CN108417405B - Multi-slice stacked structure cobalt material and preparation method for super capacitor anode - Google Patents
Multi-slice stacked structure cobalt material and preparation method for super capacitor anode Download PDFInfo
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of multi-slice stacked structure cobalt materials and preparation method for super capacitor anode, belong to nanocomposite preparation field, solves the problems, such as that existing preparation method causes the connected state between lamella and stability is poor, gap is closely spaced.The technical solution adopted by the invention is as follows: a kind of preparation method of the multi-slice stacked structure cobalt material for super capacitor anode, graphene, Co (NO3) 2, urea, NH4F powder, cetyl trimethylammonium bromide and ethyl alcohol are added to the water and carry out pyroreaction after mixing, obtains first time sediment；First time sediment is successively washed, obtains the solid of graphene and cobalt composite material after drying；Graphene is added to the solid of cobalt composite material after being mixed in ionized water, adds to Chloride Solution reaction, obtain second of sediment；Second of sediment is successively washed, obtains multi-slice stacked structure cobalt material after drying.The present invention is used to prepare super capacitor anode material.
Description
Technical field
A kind of preparation method of the multi-slice stacked structure cobalt material for super capacitor anode, is used to prepare super electricity
Container negative electrode material belongs to nanocomposite preparation field.
Background technique
With the fuel vehicle of global range class and continuing on for fossil fuel, thus bring environmental problem is increasingly convex
It is aobvious, and the message for the fuel vehicle that prohibits selling is also in the visual field for constantly entering people.At present, it has been suggested that clearly prohibit selling the fuel vehicle time
The country of table includes Norway, Holland, Germany, Britain, France and India, and Chinese Ministry of Industry and Information is in the Thailand held on the 9th of September in 2017
It is proposed on up to forum, China also actively formulates the fuel vehicle timetable that prohibits selling, this behave shows to find the need of clean energy resource
Ask very urgent, supercapacitor is the substitution of the comparative superiority of traditional combustion engine as a kind of novel green energy storage device
Product.
Supercapacitor is divided into double electric layers supercapacitor and fake capacitance supercapacitor, and later people tie both
Hybrid super capacitor is collectively formed.The performance of electrode material determines the ability of the storage charge of supercapacitor,
For double electric layers supercapacitor, the main high-specific surface area using carbon material is come adsorption charge to complete depositing for charge
Storage, and fake capacitance supercapacitor then mainly carries out the storage of charge using the redox reaction of transition metal oxide
In 2004, since graphene is found, various excellent performances were proved that people are applied to section successively
It grinds with the various aspects of life, in supercapacitor, this field is no exception.The composite wood that graphene and inorganic matter are formed
Expect widely used in fake capacitance supercapacitor, the specific surface area of graphene superelevation, good electric conductivity, unique lamella
Structure is all that supercapacitor brings new breakthrough.
Graphene is compound with cobalt material, is the more one kind for promoting cobalt material property and improving pattern studied at present
Scheme, as Chinese patent (103093974 B of CN) grows graphene with the method for chemical vapor deposition in substrate, then electricity is heavy
Product cobalt hydroxide, forms the composite material of graphene and cobalt, which is integrally in film-form.Shortcoming are as follows: experiment
Method is not complicated, easy to operate, on the other hand, the material morphology for the multi-slice stacked structure prepared, not only bad for electrolyte
Intermediate ion transports, and can not alleviate material well in electrochemistry dependence test because material caused by expanding is desorbed.
Solvent-thermal method prepares the composite material of graphene and cobalt, is popular at present and effective method, such as Chinese patent (CN
104064372 B) hydro-thermal process is carried out to the cobalt amine complex containing sodium salt, it is prepared for class graphene cobalt hydroxide nanometer thin
Film is used for electrode material for super capacitor, which has synthesized a kind of cobalt hydroxide material of membrane structure, and be equally
The graphene of membrane structure is compound, has accomplished the minimum degree of magnitude on thickness, the requirement for super electric comparison surface area, can
With its chemical property of relatively good realization, shortcoming are as follows: connected state and stability between lamella be poor, gap spacing
Small problem.
