CN110127683A - A kind of graphene dispersing solution and its preparation method and application - Google Patents
A kind of graphene dispersing solution and its preparation method and application Download PDFInfo
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- CN110127683A CN110127683A CN201910531321.7A CN201910531321A CN110127683A CN 110127683 A CN110127683 A CN 110127683A CN 201910531321 A CN201910531321 A CN 201910531321A CN 110127683 A CN110127683 A CN 110127683A
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- C01B32/00—Carbon; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention relates to a kind of graphene dispersing solution and preparation method thereof and purposes, and described method includes following steps: (1) uniform admixed graphite alkene and cetyl trimethylammonium bromide obtain surface-functionalized graphene；(2) surface-functionalized graphene obtained by mixing deionized water and step (1), is added surfactant, second of ultrasound after standing obtains uniformly mixed mixed liquor for the first time when ultrasound；(3) mixed liquor obtained by centrifugal treating step (2) collects supernatant liquid, obtains dispersion liquid；(4) mixing sodium hydride and step (3) gained dispersion liquid, heating is reacted under inert gas shielding, obtains the graphene dispersing solution after cooling.It is scattered in deionized water to graphene uniform in gained graphene dispersing solution of the invention, dispersion efficiency is high, and for viscosity down to 4239cps, graphene-structured is complete, and the electric conductivity for the graphene dispersing solution being prepared is good, and resistivity is down to 38 Ω cm.
Description
Technical field
The invention belongs to conductive material technical fields, are related to a kind of graphene conductive material more particularly to a kind of graphene
Dispersion liquid and its preparation method and application.
Background technique
Graphene is a kind of bi-dimensional cellular shape carbon material, is arranged according to hexagon by carbon atom and is formed.Carbon carbon is former
By sp between son2Hydridization is combined into, and structure is highly stable.The special structure of graphene causes to make it have many excellent property
Matter.Graphene is to have now been found that the maximum substance of hardness, and by fabulous mechanical property, theoretical specific surface area is big, is had prominent
Heating conduction out, and graphene has good electric conductivity, at room temperature, electron mobility is up to 20000cm2/(V·
s).However, the big specific surface area of graphene often makes it reunite together, the adsorption capacity of itself and influence are not only reduced
The performance of graphene itself excellent properties, to influence the improvement of graphene enhancing composite property.
106115668 A of CN discloses the dispersing method and graphene composite material of a kind of graphene, and this method makes hard
Material granule is in vibratory liquefaction and irregular movement state, and graphene oxide solution is uniformly sprayed to hard material particle table
Face obtains evenly dispersed graphene composite material.Although this method is able to solve graphene problem easy to reunite, but it is obtained
Be a kind of graphene composite material, can not including the evenly dispersed compound graphene layer of hard material particle and its surface
By graphene uniform it is dispersed in water.
108726513 A of CN discloses a kind of preparation method of graphene dispersing solution, and this method is first by graphene oxide
Graphene powder is prepared, then graphene powder is carried out to ultrasound, homogenized in a solvent, dispersing agent is added and surface is living
It is ultrasonically treated again after property agent, obtains graphene dispersing solution eventually by centrifugation.But it is super that ultrasonic wave is used for multiple times in this method
Sound, consume energy big and destructible graphene-structured, is unfavorable for improving the performance of graphene dispersing solution.
106902701 A of CN discloses a kind of graphene dispersion agent, and the graphene dispersion agent is by following mass fraction
Group is grouped as: 1-3 parts of N-Methyl pyrrolidone, 1-4 parts of cetyl benzenesulfonic acid sodium, and 1-4 parts of neopelex, poly- second
1-3 parts of alkene pyrrolidone, 1-4 parts of sodium lignin sulfonate, 1-4 parts of sodium taurocholate, 1-2 parts of cetyl trimethylammonium bromide, polyoxy
1-3 parts of ethylene laurel ether, 1-3 parts of Tween 80, polyethylene glycol is to 1-3 parts of isooctyl phenyl ether, 1-4 parts of lysine, polyvinyl alcohol
1-3 parts, 1-3 parts of polyacrylamide, 1-3 parts of polyacrylic acid, 1-3 parts of polymethylacrylic acid, 1-4 parts of polyethylene glycol oxide.Although should
Graphene dispersion agent dispersed graphite alkene and can make graphene not reunite for a long time rapidly, but dispersant used in this method is numerous
It is more, it is unfavorable for the stability of graphene performance.
