A kind of fluorine-containing surfactant modification electrical double layer capacitor electrodes is used preparation method of graphene
Technical field
The present invention relates to a kind of fluorine-containing surfactant modification electrical double layer capacitor electrodes and use preparation method of graphene.
Background technology
Graphene is a kind of novel two dimensional surface nano material, has the high and big characteristics of specific area of conductivity, is that a kind of novel double electric layer capacitor is used electrode active material.But when Graphene used as the electrical double layer capacitor electrodes active material, owing between Graphene stronger intermolecular force is arranged, Graphene took place compound easily, and its specific area is reduced.Simultaneously, the surface texture of Graphene inertia makes its electrolyte wettability and conductive ion migrate speed to be hindered, and causes the Graphene surface electric double layer to form efficient and reduces, and the equivalent series internal resistance of double electric layer capacitor increases.In order to prevent that Graphene is compound and to obtain excellent surface electrolyte wettability grapheme material, improve the energy storage density of double electric layer capacitor, reduce its equivalent series internal resistance, profit is carried out surface modification to Graphene usually.
At present; Graphene surface modification main method is to utilize surface modifier and the single dispersion graphene oxide effect that contains polar group (like hydroxyl, epoxide group etc.); Make surface modifier adsorb/be attached to the graphene oxide surface; Utilize physics or chemical method that graphene oxide is reduced to Graphene then, obtain surface modified graphite alkene material.Interaction between surface modifier and the Graphene, as pass through
πKey, ionic bond and hydrogen bond make the surface of Graphene by these minutes subcovering, prevent that Graphene is compound, improve the electrolyte wettability and the electrolyte ion of Graphene and migrate speed.
CN101775241A discloses " a kind of stearic acid modified graphene and application thereof "; This method is the feedstock production graphite oxide with the crystalline flake graphite; Add distilled water then; Ultrasonic concussion adds and adds strong reductant again after stearic acid fully reacts, and fully filters, washs, is drying to obtain stearic acid modified Graphene after the reaction.Its shortcoming is: stearic electrochemical stability is low, under the double electric layer capacitor operating voltage, is prone to decompose, and causes reduce the useful life of capacitor.Simultaneously, the compatibility of stearic hydrocarbon chain structure and fluorine-containing organic electrolyte is poor, and it is undesirable that the organic electrolyte wettability on Graphene surface and the migration rate of electrolyte ion improve effect.
CN101863465A discloses " a kind of organic solvent preparation method of graphene that is scattered in "; This method comprises the electronation of graphene oxide grafting dendroid substituting group and graphene oxide; Utilize bulky dendroid substituting group functionalization graphene oxide; Make the graphene oxide that obtains can be scattered in most of organic solvent, behind hydrazine hydrate reduction, the Graphene that obtains can also keep good organic solvent dispersive property.Its shortcoming is: dendritic compound is unfavorable for that organic electrolyte is to the Graphene wetting of surfaces; And huge dendritic morphology also hindered electrolyte ion and between graphene layer, migrated speed, can't effectively improve its energy density during as the double electric layer capacitor active material and reduce the equivalent series internal resistance.
Summary of the invention
The technical problem that the present invention will solve provides a kind of fluorine-containing surfactant modification electrical double layer capacitor electrodes and uses preparation method of graphene; The fluorine-containing surfactant modified graphene of this method preparation has good electrochemical stability and good fluorine-containing organic electrolyte wettability; Good with fluorine-containing organic electrolyte compatibility; Under high voltage, be difficult for decomposing; Can improve the Graphene surface electric double layer and form efficient and electrolyte ion transmission rate, can improve capacitor energy density and reduce the equivalent series internal resistance as electrode of super capacitor.