Summary of the invention
It is an object of the invention to: the preparation method of existing multi-slice stacked structure cobalt material is solved, complexity is not easy to grasp
Make；The material morphology for the multi-slice stacked structure prepared, not only bad for transporting for electrolyte intermediate ion, and can not be very
The problem of good alleviation material is desorbed in electrochemistry dependence test because of material caused by expanding；And cause company between lamella
Logical state and stability is poor, the closely spaced problem in gap.The present invention provides a kind of multi-discs for super capacitor anode
Layer heap stack structure cobalt material and preparation method.
The technical solution adopted by the invention is as follows:
A kind of preparation method of the multi-slice stacked structure cobalt material for super capacitor anode, which is characterized in that packet
Include following steps:
Graphene, Co (NO3) 2, urea, NH4F powder, cetyl trimethylammonium bromide and ethyl alcohol are added step 1
Pyroreaction is carried out in water after mixing, obtains first time sediment；
First time sediment is successively washed, obtains the solid of graphene and cobalt composite material after drying by step 2；
After being added to graphene with the solid of cobalt composite material and mixing in ionized water, it is anti-to add to Chloride Solution for step 3
It answers, obtains second of sediment；
Second of sediment is successively washed, obtains multi-slice stacked structure cobalt material after drying by step 4.
Further, the specific steps of the step 1 are as follows:
Step 1.1, by graphene, add water be sufficiently stirred and ultrasound；
Step 1.2, by Co (NO3) 2, urea and NH4F powder, be added in graphene solution obtained in step 1.1 and stir
It mixes uniformly；
Cetyl trimethylammonium bromide powder is added in mixed liquor obtained in step 1.2 by step 1.3, stirring
Uniformly；
Ethyl alcohol is added into the resulting mixed solution of step 1.3 in step 1.4, stirs evenly；
Step 1.4 gained liquid is transferred in ptfe autoclave by step 1.5, anti-under 100-200 degrees Celsius
It answers, the reaction time is 6-24 hours, obtains first time sediment.
Further, the specific steps of the step step 2 are as follows:
Step 2.1 takes first time sediment water and ethyl alcohol to carry out centrifuge washing；
Step 2.2,30-100 degrees Celsius at a temperature of dry centrifuge washing sediment, drying time is that 10-24 is small
When, obtain the solid of graphene and cobalt composite material.
Further, specific step is as follows for the step 3:
Solid sodium chloride is added in deionized water step 3.1, leads to nitrogen and keeps nitrogen atmosphere, Celsius at 30~70 DEG C
It is stirred under the conditions of degree, obtains sodium chloride solution；
Step 3.2, by dilute hydrochloric acid solution, be added drop-wise in sodium chloride solution, obtain Chloride Solution；
Step 3.3, by the solid of graphene and cobalt composite material, be add to deionized water, be added drop-wise to after mixing evenly
In Chloride Solution, the moment keeps nitrogen, and temperature and stirring condition are reacted, and obtains second of sediment.
Further, the concentration of graphene is 0.5-3g/L in the step 1.1.
Further, the quality of step 1.2 urea is 0.5-5 times of NH4F, and Co (NO3) 2 is 0.2~5g.
Further, the concentration of cetyl trimethylammonium bromide is 0.1-1g/L in the step 1.3.
Further, the volume of ethyl alcohol is 1-5 times of water in step 1.1 in the step 1.4.
A kind of multi-slice stacked structure cobalt material for super capacitor anode, which is characterized in that quality accounting is as follows:
CoO is 70%~90%, and graphene is 10%~30%.
Further, the lamellar spacing of the multi-slice stacked structure cobalt material is between 5nm-1000nm, by 3-10 piece
Layer monomer composition；The thickness of single lamella is between 1nm-200nm；Gap spacing between the lamella 1nm-100nm it
Between.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
One, in the present invention, prepared multi-slice stacked structure cobalt material, at high temperature, using cobalt material in graphene
Growth in situ in lamellar structure, is on the one hand utilized the high-specific surface area of graphene, and another aspect cobalt is inserted into graphene fold
At strong lamella, the spacing of graphene sheet layer is increased, not only prevents the reunion of graphene itself, and is further increased
The specific surface area of entire composite material；
Two, in the present invention, ethyl alcohol not only changes as secondary solvent, the physicochemical properties of grapheme modified solution itself
The pressure atmosphere in reaction kettle is become, has also changed the concentration of different material in reaction system, has affected in raw material reaction process
Dynamic behavior, and be coordinated with reactant, play key effect during the nucleation and growth of cobalt material, produced
New material morphology is given birth to；The material morphology for the multi-slice stacked structure prepared not only is conducive to transporting for electrolyte intermediate ion,
And it can preferably alleviate material in electrochemistry dependence test because material caused by expanding is desorbed.
