole is dissolved in the 12ml first measured in advance respectively
In alcoholic solution.When two kinds of reagents are completely dissolved in methyl alcohol, by 2-methylimidazole solution by toppling over addition cobalt nitrate hexahydrate
In solution, solution, which will become purple, be can be used.It is marked as solution 2 and stores for future use.
After again, solution 1 is poured into solution 2, carries out centrifugal treating after stirring 2h under room temperature environment, centrifugal process takes heavy
It is washed three times in starch with methanol, to remove extra 2-methylimidazole.To remove the solution of extra 2-methylimidazole again from
It takes filter residue to carry out vacuum drying 12h after the heart, obtains the crystalline material for being labeled as ZIF-67-CNT, the i.e. base of the embodiment of the present invention
Body.
Finally, weigh the matrix 50mg that has prepared, by it with 250mg selenium powder in crucible, the subsequent argon in tube furnace
The lower 600 DEG C of annealing 3h in compression ring border.After being cooled to room temperature, black powder is collected, is labeled as Se-ZIF-CNT, i.e., electricity of the invention
Pole material.
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 the electrode obtained material of the embodiment of the present invention；Fig. 2 is 1 the electrode obtained of the embodiment of the present invention
The scanning electron microscope (SEM) photograph of material.
As illustrated in fig. 1 and 2, using field emission scanning electron microscope instrument, to above-mentioned resulting electrode material powder into
Row scanning, resulting scanning electron microscope (SEM) photograph is from low power and high power scanning figure it can be seen that the diameter of regular dodecahedron structure is
300nm or so carries out selenization to matrix, still remains with the Se-ZIF- of the uniform polyhedron composition of insertion carbon nanotube
CNT composite material, the electrode material of the embodiment of the present invention.
Embodiment 2
A kind of preparation method of electrode material, comprising:
Firstly, 50mg carbon nanotube and 300mg polyvinylpyrrolidone are weighed, by carbon nanotube and polyvinylpyrrolidone
Be added in the 42.85mL methanol solution measured in advance simultaneously carry out it is pre-dispersed, to obtain good carbon nanotube dispersion effect.It will
It is labeled as solution 1 and stores for future use.
Then, it weighs 0.722g cobalt nitrate hexahydrate and 1.629g 2-methylimidazole is dissolved in the 25ml first measured in advance respectively
In alcoholic solution.When two kinds of reagents are completely dissolved in methyl alcohol, 2-methylimidazole solution is poured over six water nitre using wide-mouth bottle
In acidic cobalt solution, solution becomes purple.It is marked as solution 2 and stores for future use.
After again, solution 1 is poured into solution 2, centrifugal treating is carried out after stirring 2h under room temperature environment, precipitating is taken after centrifugation
It is washed three times in object with methanol, to remove extra 2-methylimidazole.The solution for removing extra 2-methylimidazole is centrifuged again
After take filter residue to carry out vacuum drying 12h, obtain the crystalline material for being labeled as ZIF-67-CNT, the i.e. matrix of the embodiment of the present invention.
Finally, the matrix 100mg prepared is weighed, by matrix and 500mg selenium powder in crucible, then in tube furnace
The lower 600 DEG C of annealing 3h of ar gas environment.After being cooled to room temperature, black powder is collected, is labeled as Se-ZIF-CNT, i.e., the present invention is real
Apply the electrode material of example.
Electrochemical property test is carried out to the obtained electrode material of embodiment 2:
Under 6M KOH electrolyte conditions, normal electrode is inertia Pt electrode, and reference electrode is Ag/AgCl electrode, work
Electrode is the Pt piece of carrying active substance, with three-electrode system in chi660E electrochemical workstation and blue electric system test material
Chemical property.The result of material of the present invention indicates, with relatively high specific capacity and its surely under different current densities
It is qualitative, and in 1Ag-1There is 100Fg when constant current charge-discharge-1Specific capacity.
Wherein, the method for electro-chemical test is as follows: by 80% electrode material, 10% acetylene black and 10%PVDF are mixed in
Nmp solution obtains mixture.Wherein, above 80% and 10% shared mass ratio is referred to.By resulting mixture coated in about
1.5cm2Nickel foam it is online, and 10MPa pressure pushing laminate, supercapacitor working electrode is made.In three electrodes
Its chemical property is tested in system testing.Platinum electrode and calomel electrode are used separately as to electrode and reference electrode, and electrolyte is
6.0mol L-1KOH solution.Cyclic voltammetry and constant current charge-discharge, which are tested, tests (CHI660E) in electrochemical workstation.
Embodiment 3
A kind of preparation method of electrode material, comprising:
Firstly, 50mg carbon nanotube and 300mg polyvinylpyrrolidone are weighed, by carbon nanotube and polyvinylpyrrolidone
Be added in the 42.85mL methanol solution measured in advance simultaneously carry out it is pre-dispersed, to obtain good carbon nanotube dispersion effect.It will
It is labeled as solution 1 and stores for future use.
Then, it weighs 0.722g cobalt nitrate hexahydrate and 1.629g 2-methylimidazole is dissolved in the 25ml first measured in advance respectively
In alcoholic solution.When two kinds of reagents are completely dissolved in methyl alcohol, 2-methylimidazole solution is poured over six water nitre using wide-mouth bottle
In acidic cobalt solution, solution becomes purple.It is marked as solution 2 and stores for future use.
After again, solution 1 is poured into solution 2, centrifugal treating is carried out after stirring 2h under room temperature environment, precipitating is taken after centrifugation
It is washed three times in object with methanol, to remove extra 2-methylimidazole.The solution for removing extra 2-methylimidazole is centrifuged again,
The crystalline material for being labeled as ZIF-67-CNT, the i.e. matrix of the embodiment of the present invention are obtained after taking filter residue to carry out vacuum drying 12h.