Liu Peng etc. has delivered graphene uniform the dispersion progress (material Leader, 2016,30 (10): 39-45), should
Studies have shown that passing through situ aggregation method, the functionalization of graphene, the modification of graphene, sulfonation precipitating or the side of scion grafting functional group
Method improves the dispersion performance of graphene, but does not provide specific operating method.
Therefore it provides a kind of graphene dispersing solution of good dispersion property and preparation method thereof and purposes, for improving stone
The application potential of black alkene has great importance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of graphene dispersing solution and its preparation side
Method and purposes, this method are dispersed in water in which can make graphene uniform, and dispersion efficiency is high, and dispersion stabilization is good, and this method
Small to the destruction of graphene-structured, the good dispersion property for the graphene dispersing solution being prepared, electric conductivity is excellent.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, described method includes following steps the present invention provides a kind of preparation method of graphene dispersing solution:
(1) uniform admixed graphite alkene and cetyl trimethylammonium bromide, obtain surface-functionalized graphene；
(2) mixing deionized water and graphene surface-functionalized obtained by step (1), are added surface for the first time and live when ultrasound
Property agent, second of ultrasound after standing obtain uniformly mixed mixed liquor；
(3) mixed liquor obtained by centrifugal treating step (2) collects supernatant liquid, obtains dispersion liquid；
(4) mixing sodium hydride and step (3) gained dispersion liquid, heating is reacted under inert gas shielding, after cooling
To the graphene dispersing solution.
Graphene, which is directly dissolved in water, so that graphene is reunited, and influence the electric conductivity of graphene, and the present invention passes through graphite
Electrostatic attraction between alkene and excessive cetyl trimethylammonium bromide carries out surface to graphene and is modified, then living on surface
Property agent and ultrasonic disperse under the action of make the modified graphene dispersion Yu Shuizhong in surface, and separate excessive cetyl front three
Base ammonium bromide finally restores the graphene that is partially oxidized in dispersion process under the action of sodium hydride, finally obtain purity compared with
The high and good graphene dispersing solution of dispersion effect.
Preferably, the mass ratio of step (1) graphene and cetyl trimethylammonium bromide is 1:(25-35), example
It such as can be 1:25,1:26,1:27,1:28,1:29,1:30,1:31 or 1:32, preferably 1:(27-32).Excessive hexadecane
Base trimethylammonium bromide fully can carry out surface to graphene by electrostatic attraction and be modified, and graphene is made to be dissolved in deionized water
It is separated afterwards with foreign ion, and not easy to reunite.
Preferably, step (1) mixing carries out under anaerobic, and cetyl trimethyl bromine is mixed under oxygen free condition
Change ammonium and graphene, prevents graphene from reuniting in mixed process.
Preferably, step (1) the mixed temperature be 10-30 DEG C, such as can be 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C or
30 DEG C, preferably 15-20 DEG C.
Preferably, step (2) deionized water and the liquid-solid ratio of graphene surface-functionalized obtained by step (1) are
(500-1500): 1, such as can be 500:1,600:1,700:1,800:1,900:1,1000:1,1100:1,1200:1,
1300:1,1400:1 or 1500:1, preferably (800-1200): 1.
Preferably, the power of step (2) the first time ultrasound be 270-350W, such as can be 270W, 280W,
290W, 300W, 310W, 320W, 330W, 340W or 350W, preferably 300-320W.
Preferably, the time of step (2) the first time ultrasound be 50-70min, such as can be 50min, 55min,
60min, 65min or 70min, preferably 55-65min.
Preferably, the time of step (2) described standing be 20-40min, such as can be 20min, 25min, 30min,
35min or 40min, preferably 25-35min.Standing can make between surfactant and cetyl trimethylammonium bromide
It interacts more abundant, to improve the dispersion effect of surface-functionalized graphene, makes the dispersion effect of second of ultrasound
More preferably.
