CN103420352B - A kind of high Oil repellent fluorinated graphene and preparation method thereof - Google Patents
A kind of high Oil repellent fluorinated graphene and preparation method thereof Download PDFInfo
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Abstract
Disclosed by the invention is high Oil repellent fluorinated graphene and preparation method thereof, the step of its method is: first by the aqueous dispersions of conventional improvement Hummers legal system for graphene oxide, then be refrigerated in liquid nitrogen by the aqueous dispersions of graphene oxide after being frozen into solid completely, lyophilize obtains honeycomb-shaped oxidizing Graphene; Again by honeycomb-shaped oxidizing Graphene under rare gas element and fluorine gas mixed atmosphere, heat up carry out fluoridation, be cooled to room temperature.Does is Oil repellent 55 ~ 70 in prepared high Oil repellent fluorinated graphene? %, fluorine atom and carbon atom are with covalent linkage form keyed jointing, and weightless peak temperature is greater than 470 DEG C, Heat stability is good, and its resistance is greater than 10
12Ω.The Oil repellent of Graphene fluorochemical prepared by the present invention is high, fluoro-containing group good heat resistance, and cost is low, and technique is simple, and temperature of reaction is lower, and security is high, energy-conservation, is applicable to scale operation, has stronger application prospect.<!--1-->
Description
Technical field
The invention belongs to fluorinated graphene and preparing technical field thereof, be specifically related to a kind of high Oil repellent fluorinated graphene and preparation method thereof.
Background technology
Fluorinated graphene, as a kind of derivative of Graphene, obtains extensive concern with the physical and chemical performance of its high energy storage, uniqueness such as lubrication barrier property and wide energy gap etc.And in fluorinated graphene, the height of Oil repellent to the performance of fluorinated graphene each side, as its chemical stability, thermostability, laminated structure spacing, electrical property, magnetic property, absorption property, barrier property and lubricity etc. have direct impact.In general, the performance of the fluorinated graphene that Oil repellent is high is all better than the low fluorinated graphene of Oil repellent, thus according to the premium properties of high Oil repellent fluorinated graphene, its existing prospect being used as super lubricant and high-performance nano packing material, again because it has very wide energy gap and excellent electrical property, also more powerful application potential can be presented in electricity, prepare the electrode materials of lithium cell of high specific capacitance, high output voltage as can be used as, because of but a kind of fluorinated carbon material got most of the attention at present.
High Oil repellent fluorinated graphene not only requires that fluorine atom will be connected with covalent linkage form with carbon atom, and the ratio shared by its fluorine at least reaches 50wt%.And the Oil repellent of fluorinated graphene product is general lower at present, thermostability also has to be hoisted, can not meet more areas and better application demand.There is not document to disclose high Oil repellent preparation technology in prior art, therefore how to prepare a kind of high Oil repellent, the fluorinated graphene of high thermal stability becomes current research emphasis and technological difficulties yet.
At present, the processing method preparing fluorinated graphene has following several.
Stripping method: by the method for mechanically peel or solvent expansion, fluorographite is carried out stripping and obtain fluorinated graphene.But because productive rate is very low, prepare that gained fluorinated graphene lamella is little, the number of plies is many, poor heat stability, and Oil repellent is low, cannot be used widely (PhysicalReviewB2010 (1), 205435-205439).
Direct fluorination: namely directly use fluorination reagent (xenon difluoride) to fluoridize single-layer graphene prepared by CVD.Because this method is high to ingredient requirement, technique is loaded down with trivial details, and product poor heat stability, seriously limit its large-scale application (Small2010 (24) 2877 – 2884).
Hydro-thermal fluorination method: after graphene oxide dispersion being mixed with hydrofluoric acid (HF) is ultrasonic, is transferred in the pressure kettle that Teflon does, and places and prepare fluorinated graphene in 30 hours at 180 DEG C.But fluorine carbon mol ratio is lower than 0.5 in its gained fluorinated graphene, be far from reaching the requirement of high Oil repellent, and energy consumption is high, severe reaction conditions (Carbon2012,50,5403-5410).