Three, in the present invention, in the case where not introducing other metal salts, surfactant cetyl trimethyl bromination
The addition of ammonium, so that compound between graphene and cobalt material becomes more perfect, its in CTAB molecule be hydrophilic and lipophilic group
It interacts in a solvent, constitutes nano-reactor, form one " bridge " between graphene and cobalt material, play coupling and make
With connected state and stability between improvement lamella increase the stability of composite material；
Four, Cl-Intercalation, Cl-Passing through electrostatic interaction and Van der Waals in gap between the cobalt element on lamella
Power effect combines, and thermodynamically stable intercalation configuration, and Cl may be implemented-Introducing, increase the gap between lamella with
And the specific surface area of material improves ion permeability for surpassing in cell negative pole material, optimize the electric double layer of material with it is counterfeit
Capacity effect.
Five, the pattern of multi-slice stacked structure is conducive to transporting for electrolyte intermediate ion in the present invention, improves the electricity of material
Chemical property, and very thin lamellar spacing, increase the specific surface area of material, reduce the specific gravity of invalid active material, then
In addition the composite construction with graphene, the strong conductive capability of graphene makes entire material all in connected state, reduces nothing
The active material of method participation electrochemical action；
Six, the present invention in from active material itself, CoO will be in the form of dissolution-deposition in potassium hydroxide electrolyte
It is changed into β-Co (OH) 2, β-Co (OH) 2 and is changed into β-CoOOH with good conductivity, composite material shape in charging oxidation process
At a conductive network；When electrode discharge, β-CoOOH, which is not effectively reversible, is changed into β-Co (OH) 2；Therefore, because charging oxidation shape
At β-CoOOH there is good electron conduction, can greatly increase nickel electrode depth of discharge, improve active material utilization and
Discharge potential.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of multi-slice stacked structure cobalt material of the present invention；
Fig. 2 is the electron scanning micrograph of 1 gained final product of the embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
The preparation method of existing multi-slice stacked structure cobalt material is solved, it is complicated, not easy to operate；The multi-disc layer heap prepared
The material morphology of stack structure not only bad for transporting for electrolyte intermediate ion, and can not alleviate material in electrification well
The problem of being desorbed when learning dependence test because of material caused by expanding；And cause connected state and stability between lamella
Difference, the closely spaced problem in gap.
The present invention uses solvent-thermal method, under hot conditions, cobalt material growth in situ on the surface of graphene, and this composite wood
On the one hand the high-specific surface area of graphene is utilized in material, and cobalt is inserted at the strong lamella of graphene fold, increases graphite
The spacing of alkene lamella, not only prevents the reunion of graphene itself, and further increases the specific surface area of entire composite material.
Different from the compound of simple graphene and material, the present invention it is also creative ethyl alcohol is added in graphene solution as auxiliary
Cosolvent has modified the physicochemical properties of graphene solution itself.The addition of ethyl alcohol not only changes the pressure in reaction kettle
Atmosphere also changes the concentration of different material in reaction system, affects dynamic behavior in raw material reaction process, and with it is anti-
It answers object to be coordinated, plays key effect during the nucleation and growth of cobalt material, produce new material morphology.Surface
The addition of activating agent CTAB so that compound between graphene and cobalt material becomes more perfect, its in CTAB molecule it is hydrophilic with
Lipophilic group interacts in a solvent, constitutes nano-reactor, forms one " bridge " between graphene and cobalt material, plays
Coupled action increases the stability of composite material.The present invention is based on fake capacitance supercapacitors, elaborate graphene and cobalt shape
At composite material in supercapacitor application and material preparation method.