Preferably, the power of step (2) second ultrasound is 650-750W, for example, can be 650W, 660W,
670W, 680W, 690W, 700W, 710W, 720W, 730W, 740W or 750W, preferably 680-720W.
Preferably, the time of step (2) second ultrasound is 50-70min, for example, can be 50min, 55min,
60min, 65min or 70min, preferably 55-65min.
The first time ultrasound of present invention application low-power disperses surface with the technology that high-power second of ultrasound combines
The graphene of functionalization is for the first time tentatively ultrasonically treated surface-functionalized graphene using low-power when ultrasound, and
Surfactant is added in first time ultrasonic procedure, makes between surfactant and cetyl trimethylammonium bromide preferably
Interaction, improves the dispersion effect of surface-functionalized graphene；Power is higher when second of ultrasound, and living by surface
Property agent effect surface-functionalized graphene stable structure, spread more evenly across in second ultrasound in deionized water
In.
Preferably, step (2) described surfactant includes in sodium glycocholate, odium stearate or lauric acid amide of ethanol
Any one or at least two combination, it is typical but non-limiting combination include sodium glycocholate and odium stearate combination,
The combination of the combination of odium stearate and lauric acid amide of ethanol, sodium glycocholate and lauric acid amide of ethanol or sodium glycocholate,
The combination of odium stearate and lauric acid amide of ethanol, preferably sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol
Combination.
Preferably, the mass ratio of the sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol is (2-4): 1:(5-
8), such as 2:1:5,2:1:6,2:1:7,2:1:8,3:1:5,3:1:6,3:1:7,3:1:8,4:1:5,4:1:6,4:1 be can be:
7 or 4:1:8, preferably 3:1:6.
The present invention is by the surfactant that selection specifically forms to improve dividing for the graphene dispersing solution being prepared
Performance is dissipated, when the mass ratio of sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol in surfactant is more than institute of the present invention
When numberical range to be protected, the dispersion performance of gained graphene dispersing solution declines.
Preferably, the mass ratio of graphene surface-functionalized obtained by the additional amount Yu step (1) of the surfactant
For (1-10): 100, such as can be 1:100,2:100,3:100,4:100,5:100,6:100,7:100,8:100,9:100
Or 10:100, preferably (2-6): 100.
Preferably, step (2) the addition surfactant is to be initially added into table when ultrasound carries out 1/3-2/3 for the first time
Face activating agent, and be added completely at the end of ultrasound for the first time.Surfactant is added in first time ultrasonic procedure in the present invention,
Make surfactant under ultrasonication more evenly with the cetyl trimethylammonium bromide in surface-functionalized graphene
Interaction, improves the dispersion effect of the surfactant graphene surface-functionalized to gained.
Preferably, the revolving speed of step (3) described centrifugation be 80-150r/min, such as can be 80r/min, 90r/min,
100r/min, 110r/min, 120r/min, 130r/min, 140r/min or 150r/min, preferably 100-120r/min.
Preferably, the time of the centrifugation be 10-35min, such as can be 10min, 15min, 20min, 25min,
30min or 35min, preferably 15-30min.
Centrifugal process of the present invention can remove excessive cetyl trimethylammonium bromide, and removing can in graphene
A small amount of foreign ion existing for energy.
Preferably, the quality of the additional amount of step (4) described sodium hydride and graphene surface-functionalized obtained by step (1)
Than for (2-4): 100, such as can be 2:100,3:100 or 4:100, preferably 3:100.
Preferably, the temperature of step (4) described reaction be 70-100 DEG C, such as can be 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C,
90 DEG C, 95 DEG C or 100 DEG C, preferably 80-90 DEG C.
Preferably, the time of step (4) described reaction be 90-150min, such as can be 90min, 100min,
110min, 120min, 130min, 140min or 150min, preferably 120-130min.
Preferably, step (4) described inert gas includes any one in nitrogen, argon gas or neon or at least two
Combination.