What disclose in prior art belongs to direct fluorination, also just like " preparation method of fluorinated graphene " disclosed in CN102530910A and CN102530911A, Graphene and fluorine simple substance react by the former, it is only prepared fluorinated graphene, and in fluorinated graphene, Oil repellent is only 0.5 ~ 30%.The latter is that in its obtained fluorinated graphene, the amount of being rich in is only " 0 ~ 10.5% ", and corresponding thermostability is also lower, and the two is fluoridized after all needing that graphene oxide is reduced into Graphene, and technique is comparatively loaded down with trivial details by Graphene and fluorizating agent reaction.Though a kind of method that patent CN1026107941A discloses direct fluorinated graphene prepares fluorinated graphene, the Oil repellent in its gained modified graphene is maximum is still only 30%, does not reach the requirement of high Oil repellent fluorinated graphene.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of preparation method of high Oil repellent fluorinated graphene, not only Oil repellent is high for the fluorinated graphene prepared of the method, and thermostability is also high, and technique is simple.
Another object of the present invention is to provide a kind of Oil repellent of being obtained by aforesaid method and all high fluorinated graphene of thermostability.
The preparation method of high Oil repellent fluorinated graphene provided by the invention, the processing step of the method is as follows:
(1) first by the aqueous dispersions of conventional improvement Hummers legal system for graphene oxide, be then refrigerated in liquid nitrogen by the aqueous dispersions of graphene oxide after being frozen into solid completely, lyophilize obtains honeycomb-shaped oxidizing Graphene;
(2) graphene oxide step (1) obtained, under rare gas element and fluorine gas mixed atmosphere, heats up and carries out fluoridation, be cooled to room temperature.
In above preparation method's step (1), the time of liquid nitrogen freezing is 100 ~ 600s.
In above preparation method's step (1), lyophilize is 1 ~ 3wt% to the water content of graphene oxide.
In above preparation method's step (2), before intensification fluoridation, the initial partial pressure of fluorine gas is 3 ~ 80KPa, preferably 50 ~ 80KPa.
The control condition of fluoridizing that heats up in above preparation method's step (2) is: be warming up to 80 ~ 250 DEG C with the temperature rise rate of 1 ~ 20 DEG C/min, and be incubated 10 ~ 600 minutes, be preferably warming up to 150 ~ 250 DEG C with the temperature rise rate of 3 ~ 20 DEG C/min, and be incubated 60 ~ 600 minutes.
Described in above preparation method's step (2), rare gas element is at least one in nitrogen, argon gas, helium and carbon dioxide, preferred nitrogen.
The high Oil repellent fluorinated graphene prepared by aforesaid method provided by the invention, the Oil repellent of this fluorinated graphene is 55 ~ 70%, and fluorine atom and carbon atom are with covalent linkage form keyed jointing, and weightless peak temperature is greater than 470 DEG C, and its resistance is greater than 10
12Ω.
Compared with prior art, the present invention has following beneficial effect:
1, because method provided by the invention can allow the graphene oxide be dispersed in water, the honeycomb-shaped oxidizing Graphene that specific surface area is larger is obtained after liquid-nitrogen freeze drying, thus make the diffusion of fluorine gas in graphene oxide in fluorination process easier, more abundant, and can fully contact with graphene oxide, not only facilitate fully carrying out fast of fluoridation, and raising degree of fluorination, make fluorinated graphene Oil repellent up to 55 ~ 70%, to be also that the fluorinated graphene of the high Oil repellent of preparation provides a kind of new approach and new thought simultaneously.
2, because the water content control of the graphene oxide of freezing rear drying is 1 ~ 3wt% by method provided by the invention, such water content can not only provide appropriate moisture and fluorine gas to react and generate hydrogen fluoride, and the fluoridation of hydrogen fluoride to fluorine gas and graphene oxide can be utilized to carry out situ catalytic, fluoridation is carried out more smooth, more abundant, more thorough, thus improve degree of fluorination, prepare the fluorinated graphene of high Oil repellent.On the other hand, such water content also ensure that and fluorinated graphene lamella will be caused to produce too much defect because fluoridation is too violent.