Technical solution of the present invention is:
A kind of fluorine-containing surfactant modification electrical double layer capacitor electrodes is used preparation method of graphene, and its concrete steps are:
1, preparation graphene oxide dispersion liquid and fluorine-containing surfactant solution
Graphene oxide and fluorine-containing surfactant are dispersed in respectively in the deionized water, described fluorine-containing surfactant be Sodium perfluorooctanoate, perfluoro octyl sulfonic acid sodium, perfluoro octyl sulfonic acid potassium, perfluoro octyl sulfonic acid ammonium, full-fluorine octyl sulfuryl fluoride, perfluoro butyl sulfonic acid fluoride, perfluoro butyl potassium sulfonate, perfluorinated nonene oxygen base benzene sulfonic acid sodium salt,
N-propyl group-perfluoro capryl sulphonyl ammonia potassium glutamate, perfluoro triethylamine, perfluamine, perfluorotributylamine,
N-ethyl perfluorinated octyl sulfuryl amine,
N-ethyl-
N-ethoxy perfluorinated octyl sulfuryl amine,
N-propyl group-
N-ethoxy perfluorinated octyl sulfuryl amine,
N-ethoxy perfluorinated octyl sulfuryl amine, perfluorinated octyl sulfuryl amine, perfluoroalkyl polyethers, perfluoroalkyl ethyoxyl ether alcohol, perfluoroalkyl betaine, perfluoro capryl sulphonyl season iodide, perfluoro capryl quaternary amine iodide, iodate
N-perfluor caprylamide propyl group-
N,
N,
N-three four basic ammoniums, perfluoro octyl sulfonic acid tetraethyl amine,
N-perfluor caprylamide propyl group-
N, N, N-three four basic ammoniums,
NAt least a in the hot sulfonamido propyl-triethoxysilicane of-perfluor, two (perfluoro butyl sulphonyl) imines lithium, perfluoro alkyl sulfonic acid, perfluoro carboxylic acid, perfluoroalkyl amine, perfluor tertiary amine, the perfluoropropene acid polymer, graphene oxide dispersion liquid and fluorine-containing surfactant solution;
2, the surface modification of graphene oxide
Graphene oxide dispersion liquid and fluorine-containing surfactant solution are mixed; The mass ratio of said fluorine-containing surfactant and graphene oxide is 1:1 ~ 1:10, under 20 ℃ ~ 100 ℃, 500rpm ~ 2000rpm, stirs 1h ~ 24h, is cooled to room temperature; Suction filtration; Keep filter cake,, obtain the modified oxidized graphene powder of fluorine-containing surfactant at 160 ℃ ~ 180 ℃ following vacuumize 6h ~ 24h;
3, the reduction of surface modification graphene oxide
With the modified oxidized graphene powder of fluorine-containing surfactant, join in the gaseous reducing agent, the mass ratio of described reducing agent and graphene oxide is 1:1 ~ 5:1, under 60 ℃ ~ 120 ℃, reduction reaction 12h ~ 48h obtains the fluorine-containing surfactant modified graphene.
Said fluorine-containing surfactant be perfluoro octyl sulfonic acid sodium, perfluoro butyl sulfonic acid fluoride, perfluorinated nonene oxygen base benzene sulfonic acid sodium salt, perfluamine, perfluorotributylamine,
N-propyl group-
NA kind of in-ethoxy perfluorinated octyl sulfuryl amine, perfluorinated octyl sulfuryl amine, perfluoroalkyl polyethers, perfluoroalkyl betaine, perfluoro octyl sulfonic acid tetraethyl amine, perfluoro carboxylic acid, the perfluoropropene acid polymer.
Said fluorine-containing surfactant is a kind of in perfluoro octyl sulfonic acid sodium, perfluoroalkyl polyethers, perfluamine, perfluoro capryl quaternary amine, perfluoroalkyl betaine, perfluoro carboxylic acid, the perfluoropropene acid polymer.
Said dispersion is ultrasonic dispersing or ball milling, and jitter time is 6h ~ 48h.
During preparation graphene oxide dispersion liquid, the mass volume ratio of graphene oxide and deionized water is 0.5mg/mL ~ 2.0mg/mL.
The concentration of said fluorine-containing surfactant solution is 500mg/L ~ 2500mg/L.
During surface modification, temperature is 50 ℃ ~ 60 ℃, and mixing time is 6h ~ 12h.
Said reducing agent is anhydrous hydrazine or hydrazine hydrate.
During said reduction reaction, temperature is 80 ℃ ~ 100 ℃.
The present invention is that dehydration complexing suction-operated takes place oxy radicals such as the epoxy radicals of utilizing the polar group of fluorine-containing surfactant and graphene oxide surface, hydroxyl, obtains the modified oxidized Graphene of fluorine-containing surfactant; Under the effect of vapour phase reduction agent, graphene oxide can fully be reduced to Graphene, and it is residual to have reduced in the product reducing agent; The vapour phase reduction process can effectively prevent the loss of fluorine-containing surfactant, fluorine-containing surfactant is better adsorbed or is attached to the Graphene surface, obtains the fluorine-containing surfactant modified graphene, and fluorine-containing surfactant modified graphene reaction equation is following:
Its beneficial effect is:
1, technology is simple, raw material is cheap and easy to get, production cost is low, is fit to suitability for industrialized production.