Preferably, sodium hydride is formed after mixing with dispersion liquid obtained by step (3) when step (4) described heating is reacted
Dispersion liquid circulates, and improves the mixed effect of each ion in solution, improves dispersion efficiency.
Preferably, after step (4) described cooling temperature be 20-30 DEG C, such as can be 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C,
24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C or 30 DEG C, preferably 24-28 DEG C.
As the optimal technical scheme of first aspect present invention the method, described method includes following steps:
(1) 1:(25-35 in mass ratio under 10-30 DEG C, oxygen free condition) admixed graphite alkene and cetyl trimethyl bromine
Change ammonium, obtains surface-functionalized graphene；
(2) liquid-solid ratio (500-1500) is pressed: surface-functionalized graphene obtained by 1 mixing deionized water and step (1),
First time ultrasound 50-70min under 270-350W power, is initially added into (2- in mass ratio when ultrasound carries out 1/3-2/3 for the first time
4) surfactant of sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol composition: 1:(5-8), and it is super in first time
It is added completely at the end of sound, the additional amount of surfactant and the mass ratio of graphene surface-functionalized obtained by step (1) are
(1-10): 100,20-40min is stood, then second of ultrasound 50-70min under 650-750W power, obtains uniformly mixed mix
Close liquid；
(3) mixed liquor 10-35min obtained by centrifugal treating step (2) under 80-150r/min revolving speed, collects supernatant liquid, obtains
To dispersion liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 70-100 DEG C is warming up under nitrogen protection and carries out reaction 90-
150min obtains the graphene dispersing solution, surface work obtained by the additional amount of sodium hydride and step (1) after being cooled to 20-30 DEG C
The mass ratio of the graphene of energyization is (2-4): 100.
Second aspect, the present invention provides the graphene dispersing solutions that method as described in relation to the first aspect is prepared.
The third aspect, the present invention provides the use that the graphene dispersing solution as described in second aspect is used to prepare electrode slurry
On the way.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
(1) preparation method of graphene dispersing solution of the present invention is simple, passes through cetyl trimethylammonium bromide and spy
The cooperation for determining surfactant is scattered in deionized water with making graphene uniform, and dispersion efficiency is high, and dispersion performance is good, preparation
The viscosity of obtained graphene dispersing solution is down to 4239cps；
(2) centrifugation used in graphene dispersing solution preparation process of the present invention is the excessive cetyl trimethyl of separation
The supplementary means of ammonium bromide and foreign ion that may be present, centrifugal rotational speed are low；And use the method dispersion of substep ultrasound
Graphene ensure that the integrality of graphene-structured, be that the electric conductivity for the graphene dispersing solution being prepared is good, resistivity
Down to 38 Ω cm.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:30 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio at 20 °C, obtain surface work
The graphene of energyization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1000:1 mixing deionized water and step (1), 310W power
Lower first time ultrasound 60min, for the first time ultrasound when be added at one time in mass ratio the sodium glycocholate of 3:1:6, coconut oil sodium with
The surfactant of lauric acid amide of ethanol composition, the additional amount of surfactant and step (1) gained are surface-functionalized
The mass ratio of graphene is 4:100, stands 30min, and then second of ultrasound 60min under 700W power, obtains uniformly mixed
Mixed liquor；
(3) mixed liquor 25min obtained by centrifugal treating step (2) under 110r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 85 DEG C is warming up under nitrogen protection and carries out reaction 125min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Embodiment 2
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:30 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 20 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1000:1 mixing deionized water and step (1), 310W power
Lower first time ultrasound 60min, for the first time ultrasound when be added at one time in mass ratio the sodium glycocholate of 3:1:6, coconut oil sodium with
The surfactant of lauric acid amide of ethanol composition, the additional amount of surfactant and step (1) gained are surface-functionalized
The mass ratio of graphene is 4:100, stands 30min, and then second of ultrasound 60min under 700W power, obtains uniformly mixed
Mixed liquor；
(3) mixed liquor 25min obtained by centrifugal treating step (2) under 110r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 85 DEG C is warming up under nitrogen protection and carries out reaction 125min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Embodiment 3
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:30 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 20 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1000:1 mixing deionized water and step (1), 310W power