Lamella is to be respectively provided with positive and negative different ion on lamella and gap from the characteristics of lamella stacked structure to protect
It holds total and is in stable structure and charge stable state, the distinctive ion-exchange capacity of interlayer anion and exchange are held
Amount has been the applications expanding of layer structure material, and ion exchange, such as NO3 may be implemented in new field, a large amount of anion-、
Cl-、F-、SO4 2-And CO3 2-Deng the intercalation of different anions can carry out the function of different aspect to material strips, and the present invention mainly uses
Cl-Intercalation, Cl-It is mutually being tied between the cobalt element on lamella by electrostatic interaction and van der Waals interaction in gap
It closes, thermodynamically stable intercalation configuration, and Cl may be implemented-Introducing, increase the gap between lamella and the ratio of material
Surface area improves ion permeability, optimizes the electric double layer and fake capacitance effect of material for surpassing in cell negative pole material.
Embodiment 1
1) graphene concentration is 0.5-3g/L, weighs graphene, and 13-20mL water is added be sufficiently stirred and ultrasound；
2) the cobalt nitrate Co (NO of 0.5g is weighed3)2, the urea of 50-500mg and the NH of 100mg4F powder, is added to step
1) it in the graphene solution obtained, stirs 10 minutes；
3) it weighs 2.5-25mg cetyl trimethylammonium bromide (CTAB) powder and is added to the mixed liquor that step 1) obtains
In, it stirs 10 minutes；
4) it measures 5-13mL ethyl alcohol to be added in above-mentioned mixed solution, stir 10 minutes；
5) liquid for obtaining step 4) is transferred in ptfe autoclave, is reacted under 100-200 degrees Celsius, instead
It is 6-24 hours between seasonable, obtains first time sediment；
6) first time sediment water and ethyl alcohol is taken to carry out centrifuge washing；
7) 30-100 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 10-200g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, taken the photograph 50
It is stirred evenly under the conditions of family name's degree；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 1-20g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water,
Stirring is added drop-wise in the solution for the chloride ion-containing that step 9) obtains after 1 hour；
11) moment keeps nitrogen, temperature and stirring condition, and second of sediment centrifugation after reaction 6-24 hours is washed
It washs, dry to get the structural schematic diagram of composite material as shown in Figure 1.Embodiment 2
1) graphene concentration is 0.5g/L, weighs graphene, and 13mL water is added be sufficiently stirred and ultrasound；
2) Co (NO of 0.5g is weighed3)2, the urea of 50mg and the NH of 100mg4F powder is added to the stone that step 1) obtains
In black alkene solution, stir 10 minutes；
3) it weighs 2.5mg CTAB powder to be added in the mixed liquor that step 2) obtains, stir 10 minutes；
4) it measures 13mL ethyl alcohol to be added in the mixed solution that step 3) obtains, stir 10 minutes；
5) liquid for obtaining step 4) is transferred in ptfe autoclave, is reacted at one hundred and twenty degrees centigrade, when reaction
Between be 12 hours, obtain first time sediment；
6) first time precipitate object water and ethyl alcohol is taken to carry out centrifuge washing；
7) 70 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 10g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, at 50 degrees Celsius
Under the conditions of stir；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 1g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water, is stirred
It is added drop-wise to after 1 hour in the solution for the chloride ion-containing that step 9) obtains；
11) moment keeps nitrogen, temperature and stirring condition, second of sediment centrifuge washing after reaction 6 hours, dry
The dry structural schematic diagram to get composite material as shown in Figure 1.
Embodiment 3
1) graphene concentration is 3g/L, weighs graphene, and 20mL water is added be sufficiently stirred and ultrasound；
2) Co (NO of 0.5g is weighed3)2, the urea of 500mg and the NH of 100mg4F powder is added to the stone that step 1) obtains
In black alkene solution, stir 10 minutes；
3) it weighs 25mg CTAB powder to be added in the mixed liquor that step 2) obtains, stir 10 minutes；
4) it measures 5mL ethyl alcohol to be added in the mixed solution that step 3) obtains, stir 10 minutes；
5) liquid for obtaining step 4) is transferred in ptfe autoclave, is reacted under 150 degrees Celsius, when reaction
Between be 15 hours, obtain first time sediment；
6) first time sediment water and ethyl alcohol is taken to carry out centrifuge washing；
7) 70 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 200g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, at 50 degrees Celsius
Under the conditions of stir；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 20g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water, stirs
It is added drop-wise in the solution for the chloride ion-containing that step 9) obtains after mixing 1 hour；
11) moment keeps nitrogen, temperature and stirring condition, second of sediment centrifuge washing after reaction 24 hours,
The dry structural schematic diagram to get composite material as shown in Figure 1.