2, the fluorine-containing surfactant modified graphene that makes has strengthened the interlamellar spacing between the Graphene, has prevented the reunion of Graphene, has improved the specific area of Graphene.
3, fluorine-containing surfactant modified graphene and fluorine-containing organic system electrolyte, fluorine-containing adhesive all have the good interface compatibility; But improved between the wettability, conductive ion transmission rate, electrode active material of modified graphene bond strength and to fluorine-containing organic system electrolyte compatibility; Thereby improve the formation efficient of electric double layer; Can improve capacitor energy density as electrode of super capacitor, reduce the internal resistance of ultracapacitor equivalent series.
4, fluorine-containing surfactant stability is high, has guaranteed that the modified graphene electrode super capacitor has big capacity, low internal resistance and feature of long life.
Description of drawings
Fig. 1 is the unmodified Graphene (a) of Comparative Examples of the present invention, the perfluoro octyl sulfonic acid sodium modified graphene (b) of embodiment 1, the infrared analysis spectrogram of perfluoro octyl sulfonic acid natrium surfactant (c);
Fig. 2 is the scanning electron microscope diagram of the perfluoroalkyl ethyoxyl ether alcohol modified graphene of the embodiment of the invention 2;
Fig. 3 is the constant current charge-discharge curve chart of the perfluoroalkyl ethyoxyl ether alcohol modified graphene electrode of the embodiment of the invention 2;
Fig. 4 is the Nyquist curve chart of the quaternary ammonium salt modified Graphene electrodes of perfluoro capryl of the embodiment of the invention 3;
Fig. 5 is the constant current charge-discharge curve chart of the unmodified Graphene electrodes of Comparative Examples of the present invention;
Fig. 6 is the Nyquist curve chart of the unmodified Graphene electrodes of Comparative Examples of the present invention.
Embodiment
Embodiment 1
The preparation of fluorine-containing surfactant modified graphene:
1, preparation graphene oxide dispersion liquid and fluorine-containing surfactant solution
50mg graphene oxide powder is joined in the deionized water of 100mL, and the frequency ultrasonic wave dispersion 48h with 20kHz gets the graphene oxide dispersion liquid; (infrared spectrum is shown in Fig. 1 c) joins in the deionized water of 10mL with 5mg perfluoro octyl sulfonic acid sodium, and the frequency ultrasonic wave dispersion 6h with 20kHz gets the perfluoro octyl sulfonic acid sodium solution;
2, the surface modification of graphene oxide
The perfluoro octyl sulfonic acid sodium solution of step 1 preparation is joined in the graphene oxide dispersion liquid, stir 12h down at 20 ℃, 500rpm, suction filtration keeps filter cake, at 180 ℃ of following vacuumize 24h, and must the modified oxidized graphene powder of perfluoro octyl sulfonic acid sodium;
3, the reduction of surface modification graphene oxide
The modified oxidized graphene powder of perfluoro octyl sulfonic acid sodium is wrapped up with filter paper, transfer to and be equipped with on the support of there-necked flask that the 62.5mg mass concentration is 80% hydrazine hydrate, under 60 ℃; Reduction reaction 48h; Suction filtration gets black powder shape solid product, i.e. perfluoro octyl sulfonic acid sodium modified graphene; Infrared spectrum is shown in Fig. 1 b, and scanning electron microscopy is as shown in Figure 2, and the BET specific area is 1205 m
2/ g.
Can know that from Fig. 1 the modified oxidized Graphene of perfluoro octyl sulfonic acid sodium that makes has the characteristic peak of perfluoro octyl sulfonic acid sodium, the perfluoro octyl sulfonic acid sodium molecule that shown the Graphene surface attachment; Can know that from Fig. 2 the modified oxidized Graphene length of perfluoro octyl sulfonic acid sodium is that micron order, thickness are nano level monodispersed fold lamellar structure.