Lower first time ultrasound 60min is initially added into the sodium glycocholate of 3:1:6, coconut oil in mass ratio when ultrasound carries out 1/2 for the first time
The surfactant of sodium and lauric acid amide of ethanol composition, and be added completely at the end of ultrasound for the first time, surfactant
Additional amount and step (1) obtained by the mass ratio of surface-functionalized graphene be 4:100, stand 30min, then 700W power
Lower second of ultrasound 60min, obtains uniformly mixed mixed liquor；
(3) mixed liquor 25min obtained by centrifugal treating step (2) under 110r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 85 DEG C is warming up under nitrogen protection and carries out reaction 125min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Embodiment 4
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:32 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 15 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1200:1 mixing deionized water and step (1), 320W power
Lower first time ultrasound 55min is initially added into the sodium glycocholate of 2:1:8, coconut oil in mass ratio when ultrasound carries out 1/2 for the first time
The surfactant of sodium and lauric acid amide of ethanol composition, and be added completely at the end of ultrasound for the first time, surfactant
Additional amount and step (1) obtained by the mass ratio of surface-functionalized graphene be 6:100, stand 25min, then 720W power
Lower second of ultrasound 55min, obtains uniformly mixed mixed liquor；
(3) mixed liquor 15min obtained by centrifugal treating step (2) under 120r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 90 DEG C is warming up under nitrogen protection and carries out reaction 120min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Embodiment 5
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:27 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 25 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 800:1 mixing deionized water and step (1), 300W power
Lower first time ultrasound 65min is initially added into the sodium glycocholate of 4:1:5, coconut oil in mass ratio when ultrasound carries out 1/2 for the first time
The surfactant of sodium and lauric acid amide of ethanol composition, and be added completely at the end of ultrasound for the first time, surfactant
Additional amount and step (1) obtained by the mass ratio of surface-functionalized graphene be 2:100, stand 35min, then 680W power
Lower second of ultrasound 65min, obtains uniformly mixed mixed liquor；
(3) mixed liquor 30min obtained by centrifugal treating step (2) under 100r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 80 DEG C is warming up under nitrogen protection and carries out reaction 130min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Embodiment 6
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:35 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 10 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1500:1 mixing deionized water and step (1), 350W power
Lower first time ultrasound 50min is initially added into the sodium glycocholate of 2:1:5, coconut oil in mass ratio when ultrasound carries out 1/3 for the first time
The surfactant of sodium and lauric acid amide of ethanol composition, and be added completely at the end of ultrasound for the first time, surfactant
Additional amount and step (1) obtained by the mass ratio of surface-functionalized graphene be 10:100, stand 40min, then 750W function
Second of ultrasound 50min, obtains uniformly mixed mixed liquor under rate；
(3) mixed liquor 10min obtained by centrifugal treating step (2) under 150r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 70 DEG C is warming up under nitrogen protection and carries out reaction 150min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 4:100.
Embodiment 7
A kind of preparation method of graphene dispersing solution is present embodiments provided, described method includes following steps:
(1) 1:25 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 30 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 500:1 mixing deionized water and step (1), 270W power
Lower first time ultrasound 70min is initially added into the sodium glycocholate of 4:1:8, coconut oil in mass ratio when ultrasound carries out 2/3 for the first time
The surfactant of sodium and lauric acid amide of ethanol composition, and be added completely at the end of ultrasound for the first time, surfactant
Additional amount and step (1) obtained by the mass ratio of surface-functionalized graphene be 1:100, stand 20min, then 650W power
Lower second of ultrasound 70min, obtains uniformly mixed mixed liquor；
(3) mixed liquor 35min obtained by centrifugal treating step (2) under 80r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 100 DEG C is warming up under nitrogen protection and carries out reaction 90min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 2:100.
Embodiment 8
A kind of preparation method of graphene dispersing solution is present embodiments provided, the method is living except step (2) surface
Property agent be made of the sodium glycocholate of 3:6 with lauric acid amide of ethanol, surface obtained by the additional amount of surfactant and step (1)
The mass ratio of the graphene of functionalization is outside 4:100, remaining is same as Example 3.
