CN103420352A - High-fluoride-content graphite fluoride and preparation method thereof - Google Patents
High-fluoride-content graphite fluoride and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-fluoride-content graphite fluoride and a preparation method thereof. The method comprises the following steps: preparing aqueous dispersion liquid of graphite oxide with a conventional improved Hummers method, then freezing the aqueous dispersion liquid of graphite oxide in liquid nitrogen to be completely frozen into solid, and freezing and drying to obtain cellular graphite oxide; under a mixed atmosphere of inert gas and fluoride, warming the cellular graphite oxide for fluoridation, and cooling to room temperature. The fluoride content of the prepared high-fluoride-content graphite fluoride is 55-70 percent, fluorine atoms are bonded with carbon atoms in a covalent bond mode, weightlessness peak temperature is larger than 470 DEG C, the heat stability is good, and the resistance is larger than 1012 omega. The prepared graphite fluoride has the advantages of high fluoride content, good heat resistance of fluorine-containing groups, low cost, simple process, lower reaction temperature, high safety and energy saving, is suitable for mass production, and has a better application prospect.
Description
Technical field
The invention belongs to fluorinated graphene and preparing technical field thereof, be specifically related to a kind of high fluorine content fluorinated graphene and preparation method thereof.
Background technology
Fluorinated graphene is as a kind of derivative of Graphene, and the physical and chemical performance that stores, lubricates the uniquenesses such as barrier property and wide energy gap with its high-energy obtains extensive concern.And, in fluorinated graphene, the performance of the height of fluorine content to the 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 fluorine content is high all is better than the fluorinated graphene that fluorine content is low, thereby according to the premium properties of high fluorine content fluorinated graphene, its existing prospect as super lubricant and high-performance nano packing material, there is very wide energy gap and excellent electrical property because of it again, also can present more powerful application potential aspect electricity, prepare the electrode materials of the lithium cell of high specific capacitance, high output voltage as can be used as, thereby be a kind of fluorinated carbon material got most of the attention at present.
High fluorine content fluorinated graphene not only requires fluorine atom will be connected with the covalent linkage form with carbon atom, and the shared ratio of its fluorine at least reaches 50 wt%.And the fluorine content of fluorinated graphene product is generally lower at present, it is to be hoisted that thermostability also has, and can not meet more areas and better application demand.In prior art, also do not have document to disclose high fluorine content preparation technology, the fluorinated graphene that therefore how to prepare a kind of high fluorine content, high thermal stability becomes current research emphasis and technological difficulties.
At present, the processing method for preparing fluorinated graphene has following several.
Stripping method: fluorographite is peeled off and obtained fluorinated graphene by the method for mechanically peel or solvent expansion.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 fluorine content is low, can't be used widely (Physical Review B 2010 (1), 205435-205439).
Direct fluorination method: directly use fluorination reagent (xenon difluoride) to the CVD legal system standby single-layer graphene fluoridized.Because this method is high to ingredient requirement, technique is loaded down with trivial details, and the product poor heat stability, has seriously limited its large-scale application (Small 2010 (24) 2877 – 2884).
Hydro-thermal fluorination method: the graphene oxide dispersion liquid, with after ultrasonic mixing of hydrofluoric acid (HF), is transferred in the pressure kettle that Teflon does, under 180 ℃, places and prepare fluorinated graphene in 30 hours.But in its gained fluorinated graphene, fluorine carbon mol ratio, lower than 0.5, is far from reaching the requirement of high fluorine content, and energy consumption is high, (Carbon 2012,50,5403-5410) for severe reaction conditions.
What in prior art, disclose belongs to direct fluorination method, also just like CN 102530910 A and CN 102530911 A disclosed " preparation method of fluorinated graphene ", the former reacts Graphene with fluorine simple substance, it is only to have prepared fluorinated graphene, and in fluorinated graphene, fluorine content is only 0.5～30%.The latter is by the reaction of Graphene and fluorizating agent, and in its fluorinated graphene made, 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 graphene oxide is reduced into to Graphene, and technique is comparatively loaded down with trivial details.Prepare fluorinated graphene though patent CN 1026107941 A have announced a kind of method of direct fluorinated graphene, the fluorine content maximum in its gained modified graphene is only still 30 %, does not reach the requirement of high fluorine content fluorinated graphene.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of preparation method of high fluorine content fluorinated graphene is provided, not only fluorine content is high for fluorinated graphene prepared by the method, and thermostability is also high, and technique is simple.
Another object of the present invention is to provide all high fluorinated graphenes of a kind of fluorine content made by aforesaid method and thermostability.