Get 50mg perfluoro octyl sulfonic acid sodium modified graphene and add the 0.01g quality than concentration 27% ptfe emulsion; Mechanical agitation 6h; The slurry metallizing aluminum foil current collector surface that obtains is obtained the electrode slice of 0.3 micron thick, and 80 ℃ of following vacuumize 24h are electrolyte with tetraethylammonium tetrafluoroborate/acetonitrile of 0.8mol/L; With the porous polypropylene is diaphragm paper, is assembled into double electric layer capacitor.
Embodiment 2
The preparation of fluorine-containing surfactant modified graphene:
1, preparation graphene oxide dispersion liquid and fluorine-containing surfactant solution
50mg graphene oxide powder is added in the 50mL deionized water, and the frequency ultrasonic wave dispersion 6h with 100kHz obtains the graphene oxide dispersion liquid; 10mg perfluoroalkyl ethyoxyl ether alcohol is joined in the deionized water of 10mL, and the frequency ultrasonic wave dispersion 12h with 100kHz gets perfluoroalkyl ethyoxyl ether alcohol solution;
2, the surface modification of graphene oxide
The perfluoroalkyl ethyoxyl ether alcohol solution of step 1 preparation is joined in the graphene oxide dispersion liquid, stir 12h down at 50 ℃, 1000rpm, suction filtration keeps filter cake, at 160 ℃ of following vacuumize 6h, and must the modified oxidized graphene powder of perfluoroalkyl ethyoxyl ether alcohol;
3, the reduction of surface modification graphene oxide
The modified oxidized graphene powder of perfluoroalkyl ethyoxyl ether alcohol is wrapped up with filter paper; Transfer on the support of the there-necked flask that the 100mg anhydrous hydrazine is housed, under 80 ℃, reduction reaction 12h; Suction filtration; Black powder shape solid product, i.e. perfluoroalkyl ethyoxyl ether alcohol modified graphene, the BET specific area is 1120 m
2/ g.
Getting 50mg perfluoroalkyl ethyoxyl ether alcohol modified graphene adding 0.01g quality is 27% ptfe emulsion than concentration; Mechanical agitation 6h; The slurry metallizing aluminum foil current collector surface that obtains is obtained the electrode slice of 0.3 micron thick, and 80 ℃ of following vacuumize 24h are electrolyte with tetraethylammonium tetrafluoroborate/acetonitrile of 0.8mol/L; With the porous polypropylene is diaphragm paper, is assembled into double electric layer capacitor; 2000 times the constant current charge-discharge curve is as shown in Figure 3.
Embodiment 3
The preparation of fluorine-containing surfactant modified graphene:
1, preparation graphene oxide dispersion liquid and fluorine-containing surfactant solution
50mg graphene oxide powder is added in the 25mL deionized water, disperse 12h, obtain the graphene oxide dispersion liquid with ball milling; 50mg perfluoro capryl quaternary amine is joined in the deionized water of 100mL, and the frequency ultrasonic wave dispersion 6h with 100kHz gets perfluoro capryl quaternary amine solution;
2, the surface modification of graphene oxide
The perfluoro capryl quaternary amine solution of step 1 preparation is added in the graphene oxide dispersion liquid, stir 6h down at 100 ℃, 2000rpm, suction filtration, the reservation filter cake, 170 ℃ of vacuumize 12h obtain the quaternary ammonium salt modified graphene oxide powder of perfluoro capryl;
3, the reduction of surface modification graphene oxide
The quaternary ammonium salt modified graphene oxide powder of perfluoro capryl is wrapped up with filter paper, transfer on the support of the there-necked flask that the 250mg anhydrous hydrazine is housed, under 100 ℃; Reduction reaction, 24h, suction filtration; Black powder shape solid product, i.e. the quaternary ammonium salt modified Graphene of perfluoro capryl, the BET specific area is 1302 m
2/ g.
Get the quaternary ammonium salt modified Graphene of 50mg perfluoro capryl and add the 0.01g quality than concentration 27% ptfe emulsion; Mechanical agitation 6h obtains the electrode slice of 0.3 micron thick, 80 ℃ of following vacuumize 24h with the slurry metallizing aluminum foil current collector surface that obtains; Tetraethylammonium tetrafluoroborate/acetonitrile with 0.8mol/L is an electrolyte; With the porous polypropylene is diaphragm paper, is assembled into double electric layer capacitor, and the Nyquist curve is as shown in Figure 4.