Finally, weighing the ZIF-67-CNT crystal 100mg prepared, it is then existed in crucible with 500mg selenium powder
The lower 600 DEG C of annealing 3h of ar gas environment in tube furnace.After being cooled to room temperature, black powder is collected, is labeled as Se-ZIF-CNT, i.e.,
The electrode material of the embodiment of the present invention.
Fig. 3 is 3 the electrode obtained material working electrode of the embodiment of the present invention in the different cyclic voltammograms swept under speed.Fig. 4 is
Constant current charge-discharge figure of the 3 the electrode obtained material working electrode of the embodiment of the present invention under different current densities.Fig. 5 is the present invention
The cycle performance figure of 3 the electrode obtained material of embodiment.
Referring to Fig. 3, Fig. 4 and Fig. 5, electrochemical property test is carried out to the obtained electrode material of embodiment 3:
Supercapacitor working electrode is made in gained active material in the conventional mode, and is surveyed in three-electrode system
Try its electrochemical properties.As can be seen that the electrode is respectively 1Ag in current density-1,5A·g-1,10A·g-1And 20Ag-1
When, specific capacitance is respectively 120,110,100 and 92F g-1.And as shown in figure 5, being 20Ag in current density-1Shi Xunhuan
5000 circles, remain to be maintained at 100% or so, embody good cyclical stability.
It in Fig. 4, is sorted in figure with peak value, curve from left to right successively represents electrode in current density 20Ag-1、
10A·g-1、5A·g-1And 1Ag-1When.
It should be noted that the room temperature environment in generation indicated above is 20~25 DEG C.Wherein, in process for preparation, carbon nanometer
The mass ratio of pipe and polyvinylpyrrolidone can be 1:1-10；The mass ratio of cobalt nitrate hexahydrate and 2-methylimidazole can be 1:
1-10；The volume of methanol is can dissolve carbon nanotube, polyvinylpyrrolidone, cobalt nitrate hexahydrate and 2-methylimidazole as standard
It is determined.
As it can be seen that electrode material provided by the embodiment of the present invention has excellent electrochemical capacitance performance and good stable circulation
Property.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.Moreover, particular features, structures, materials, or characteristics described
It may be combined in any suitable manner in any one or more of the embodiments or examples.In addition, without conflicting with each other, this
The technical staff in field can be by the spy of different embodiments or examples described in this specification and different embodiments or examples
Sign is combined.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic." first " is defined as a result, the feature of " second " can be expressed or hidden
It include at least one this feature containing ground.In the description of the present invention, the meaning of " plurality " is two or more, unless otherwise
Clear specific restriction.
More than, only a specific embodiment of the invention, but scope of protection of the present invention is not limited thereto, and it is any to be familiar with
Those skilled in the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all cover
Within protection scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
Claims (10)
1. a kind of electrode material, which is characterized in that including matrix, described matrix includes metal organic frame and is formed in the gold
Belong to the carbon nanotube on organic frame, described matrix passes through selenization.
2. electrode material according to claim 1, which is characterized in that the metal organic frame is ZIF-67 skeleton.
3. a kind of preparation method of electrode material characterized by comprising
Carbon nano tube dispersion liquid and metal organic dispersions are formed into mixed liquor；
The mixed liquor is dried, matrix is formed；
In the case where protecting atmosphere to described matrix selenization, electrode material is obtained.
4. preparation method according to claim 3, which is characterized in that described that carbon nano tube dispersion liquid and metal is organic
Dispersion liquid is formed before mixed liquor, further includes:
Carbon nanotube is mixed with polyvinylpyrrolidone, forms carbon nano tube dispersion liquid in a solvent；
Cobalt nitrate hexahydrate solution and 2-methylimidazole solution are mixed, metal organic dispersions are formed.
5. the preparation method according to claim 4, which is characterized in that the solvent is methanol.
6. the preparation method according to claim 4, which is characterized in that described by cobalt nitrate hexahydrate solution and 2-methylimidazole
Solution mixing, forms metal organic dispersions, comprising:
Cobalt nitrate hexahydrate dissolution is uniformly dispersed in methyl alcohol, forms the cobalt nitrate hexahydrate solution；
2-methylimidazole dissolution is uniformly dispersed in methyl alcohol, forms the 2-methylimidazole solution；
The cobalt nitrate hexahydrate solution, the empurpled metal organic dispersions of shape are added in the 2-methylimidazole solution.
7. preparation method according to claim 3, which is characterized in that it is described that the mixed liquor is dried, form base
Body, comprising:
The mixed liquor is started the cleaning processing, the mixed liquor after being cleaned；
Mixed liquor after the cleaning is subjected to centrifugal treating, obtains filter residue；
The filter residue is subjected to vacuum drying treatment, obtains described matrix.
8. preparation method according to claim 7, which is characterized in that it is described that the mixed liquor is started the cleaning processing, it obtains
Mixed liquor after to cleaning, comprising:
The mixed liquor is subjected to centrifugal treating, obtains sediment；
In methyl alcohol by sediment dissolution, the mixed liquor after obtaining the cleaning；
The cleaning treatment is at least twice.
9. preparation method according to claim 3, which is characterized in that it is described in the case where protecting atmosphere to described matrix selenizing at
Reason, obtains electrode material, comprising: under vacuum conditions, make annealing treatment to selenium powder and the filter residue, obtain electrode material；
Or, being made annealing treatment to selenium powder and the filter residue under atmosphere of inert gases, obtaining electrode material.
10. a kind of supercapacitor, which is characterized in that including electrode material as claimed in claim 1 or 2.
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Application publication date: 20190719 |