3, due to the carbon-fluorine bond in fluorinated graphene provided by the invention mainly with covalent linkage for main (see figure 2), its thermostability itself is better than half ionic linkage, in addition high Oil repellent can make again the covalency of carbon-fluorine bond improve further, thus prepared the thermally-stabilised of fluorinated graphene is significantly improved, and its weightless peak temperature can be greater than 470 DEG C (see tables).
4, due to method provided by the invention be lower fluoridize temperature (80 ~ 250 DEG C) under, directly to be fluoridized as fluorination reagent by fluorine gas and prepare high Oil repellent fluorinated graphene, thus process safety is higher, is applicable to scale operation, can energy consumption be reduced again, reduce production cost.
5, because high Oil repellent fluorinated graphene provided by the invention has good thermotolerance and wide energy gap, and good resistive performance, thus at super solid lubricant, thermally stable polymer field of nanocomposite materials, and the field such as lithium ion battery has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of cellular graphene oxide prepared by the present invention.
Fig. 2 is the infrared spectrum of the fluorinated graphene that comparative example and the present invention obtain.Wherein a is the fluorinated graphene that comparative example 1 obtains, the fluorinated graphene that b comparative example 2 is obtained, and c is the fluorinated graphene that comparative example 3 obtains, and d is the fluorinated graphene that the embodiment of the present invention 1 obtains.
As can be seen from the figure, there is very strong absorption spike at 1212.5cm-1 place in the Graphene fluorochemical obtained in embodiment 1, the absorption peak of what this peak was corresponding is C-F covalent linkage.The absorption peak of product near 1200cm-1 of comparative example 2 and 3 is an acromion, can think and to be made up of two peaks of 1212.5cm-1 and 1159.3cm-1, but 1159.3cm-1 corresponding be the absorption peak of C-F half ionic linkage, and their absorption peak strength is weak compared with embodiment 1 products therefrom absorption peak.The infrared spectra of comparative example 1 product is unobvious near 1200cm-1 obtains absorption peak.This illustrates in fluorinated graphene prepared by the inventive method and defines stable covalent linkage between fluorine and carbon, thus its thermostability is higher.
Fig. 3 is the x-ray photoelectron energy spectrogram of the fluorinated graphene that the embodiment of the present invention 5, embodiment 2 and comparative example 1 obtains.
As can be seen from the figure, the Graphene fluorochemical of the embodiment of the present invention 2 and 5 combines at the 698eV of spectrogram can locate the power spectrum peak all having fluorine element, and comparative example 1 does not have, and this illustrates that in fluorinated graphene prepared by the inventive method, Oil repellent substantially increases.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are only used to further illustrate the present invention; limiting the scope of the invention can not be interpreted as; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the content of the invention described above, still belong to protection scope of the present invention
What deserves to be explained is: 1) the fluorine-containing massfraction of following examples products therefrom is by x-ray photoelectron power spectrum test gained.2) thermogravimetic analysis (TGA) is carried out to fluorinated graphene prepared by following examples and comparative example, the results are shown in subordinate list.