The preparation method of high fluorine content fluorinated graphene provided by the invention, the processing step of the method is as follows:
(1), first by the aqueous dispersions of the standby graphene oxide of conventional improvement Hummers legal system, after then the aqueous dispersions of graphene oxide being refrigerated in liquid nitrogen and being frozen into solid fully, lyophilize obtains cellular graphene oxide;
(2) graphene oxide step (1) made, under rare gas element and fluorine gas mixed atmosphere, heats up and carries out fluoridation, is cooled to room temperature and gets final product.
In above preparation method's step (1), the time of liquid nitrogen freezing is 100 ~ 600 s.
In above preparation method's step (1), lyophilize to the water content of graphene oxide is 1～3 wt %.
In above preparation method's step (2), the initial partial pressure of the front fluorine gas of intensification fluoridation is 3 ~ 80KPa, preferably 50 ~ 80KPa.
The control condition of fluoridizing that heats up in above preparation method's step (2) is: the temperature rise rate with 1 ~ 20 ℃/min is warming up to 80 ~ 250 ℃, and is incubated 10 ~ 600 minutes, and preferably the temperature rise rate with 3 ~ 20 ℃/min is warming up to 150 ~ 250 ℃, and is incubated 60 ~ 600 minutes.
Rare gas element described in above preparation method's step (2) is at least one in nitrogen, argon gas, helium and carbon dioxide, preferred nitrogen.
The high fluorine content fluorinated graphene prepared by aforesaid method provided by the invention, the fluorine content 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 ℃, and its resistance is greater than 10
12Ω.
Compared with prior art, the present invention has following beneficial effect:
1, because can allowing, method provided by the invention is dispersed in the graphene oxide in water, obtain the cellular graphene oxide that specific surface area is larger after liquid-nitrogen freeze drying, thereby make in fluorination process the diffusion of fluorine gas in graphene oxide easier, more abundant, and can fully contact with graphene oxide, not only promoted fully carrying out fast of fluoridation, and raising degree of fluorination, make fluorinated graphene fluorine content up to 55～70 %, also for the fluorinated graphene for preparing high fluorine content, to provide a kind of new approach and new thought simultaneously.
2, because method provided by the invention is 1～3 wt % by the control of the water content of the graphene oxide of freezing rear drying, such water content can not only provide appropriate moisture to react with fluorine gas and generate hydrogen fluoride, and can utilize hydrogen fluoride to carry out situ catalytic to the fluoridation of fluorine gas and graphene oxide, make fluoridation carry out more smooth, more abundant, more thorough, thus degree of fluorination improved, prepare the fluorinated graphene of high fluorine content.On the other hand, such water content has also guaranteed can not cause the fluorinated graphene lamella to produce too much defect because fluoridation is too violent.
3, because the carbon-fluorine bond in fluorinated graphene provided by the invention mainly be take covalent linkage as main (see figure 2), its thermostability itself is better than half ionic linkage, high fluorine content can make again the covalency of carbon-fluorine bond further improve in addition, thereby the thermally-stabilised of prepared fluorinated graphene be significantly improved, its weightless peak temperature can be greater than 470 ℃ (in Table).
4, because method provided by the invention is to hang down and fluoridizing at temperature (80 ~ 250 ℃), directly fluoridize to prepare high fluorine content fluorinated graphene by fluorine gas as fluorination reagent, thereby process safety is higher, is applicable to scale operation, can reduce energy consumption again, reduce production costs.
5, because high fluorine content fluorinated graphene provided by the invention has thermotolerance and wide energy gap preferably, and good resistive performance, thereby at super solid lubricant, the thermally stable polymer field of nanocomposite materials, and the field such as lithium ion battery has a good application prospect.
The accompanying drawing explanation
The scanning electron microscope picture that Fig. 1 is the cellular graphene oxide for preparing of the present invention.
The infrared spectrum that Fig. 2 is the fluorinated graphene that makes of Comparative Examples and the present invention.Wherein a is the fluorinated graphene that Comparative Examples 1 makes, the fluorinated graphene that b Comparative Examples 2 makes, and c is the fluorinated graphene that Comparative Examples 3 makes, d is the fluorinated graphene that the embodiment of the present invention 1 makes.
As can be seen from the figure, in embodiment 1, resulting Graphene fluorochemical very strong absorption spike occurs at 1212.5 cm-1 places, and what this peak was corresponding is the absorption peak of C-F covalent linkage.Comparative Examples 2 and near 3 the absorption peak of product 1200 cm-1 are an acromion, can think that two peaks by 1212.5 cm-1 and 1159.3 cm-1 form, yet what 1159.3 cm-1 were corresponding is the absorption peak of C-F half ionic linkage, and their absorption peak strength than embodiment 1 products therefrom absorption peak a little less than.The infrared spectra of Comparative Examples 1 product does not have the obvious absorption peak that obtains near 1200 cm-1.Formed stable covalent linkage between fluorine and carbon in fluorinated graphene prepared by this explanation the inventive method, thereby its thermostability is higher.