Embodiment 9
A kind of preparation method of graphene dispersing solution is present embodiments provided, the method is living except step (2) surface
Property agent be made of the sodium glycocholate of 3:1 with coconut oil sodium, it is surface-functionalized obtained by the additional amount of surfactant and step (1)
The mass ratio of graphene is outside 4:100, remaining is same as Example 3.
Embodiment 10
A kind of preparation method of graphene dispersing solution is present embodiments provided, the method is living except step (2) surface
Property agent be made of the coconut oil sodium of 1:6 with lauric acid amide of ethanol, surface obtained by the additional amount of surfactant and step (1)
The mass ratio of the graphene of functionalization is outside 4:100, remaining is same as Example 3.
Comparative example 1
This comparative example provides a kind of preparation method of graphene dispersing solution, and described method includes following steps:
(1) 1:30 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 20 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1000:1 mixing deionized water and step (1), 700W power
Lower ultrasound 120min is initially added into the sodium glycocholate of 3:1:6, coconut oil sodium and cocounut oil in mass ratio when ultrasound carries out 30min
The surfactant of sour diglycollic amide composition, and being added completely into when ultrasound carries out 60min, the additional amount of surfactant with
The mass ratio of surface-functionalized graphene obtained by step (1) is 4:100, stands 30min, obtains mixed liquor；
(3) mixed liquor 25min obtained by centrifugal treating step (2) under 110r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 85 DEG C is warming up under nitrogen protection and carries out reaction 125min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Comparative example 2
This comparative example provides a kind of preparation method of graphene dispersing solution, and described method includes following steps:
(1) 1:30 admixed graphite alkene and cetyl trimethylammonium bromide in mass ratio under 20 DEG C, oxygen free condition, obtain table
The graphene of face functionalization；
(2) by graphene surface-functionalized obtained by liquid-solid ratio 1000:1 mixing deionized water and step (1), 310W power
Lower ultrasound 120min is initially added into the sodium glycocholate of 3:1:6, coconut oil sodium and cocounut oil in mass ratio when ultrasound carries out 30min
The surfactant of sour diglycollic amide composition, and be added completely into ultrasonic 60min, the additional amount and step of surfactant
(1) mass ratio of the surface-functionalized graphene of gained is 4:100, stands 30min, obtains mixed liquor；
(3) mixed liquor 25min obtained by centrifugal treating step (2) under 110r/min revolving speed, collects supernatant liquid, is dispersed
Liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 85 DEG C is warming up under nitrogen protection and carries out reaction 125min,
The graphene dispersing solution, additional amount and the graphite surface-functionalized obtained by step (1) of sodium hydride are obtained after being cooled to 25 DEG C
The mass ratio of alkene is 3:100.
Solid content, viscosity and the electricity for the graphene dispersing solution that measurement embodiment 1-10 and comparative example 1-2 is prepared
Resistance rate.
Wherein, the condition of solid content is measured are as follows: weigh sky surface plate, weight is denoted as m1, and 3g slurry is applied to surface plate
Surface, weighing, weight are denoted as m2, the surface plate for being coated with slurry are put into 140 DEG C of baking ovens, 0.5h are dried, after being cooled to room temperature
It weighs again, weight is denoted as m3, then solid content=(m3-m1)/(m2-m1) × 100%.
Measure the condition of viscosity are as follows: rotational viscometer 4# rotor is inserted into starches at room temperature by mechanical stirring 3min under 750rpm
It in material, and is tested under the conditions of 12rpm, is read after number on viscosimeter scale is stablized.
The condition of measured resistivity is that the graphene dispersing solution that embodiment 1-10 and comparative example 1-2 are prepared uses
Slurry after homogenate is coated on PI film by 200 μm of coating blade, 140 DEG C of drying 1h, then uses the four of model RTS-8
Test instrument probe is tested, and to 9 points are weighed, the average value of 9 point institute measuring resistance rates is institute's value.
The determination data of solid content, viscosity and resistivity is as shown in table 1.
Table 1
As shown in Table 1, the solid content for the graphene dispersing solution that 1-7 of the embodiment of the present invention is prepared is 54.97-
59.84%, viscosity 4239-5439cps, resistivity are 38-56 Ω m.