As follows for the concrete grammar of the aqueous dispersions of graphene oxide by conventional modification Hummers legal system in embodiment 1 ~ 6:
By the aqueous dispersions of modification Hummers legal system for graphene oxide.In three-necked flask, add 300 order Graphite Powder 99 5g and SODIUMNITRATE 3.8g, under ice-water bath and agitation condition, slowly pour the 300ml98% vitriol oil into, and control temperature of reaction at about 4 DEG C.Continue to stir, and slowly added 23g potassium permanganate within one hour, control temperature of reaction at about 20 DEG C.After adding, remove ice-water bath and at room temperature stir 1h.The 600ml5% dilute sulphuric acid prepared slowly is added in three-necked flask under intensively stirred condition, and carries out oil bath heat treated, make temperature of reaction increase.When temperature rises to 98 DEG C, stop heating, and the strict temperature of reaction that controls is at 98 ± 2 DEG C, reaction 2h.Remove oil bath device, when temperature is reduced to 60 DEG C, the concentration pouring 20ml into is 30%H
2o
2the aqueous solution, continues stirring reaction 2h.The mixed solution of preparation is carried out centrifuging treatment, after centrifugal by obtain product with after a large amount of deionized water wash, continue centrifugal.This step repeatedly, until mixed solution pH value reaches 4 ~ 5.Again mixture is poured in beaker, put into Vltrasonic device supersound process 30min, obtain graphene oxide aqueous dispersions.Shaped through liquid nitrogen freezing by aqueous dispersions, freezing time is 10s, and products therefrom is through the obtained honeycomb-shaped oxidizing Graphene of Freeze Drying Equipment drying.
Embodiment 1
It is 1% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 100s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in nitrogen replacement reactor three times, be filled with fluorine gas and nitrogen again, and control fluorine gas in the reactor initial partial pressure be 3KPa, then be warming up to 200 DEG C with the temperature rise rate of 1 DEG C/min and be incubated 30 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 56%, and the massfraction of carbon is 44%.
Embodiment 2
It is 1% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 300s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in nitrogen replacement reactor three times, be filled with fluorine gas and nitrogen again, and control fluorine gas in the reactor initial partial pressure be 30KPa, then be warming up to 250 DEG C with the temperature rise rate of 5 DEG C/min and be incubated 10 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 55%, and the massfraction of carbon is 45%.
Embodiment 3
It is 2% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 200s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in nitrogen replacement reactor three times, be filled with fluorine gas, nitrogen and argon gas again, and control fluorine gas in the reactor initial partial pressure be 50KPa, then be warming up to 200 DEG C with the temperature rise rate of 5 DEG C/min and be incubated 120 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 64%, and the massfraction of carbon is 36%.
Embodiment 4
It is 2% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 600s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in argon replaces reactor three times, be filled with fluorine gas and nitrogen again, and control fluorine gas in the reactor initial partial pressure be 70KPa, then be warming up to 80 DEG C with the temperature rise rate of 3 DEG C/min and be incubated 360 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 62%, and the massfraction of carbon is 38%.
Embodiment 5
It is 3% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 600s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in nitrogen replacement reactor three times, be filled with fluorine gas and nitrogen again, and control fluorine gas in the reactor initial partial pressure be 80KPa, then be warming up to 150 DEG C with the temperature rise rate of 10 DEG C/min and be incubated 60 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 67%, and the massfraction of carbon is 33%.
Embodiment 6
It is 3% that the aqueous dispersions of prepared graphene oxide is dried to water content with Freeze Drying Equipment after freezing 500s in liquid nitrogen, obtains cellular graphene oxide; Graphene oxide is placed in airtight vacuum reactor, vacuumize with after the air in nitrogen replacement reactor three times, be filled with fluorine gas, nitrogen and carbonic acid gas again, and control fluorine gas in the reactor initial partial pressure be 60KPa, then be warming up to 250 DEG C with the temperature rise rate of 20 DEG C/min and be incubated 600 minutes, question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction recording fluorine element in this functionalized graphene is 70%, and the massfraction of carbon is 30%.
Comparative example 1
Multi-layer graphene microplate is placed in airtight vacuum reactor, after the air in nitrogen replacement reactor three times, again vacuumize, be warming up to 250 DEG C with 5 DEG C/min temperature rise rate, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, and control fluorine gas in the reactor dividing potential drop be 80KPa, in 250 DEG C of reactions 360 minutes, after reaction terminates, question response device naturally cooling, gets product.
The massfraction recording fluorine element in this functionalized graphene is 17%, and the massfraction of carbon is 83%.