The x-ray photoelectron energy spectrogram that Fig. 3 is the fluorinated graphene that makes of the embodiment of the present invention 5, embodiment 2 and Comparative Examples 1.
As can be seen from the figure, the embodiment of the present invention 2 and 5 Graphene fluorochemical are at the 698eV of spectrogram in conjunction with the power spectrum peak that can locate all to have fluorine element, and Comparative Examples 1 does not have, and in fluorinated graphene prepared by this explanation the inventive method, fluorine content has improved greatly.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples only are used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention; 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) fluorinated graphene prepared by following examples and Comparative Examples carries out thermogravimetic analysis (TGA), 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:
Aqueous dispersions by the standby graphene oxide of modification Hummers legal system.Add 300 order Graphite Powder 99 5 g and SODIUMNITRATE 3.8 g in three-necked flask, slowly pour 300 ml 98% vitriol oils under ice-water bath and agitation condition, and control temperature of reaction 4 ℃ of left and right.Continue to stir, and slowly added 23 g potassium permanganate within one hour, control temperature of reaction 20 ℃ of left and right.After adding, remove ice-water bath and at room temperature stir 1h.During 600 ml 5% dilute sulphuric acids that prepare are slowly added to three-necked flask under intensively stirred condition, and carry out the oil bath heat treated, make temperature of reaction increase.When temperature rises to 98 ℃, stop heating, and strictly control temperature of reaction at 98 ± 2 ℃, reaction 2h.Remove oil bath device, when temperature is reduced to 60 ℃, the concentration of pouring 20 ml into is 30 % H
2O
2The aqueous solution, continue stirring reaction 2h.The mixed solution of preparation is carried out to centrifuging treatment, centrifugal after by the product that obtains with after a large amount of deionized water wash, continue centrifugal.This step repeatedly, until the pH of mixed value reaches 4 ~ 5.Again mixture is poured in beaker, put into Vltrasonic device supersound process 30 min, obtain the graphene oxide aqueous dispersions.Aqueous dispersions is finalized the design through liquid nitrogen freezing, and freezing time is 10s, and products therefrom makes cellular graphene oxide through the Freeze Drying Equipment drying.
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 to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, vacuumize, be filled with again fluorine gas and nitrogen, and control fluorine gas initial partial pressure in reactor is 3 KPa, then be warming up to 200 ℃ and be incubated 30 minutes with the temperature rise rate of 1 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records 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 to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, vacuumize, be filled with again fluorine gas and nitrogen, and control fluorine gas initial partial pressure in reactor is 30 KPa, then be warming up to 250 ℃ and be incubated 10 minutes with the temperature rise rate of 5 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records 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 to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, vacuumize, be filled with again fluorine gas, nitrogen and argon gas, and control fluorine gas initial partial pressure in reactor is 50 KPa, then be warming up to 200 ℃ and be incubated 120 minutes with the temperature rise rate of 5 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records 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 to airtight vacuum reactor, with after the air in the argon replaces reactor three times, vacuumize, be filled with again fluorine gas and nitrogen, and control fluorine gas initial partial pressure in reactor is 70 KPa, then be warming up to 80 ℃ and be incubated 360 minutes with the temperature rise rate of 3 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records 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 to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, vacuumize, be filled with again fluorine gas and nitrogen, and control fluorine gas initial partial pressure in reactor is 80 KPa, then be warming up to 150 ℃ and be incubated 60 minutes with the temperature rise rate of 10 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records 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 to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, vacuumize, be filled with again fluorine gas, nitrogen and carbonic acid gas, and control fluorine gas initial partial pressure in reactor is 60 KPa, then be warming up to 250 ℃ and be incubated 600 minutes with the temperature rise rate of 20 ℃/min, the question response device naturally cools to room temperature, takes out fluorinated graphene.
The massfraction that records fluorine element in this functionalized graphene is 70%, and the massfraction of carbon is 30%.
Comparative Examples 1
The multi-layer graphene microplate is placed in to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, again vacuumize, be warming up to 250 ℃ with 5 ℃/min temperature rise rate, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, and control fluorine gas dividing potential drop in reactor is 80KPa, in 250 ℃ of reactions 360 minutes, after reaction finishes, question response device naturally cooling, get product.
The massfraction that records fluorine element in this functionalized graphene is 17 %, and the massfraction of carbon is 83 %.