Embodiment 8 provides a kind of preparation method of graphene dispersing solution, compared with Example 3, the surface in embodiment 8
Activating agent does not add coconut oil sodium, and for the solid content of gained graphene dispersing solution at 53.09%, viscosity is increased to 5618cps,
And resistivity is increased to 67 Ω m.The electric conductivity for the electrode slurry that the graphene dispersing solution that embodiment 8 provides is prepared omits
It is worse than the electric conductivity for the cell size that the graphene dispersing solution that embodiment 1 provides is prepared.
Embodiment 9 provides a kind of preparation method of graphene dispersing solution, compared with Example 3, the surface in embodiment 9
Activating agent does not add lauric acid amide of ethanol, and at 57.15%, viscosity is increased to the solid content of gained graphene dispersing solution
5936cps, and resistivity is increased to 62 Ω m.The electrode slurry that the graphene dispersing solution that embodiment 9 provides is prepared is led
The electric conductivity for the cell size that the graphene dispersing solution that electrical property is slightly worse than the offer of embodiment 1 is prepared.
Embodiment 10 provides a kind of preparation method of graphene dispersing solution, compared with Example 3, the table in embodiment 10
Without addition sodium glycocholate in the activating agent of face, at 56.72%, viscosity is increased to the solid content of gained graphene dispersing solution
5749cps, and resistivity is increased to 71 Ω m.The electrode slurry that the graphene dispersing solution that embodiment 10 provides is prepared
The electric conductivity for the cell size that the graphene dispersing solution that electric conductivity is slightly worse than the offer of embodiment 1 is prepared.
By embodiment 8-10 it is found that the viscosity and resistance of the pairs of last gained graphene dispersing solution of the group of surfactant
There is important influences for rate, when the group of surfactant becomes sodium glycocholate, the coconut palm that mass ratio forms for (2-4): 1:(5-8)
Enuatrol and when lauric acid amide of ethanol, the viscosity of gained graphene dispersing solution is lower, is 4239-5439cps, and resistivity
It is lower, it is 38-56 Ω m.
Comparative example 1 provides a kind of preparation method of graphene dispersing solution, compared with Example 3, in comparative example 1 not
Using the method for substep ultrasound, but ultrasound 120min, the solid content of gained graphene dispersing solution are under 700W power
58.52%, but viscosity is increased to 7150cps, and conductivity is increased to 73 Ω m.
Comparative example 2 provides a kind of preparation method of graphene dispersing solution, compared with Example 3, in comparative example 2 not
Using the method for substep ultrasound, but ultrasound 120min, the solid content of gained graphene dispersing solution are under 310W power
56.96%, but viscosity is increased to 7327cps, and conductivity is increased to 72 Ω m.
In conclusion the preparation method of graphene dispersing solution of the present invention is simple, pass through cetyl trimethyl bromination
The cooperation of ammonium and specific surfactant is scattered in deionized water with making graphene uniform, and dispersion efficiency is high, dispersion performance
Good, the viscosity of the graphene dispersing solution being prepared is down to 4239cps；And use the method dispersed graphite of substep ultrasound
Alkene ensure that the integrality of graphene-structured, be that the electric conductivity for the graphene dispersing solution being prepared is good, resistivity down to
38Ω·cm。
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of graphene dispersing solution, which is characterized in that described method includes following steps:
(1) uniform admixed graphite alkene and cetyl trimethylammonium bromide, obtain surface-functionalized graphene；
(2) mixing deionized water and graphene surface-functionalized obtained by step (1), are added surface-active when ultrasound for the first time
Agent, second of ultrasound, obtains uniformly mixed mixed liquor after standing；
(3) mixed liquor obtained by centrifugal treating step (2) collects supernatant liquid, obtains dispersion liquid；
(4) mixing sodium hydride and step (3) gained dispersion liquid, heating is reacted under inert gas shielding, obtains institute after cooling
State graphene dispersing solution.