Embodiment 4
1) graphene concentration is 1g/L, weighs graphene, and 16mL water is added be sufficiently stirred and ultrasound；
2) Co (NO of 0.5g is weighed3)2, the urea of 150mg and the NH of 100mg4F powder is added to the stone that step 1) obtains
In black alkene solution, stir 10 minutes；
3) it weighs 10mg CTAB powder to be added in the mixed liquor that step 2) obtains, stir 10 minutes；
4) it measures 8mL ethyl alcohol to be added in the mixed solution that step 3) obtains, stir 10 minutes；
5) liquid for obtaining step 4) is transferred in ptfe autoclave, is reacted under 150 degrees Celsius, when reaction
Between be 12 hours, obtain first time sediment；
6) first time sediment water and ethyl alcohol is taken to carry out centrifuge washing；
7) 70 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 100g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, at 50 degrees Celsius
Under the conditions of stir；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 10g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water, stirs
It is added drop-wise in the solution for the chloride ion-containing that step 9) obtains after mixing 1 hour；
11) moment keeps nitrogen, temperature and stirring condition, second of sediment centrifuge washing after reaction 12 hours,
The dry structural schematic diagram to get composite material as shown in Figure 1.
Embodiment 5
1) graphene concentration is 1g/L, weighs graphene, and 16mL water is added be sufficiently stirred and ultrasound；
2) Co (NO of 0.5g is weighed3)2, the urea of 150mg and the NH of 100mg4F powder is added to the stone that step 1) obtains
In black alkene solution, stir 10 minutes；
3) it weighs 10mg CTAB powder to be added in the mixed liquor that step 2) obtains, stir 10 minutes；
4) it measures 8mL ethyl alcohol to be added in the mixed solution that step 3) obtains, stir 10 minutes；
5) aforesaid liquid is transferred in ptfe autoclave, is reacted under 180 degrees Celsius, the reaction time is 24 small
When, obtain first time sediment；
6) first time sediment water and ethyl alcohol is taken to carry out centrifuge washing；
7) 70 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 150g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, at 50 degrees Celsius
Under the conditions of stir；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 15g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water, stirs
It is added drop-wise in the solution for the chloride ion-containing that step 9) obtains after mixing 1 hour；
11) moment keeps nitrogen, temperature and stirring condition, second of sediment centrifuge washing after reaction 24 hours,
The dry structural schematic diagram to get composite material as shown in Figure 1.
Embodiment 6
1) graphene concentration is 0.5g/L, weighs graphene, and 13mL water be sufficiently stirred and ultrasound；
2) Co (NO of 0.5g is weighed3)2, the urea of 500mg and the NH of 100mg4F powder is added to the stone that step 1) obtains
In black alkene solution, stir 10 minutes；
3) it weighs 10mg CTAB powder to be added in the mixed liquor that step 2) obtains, stir 10 minutes；
4) it measures 13mL ethyl alcohol to be added in the mixed solution that step 3) obtains, stir 10 minutes；
5) aforesaid liquid is transferred in ptfe autoclave, is reacted at one hundred and twenty degrees centigrade, the reaction time is 12 small
When, obtain first time sediment；
6) first time sediment water and ethyl alcohol is taken to carry out centrifuge washing；
7) 100 degrees Celsius at a temperature of it is 12 hours dry, obtain the solid of graphene and cobalt composite material；
8) it weighs 180g NaCl solid to be added in the deionized water of 1L, leads to nitrogen and keep nitrogen atmosphere, at 50 degrees Celsius
Under the conditions of stir；
9) 10mL dilute hydrochloric acid solution is measured, is added drop-wise in the sodium chloride solution that step 8) obtains；
10) solid that 15g reacts obtained graphene and cobalt composite material before is weighed, is add to deionized water, stirs
It is added drop-wise in the solution for the chloride ion-containing that step 9) obtains after mixing 1 hour；
11) moment keeps nitrogen, temperature and stirring condition, second of sediment centrifuge washing after reaction 12 hours,
The dry structural schematic diagram to get composite material as shown in Figure 1.
In addition to graphene, Co (NO3) 2, urea, NH4F powder, cetyl trimethyl bromination in embodiment 1- embodiment 6
Ammonium and ethyl alcohol are added to the water outside the sequence of mixing, can also be mixed by other addition sequences or be added to the water simultaneously.