Comparative example 2
Multilayer graphene oxide microplate is placed in airtight vacuum reactor, after the air in nitrogen replacement reactor three times, again vacuumize, be warming up to 250 DEG C, leave standstill 30 minutes, after chemical luminous energy group in graphene microchip to be oxidized removes, be filled with fluorine gas and nitrogen in reactor, control fluorine gas in the reactor dividing potential drop is 100KPa, keep temperature 250 DEG C of fluoridations 480 minutes, after reaction terminates, question response device naturally cooling, takes out product.
The massfraction recording fluorine element in this functionalized graphene is 30%, and the massfraction of carbon is 70%.
Comparative example 3
Prepare honeycomb-shaped oxidizing Graphene, controlling water content is 3%, is placed in airtight vacuum reactor, and with after the air in nitrogen replacement reactor three times, again vacuumize, be warming up to 50 DEG C, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, control fluorine gas in the reactor dividing potential drop is 80KPa, keep temperature 50 C fluoridation 2 hours, after reaction terminates, question response device naturally cooling, takes out product.
The massfraction recording fluorine element in this functionalized graphene is 54%, and the massfraction of carbon is 46%.
But the massfraction testing its fluorine element after this Graphene fluorochemical is processed 480 minutes under 250 DEG C of vacuum conditions is 14%, the massfraction of carbon is 86%.
Comparative example 4
Prepare honeycomb-shaped oxidizing Graphene, controlling water content is 0.3%.Be placed in airtight vacuum reactor, after the air in nitrogen replacement reactor three times, again vacuumize, be warming up to 50 DEG C, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, control fluorine gas in the reactor dividing potential drop is 80KPa, temperature 50 C is kept to react 600 minutes, after reaction terminates, question response device naturally cooling, takes out sample.
The massfraction recording fluorine element in this functionalized graphene is 31%, and the massfraction of carbon is 69%.
Table.
As can be known from the above table, the weightless peak temperature of high Oil repellent fluorinated graphene prepared in the embodiment of the present invention 1 ~ 6 is all more than 470 DEG C, the thermostability of tool/high, and in comparative example the weightless peak temperature of fluorinated graphene all more than 400 DEG C, wherein embodiment 9 be only 245 DEG C.
Claims (7)
1. a preparation method for high Oil repellent fluorinated graphene, is characterized in that the method comprises the following steps:
(1) first by the aqueous dispersions of conventional improvement Hummers legal system for graphene oxide, be then refrigerated in liquid nitrogen by the aqueous dispersions of graphene oxide after being frozen into solid completely, lyophilize obtains honeycomb-shaped oxidizing Graphene;
(2) graphene oxide step (1) obtained, under rare gas element and fluorine gas mixed atmosphere, heats up and carries out fluoridation, be cooled to room temperature,
In its step (1), lyophilize to the water content in graphene oxide is 1 ~ 3wt%.
2. the preparation method of high Oil repellent fluorinated graphene according to claim 1, before it is characterized in that step (2) intensification fluoridation, the initial partial pressure of fluorine gas is 3 ~ 80KPa.
3. the preparation method of high Oil repellent fluorinated graphene according to claim 1 or 2, the method for fluoridizing that it is characterized in that heating up in step (2) is: be warming up to 80 ~ 250 DEG C with the temperature rise rate of 1 ~ 20 DEG C/min, and be incubated 10 ~ 600 minutes.
4. the preparation method of high Oil repellent fluorinated graphene according to claim 1 or 2, is characterized in that the time of liquid nitrogen freezing in step (1) is 100 ~ 600s.
5. the preparation method of high Oil repellent fluorinated graphene according to claim 3, is characterized in that the time of liquid nitrogen freezing in step (1) is 100 ~ 600s.
6. the preparation method of high Oil repellent fluorinated graphene according to claim 1 or 2, is characterized in that described in step (2), rare gas element is at least one in nitrogen, argon gas, helium and carbon dioxide.
7. the preparation method of high Oil repellent fluorinated graphene according to claim 5, is characterized in that described in step (2), rare gas element is at least one in nitrogen, argon gas, helium and carbon dioxide.
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