2. the method according to claim 1, wherein step (1) graphene and cetyl trimethyl bromine
The mass ratio for changing ammonium is 1:(25-35), preferably 1:(27-32)；
Preferably, step (1) mixing carries out under anaerobic；
Preferably, step (1) the mixed temperature is 10-30 DEG C, preferably 15-20 DEG C.
3. method according to claim 1 or 2, which is characterized in that obtained by step (2) deionized water and step (1)
The liquid-solid ratio of surface-functionalized graphene is (500-1500): 1, preferably (800-1200): 1.
4. method according to claim 1-3, which is characterized in that the power of step (2) the first time ultrasound
For 270-350W, preferably 300-320W；
Preferably, the time of step (2) the first time ultrasound is 50-70min, preferably 55-65min；
Preferably, the time of step (2) described standing is 20-40min, preferably 25-35min；
Preferably, the power of step (2) second of ultrasound is 650-750W, preferably 680-720W；
Preferably, the time of step (2) second of ultrasound is 50-70min, preferably 55-65min.
5. method according to claim 1-4, which is characterized in that step (2) described surfactant includes sweet
In sodium taurocholate, coconut oil sodium or lauric acid amide of ethanol any one or at least two combination, preferably sodium glycocholate,
The combination of coconut oil sodium and lauric acid amide of ethanol；
Preferably, the mass ratio of the sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol is (2-4): 1:(5-8), it is excellent
It is selected as 3:1:6；
Preferably, the mass ratio of graphene surface-functionalized obtained by the additional amount Yu step (1) of the surfactant is (1-
10): 100, preferably (2-6): 100.
6. method according to claim 1-5, which is characterized in that step (2) the addition surfactant is
It is initially added into surfactant when ultrasound carries out 1/3-2/3 for the first time, and is added completely at the end of ultrasound for the first time.
7. method according to claim 1-6, which is characterized in that the revolving speed of step (3) described centrifugation is 80-
150r/min, preferably 100-120r/min；
Preferably, the time of step (3) described centrifugation is 10-35min, preferably 15-30min；
Preferably, the mass ratio of graphene surface-functionalized obtained by the additional amount with step (1) of step (4) described sodium hydride is
(2-4): 100, preferably 3:100；
Preferably, the temperature of step (4) described reaction is 70-100 DEG C, preferably 80-90 DEG C；
Preferably, the time of step (4) described reaction is 90-150min, preferably 120-130min；
Preferably, temperature is 20-30 DEG C, preferably 24-28 DEG C after step (4) described cooling.
8. method according to claim 1-7, which is characterized in that described method includes following steps:
(1) 1:(25-35 in mass ratio under 10-30 DEG C, oxygen free condition) admixed graphite alkene and cetyl trimethylammonium bromide,
Obtain surface-functionalized graphene；
(2) liquid-solid ratio (500-1500) is pressed: surface-functionalized graphene, 270- obtained by 1 mixing deionized water and step (1)
First time ultrasound 50-70min under 350W power, is initially added into (2-4) in mass ratio when ultrasound carries out 1/3-2/3 for the first time:
The surfactant of sodium glycocholate, coconut oil sodium and lauric acid amide of ethanol composition 1:(5-8), and in ultrasound knot for the first time
It is added completely into when beam, the mass ratio of surface-functionalized graphene obtained by the additional amount of surfactant and step (1) is (1-
10): 100,20-40min is stood, then second of ultrasound 50-70min under 650-750W power, obtains uniformly mixed mixing
Liquid；
(3) mixed liquor 10-35min obtained by centrifugal treating step (2) under 80-150r/min revolving speed, collects supernatant liquid, is divided
Dispersion liquid；
(4) dispersion liquid obtained by sodium hydride and step (3) is mixed, 70-100 DEG C is warming up under nitrogen protection and carries out reaction 90-
150min obtains the graphene dispersing solution, surface work obtained by the additional amount of sodium hydride and step (1) after being cooled to 20-30 DEG C
The mass ratio of the graphene of energyization is (2-4): 100.
9. a kind of graphene dispersing solution that the method according to claim 1 is prepared.
10. the purposes that a kind of graphene dispersing solution as claimed in claim 9 is used to prepare electrode slurry.
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