Comparative Examples 2
Multilayer graphene oxide microplate is placed in to airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, again vacuumize, be warming up to 250 ℃, standing 30 minutes, after the chemical luminous energy group on the graphene oxide microplate removes, be filled with fluorine gas and nitrogen in reactor, controlling fluorine gas dividing potential drop in reactor is 100KPa, keep 250 ℃ of fluoridations of temperature 480 minutes, after reaction finishes, question response device naturally cooling, take out product.
The massfraction that records fluorine element in this functionalized graphene is 30 %, and the massfraction of carbon is 70%.
Comparative Examples 3
Prepare cellular graphene oxide, controlling water content is 3%, be placed in airtight vacuum reactor, and with after the air in the nitrogen replacement reactor three times, again vacuumize, be warming up to 50 ℃, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, controlling fluorine gas dividing potential drop in reactor is 80KPa, keep the temperature 50 C fluoridation 2 hours, after reaction finishes, question response device naturally cooling, take out product.
The massfraction that records fluorine element in this functionalized graphene is 54 %, and the massfraction of carbon is 46 %.
But the massfraction of this Graphene fluorochemical being processed under 250 ℃ of vacuum conditions to its fluorine element of test after 480 minutes is 14 %, and the massfraction of carbon is 86 %.
Comparative Examples 4
Prepare cellular graphene oxide, controlling water content is 0.3%.Be placed in airtight vacuum reactor, with after the air in the nitrogen replacement reactor three times, again vacuumize, be warming up to 50 ℃, be incubated 1 hour and be filled with fluorine gas and nitrogen in backward reactor, controlling fluorine gas dividing potential drop in reactor is 80KPa, keep temperature 50 C reaction 600 minutes, after reaction finishes, question response device naturally cooling, take out sample.
The massfraction that records fluorine element in this functionalized graphene is 31 %, and the massfraction of carbon is 69%.
Table.
As can be known from the above table, in the embodiment of the present invention 1 ~ 6, the weightless peak temperature of prepared high fluorine content fluorinated graphene is all over 470 ℃, tool/high thermostability, and in Comparative Examples, the weightless peak temperature of fluorinated graphene does not all surpass 400 ℃, wherein embodiment's 9 is only 245 ℃.
Claims (10)
1. the preparation method of one kind high fluorine content fluorinated graphene is characterized in that the method comprises the following steps:
(1), first by the aqueous dispersions of the standby graphene oxide of conventional improvement Hummers legal system, after then the aqueous dispersions of graphene oxide being refrigerated in liquid nitrogen and being frozen into solid fully, lyophilize obtains cellular graphene oxide;
(2) graphene oxide step (1) made, under rare gas element and fluorine gas mixed atmosphere, heats up and carries out fluoridation, is cooled to room temperature and gets final product.
2. the preparation method of high fluorine content fluorinated graphene according to claim 1, is characterized in that in step (1), lyophilize to the water content in graphene oxide is 1～3 wt %.
3. according to the preparation method of the described high fluorine content fluorinated graphene of claim 1 or 2, it is characterized in that the initial partial pressure of the front fluorine gas of step (2) intensification fluoridation is 3 ~ 80KPa.
4. according to the preparation method of the described high fluorine content fluorinated graphene of claim 1 or 2, the method for fluoridizing that it is characterized in that in step (2) heating up is: the temperature rise rate with 1 ~ 20 ℃/min is warming up to 80 ~ 250 ℃, and is incubated 10 ~ 600 minutes.
5. the preparation method of high fluorine content fluorinated graphene according to claim 3, the method for fluoridizing that it is characterized in that in step (2) heating up is: the temperature rise rate with 1 ~ 20 ℃/min is warming up to 80 ~ 250 ℃, is incubated 10 ~ 600 minutes.
6. according to the preparation method of the described high fluorine content fluorinated graphene of claim 1 or 2, it is characterized in that the time of liquid nitrogen freezing in step (1) is 100 ~ 600 s.
7. the preparation method of high fluorine content fluorinated graphene according to claim 3, is characterized in that the time of liquid nitrogen freezing in step (1) is 100 ~ 600 s.
8. the preparation method of high fluorine content fluorinated graphene according to claim 5, is characterized in that the time of liquid nitrogen freezing in step (1) is 100 ~ 600 s.
9. according to the preparation method of the described high fluorine content fluorinated graphene of claim 1 or 2, it is characterized in that rare gas element described in step (2) is at least one in nitrogen, argon gas, helium and carbon dioxide.
10. the high fluorine content fluorinated graphene that according to claim 1 prepared by method, the fluorine content that it is characterized in that 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 ℃, and resistance is greater than 10
12Ω.
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