Embodiment 4
The preparation of fluorine-containing surfactant modified graphene:
1, preparation graphene oxide dispersion liquid and fluorine-containing surfactant solution
50mg graphene oxide powder is added in the 25mL deionized water, disperse 12h, obtain the graphene oxide dispersion liquid with ball milling; The 50mg perfluoro carboxylic acid is joined in the deionized water of 100mL, the frequency ultrasonic wave dispersion 6h with 100kHz gets perfluoro carboxylic acid solution;
2, the surface modification of graphene oxide
The perfluoro carboxylic acid solution of step 1 preparation is added in the graphene oxide dispersion liquid, stir 1h down at 60 ℃, 2000rpm, suction filtration, the reservation filter cake, 170 ℃ of vacuumize 12h obtain the modified oxidized graphene powder of perfluoro carboxylic acid;
3, the reduction of surface modification graphene oxide
The modified oxidized graphene powder of perfluoro carboxylic acid is wrapped up with filter paper, transfer on the support of the there-necked flask that the 250mg anhydrous hydrazine is housed, under 120 ℃; Reduction reaction, 24h, suction filtration; Black powder shape solid product, i.e. perfluoro carboxylic acid modified graphene, the BET specific area is 1060 m
2/ g.
Get 50mg perfluoro carboxylic acid modified graphene and add the 0.01g quality than concentration 27% ptfe emulsion; Mechanical agitation 6h; The slurry metallizing aluminum foil current collector surface that obtains is obtained the electrode slice of 0.3 micron thick, and 80 ℃ of following vacuumize 24h are electrolyte with tetraethylammonium tetrafluoroborate/acetonitrile of 0.8mol/L; With the porous polypropylene is diaphragm paper, is assembled into double electric layer capacitor.
Comparative Examples
50mg graphene oxide powder is wrapped up with filter paper, transfer to and be equipped with on the support of there-necked flask that the 62.5mg mass concentration is 80% hydrazine hydrate, under 60 ℃; Reduction reaction 48h, suction filtration gets black powder shape solid product; Promptly get Graphene, infrared spectrum is shown in Fig. 1 a;
Get the 50mg Graphene and add the 0.01g quality than concentration 27% ptfe emulsion; Mechanical agitation 6h; The slurry metallizing aluminum foil current collector surface that obtains is obtained the electrode slice of 0.3 micron thick, and 80 ℃ of following vacuumize 24h are electrolyte with tetraethylammonium tetrafluoroborate/acetonitrile of 0.8mol/L; With the porous polypropylene is diaphragm paper, is assembled into double electric layer capacitor; 2000 times the constant current charge-discharge curve is as shown in Figure 5, Nyquist curve such as Fig. 6.
Can know that by Fig. 4 the impedance of the quaternary ammonium salt modified Graphene electrodes of perfluoro capryl is 0.4 Ω, can know that by Fig. 6 unmodified Graphene electrodes impedance is 1.36 Ω; The quaternary ammonium salt modified Graphene electrodes of perfluoro capryl has reduced about 70% than unmodified Graphene electrodes impedance.
Not using the Graphene BET specific area of fluorine-containing surfactant modification is 700 m
2/ g is significantly less than the graphite BET specific area of fluorine-containing surfactant modification among the embodiment 1 ~ 4.This is because the fluorine-containing surfactant on Graphene surface has effectively prevented compound between Graphene, has increased the BET specific area of Graphene.
Graphene electrodes double electric layer capacitor chemical property of the present invention is as shown in table 1:
Table 1
Can know that by table 1 perfluoroalkyl ethyoxyl ether alcohol modified graphene electrode is 198Fg than electric capacity
-1, efficiency for charge-discharge is 98.1%, unmodified Graphene electrodes is 130Fg than electric capacity
-1Efficiency for charge-discharge is 98.8%; Perfluoroalkyl ethyoxyl ether alcohol modified graphene electrode has improved 52.3% than unmodified Graphene electrodes than electric capacity mutually; Efficiency for charge-discharge does not have significant change, and this is to cause its specific capacity to increase because fluorine-containing surfactant (perfluoroalkyl ethyoxyl ether alcohol) has increased the specific area and the wettable specific area of electrolyte of Graphene, and the good electrochemical stability of fluorine-containing surfactant makes it keep favorable charge-discharge stability simultaneously.