A kind of multi-slice stacked structure cobalt material for super capacitor anode, quality accounting are as follows: CoO be 70%~
90%, graphene is 10%~30%.The lamellar spacing of the multi-slice stacked structure cobalt material between 5nm-1000nm, by
3-10 lamella monomer composition；The thickness of single lamella is between 1nm-200nm.Gap spacing between the lamella is in 1nm-
Between 100nm.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of the multi-slice stacked structure cobalt material for super capacitor anode, which is characterized in that including
Following steps:
Step 1, by graphene, Co (NO3)2, urea, NH4F powder, cetyl trimethylammonium bromide and ethyl alcohol are added to the water mixed
After closing uniformly, is reacted in ptfe autoclave, at 100-200 DEG C, obtain first time sediment；
First time sediment is successively washed, obtains the solid of graphene and cobalt composite material after drying by step 2；
Step 3 after being add to deionized water graphene with the solid of cobalt composite material and mixing, adds in Chloride Solution,
Moment keeps nitrogen, 30-70 DEG C of temperature and stirring condition to be reacted, and obtains second of sediment；
Second of sediment is successively washed, obtains multi-slice stacked structure cobalt material after drying by step 4.
2. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 1
Method, which is characterized in that the specific steps of the step 1 are as follows:
Step 1.1, by graphene, add water be sufficiently stirred and ultrasound；
Step 1.2, by Co (NO3)2, urea and NH4F powder is added in graphene solution obtained in step 1.1 and stirs
It is even；
Cetyl trimethylammonium bromide powder is added in mixed liquor obtained in step 1.2 by step 1.3, is stirred evenly；
Ethyl alcohol is added into the resulting mixed solution of step 1.3 in step 1.4, stirs evenly；
Step 1.4 gained liquid is transferred in ptfe autoclave by step 1.5, is reacted under 100-200 degrees Celsius,
Reaction time is 6-24 hours, obtains first time sediment.
3. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 2
Method, which is characterized in that the specific steps of the step 2 are as follows:
Step 2.1 takes first time sediment water and ethyl alcohol to carry out centrifuge washing；
Step 2.2,30-100 degrees Celsius at a temperature of dry centrifuge washing sediment, drying time is 10-24 hours, is obtained
To the solid of graphene and cobalt composite material.
4. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 3
Method, which is characterized in that specific step is as follows for the step 3:
Solid sodium chloride is added in deionized water step 3.1, leads to nitrogen and keeps nitrogen atmosphere, in 30~70 DEG C of degrees Celsius of items
It is stirred under part, obtains sodium chloride solution；
Step 3.2, by dilute hydrochloric acid solution, be added drop-wise in sodium chloride solution, obtain Chloride Solution；
Step 3.3, by the solid of graphene and cobalt composite material, be add to deionized water, be added drop-wise to after mixing evenly chlorine from
In sub- solution, the moment keeps nitrogen, and temperature and stirring condition are reacted, and obtains second of sediment.
5. a kind of multi-slice stacked structure cobalt material for super capacitor anode according to claim 2-4 any one
The preparation method of material, which is characterized in that the concentration of graphene is 0.5-3g/L in the step 1.1.
6. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 4
Method, which is characterized in that the quality of step 1.2 urea is NH40.5-5 times of F, Co (NO3)2For 0.2~5g.
7. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 5
Method, which is characterized in that the concentration of cetyl trimethylammonium bromide is 0.1-1g/L in the step 1.3.
8. a kind of preparation side of multi-slice stacked structure cobalt material for super capacitor anode according to claim 6
Method, which is characterized in that the volume of ethyl alcohol is 1-5 times of water in step 1.1 in the step 1.4.
It is tied 9. the multi-slice for super capacitor anode of the method preparation in any one of -8 stacks according to claim 1
Structure cobalt material, which is characterized in that quality accounting is as follows: CoO is 70%~90%, and graphene is 10%~30%.
10. a kind of multi-slice stacked structure cobalt material for super capacitor anode according to claim 9, feature
It is, the lamellar spacing of the multi-slice stacked structure cobalt material is between 5nm-1000nm, by 3-10 lamella monomer composition；
The thickness of single lamella is between 1nm-200nm；Gap spacing between the lamella is between 1nm-100nm.
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