CN104556000B - The preparation method of micropore Graphene - Google Patents
The preparation method of micropore Graphene Download PDFInfo
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- CN104556000B CN104556000B CN201410760745.8A CN201410760745A CN104556000B CN 104556000 B CN104556000 B CN 104556000B CN 201410760745 A CN201410760745 A CN 201410760745A CN 104556000 B CN104556000 B CN 104556000B
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Abstract
The present invention relates to the preparation method of a kind of technical field of nano material, be specifically related to the preparation method of a kind of micropore Graphene.The technical scheme used is: the preparation method of micropore Graphene, comprises the following steps: the first step, utilizes the dispersion liquid of the graphite oxide of high degree of dispersion prepared by Hummers method, and concentration is 3 5mg/mL.Second step, joins polyvinylpyrrolidone (PVP) in the dispersion liquid of graphite oxide, supersound process after the dissolving that stirs, and then dries up to obtain dusty material under natural environment；3rd step, the powder mull of gained is uniform, be placed on high-temperature roasting in inert atmosphere, micropore Graphene.
Description
Technical field
The present invention relates to the preparation method of a kind of technical field of nano material, be specifically related to the preparation method of a kind of micropore Graphene.
Background technology
After within 2004, Graphene is successfully prepared by the method that micromechanics is peeled off by Geim seminar of Univ Manchester UK, Graphene becomes the carbon nanomaterial most with researching value；Graphene has the highest specific surface area and prominent mechanical property, heat conductivility and electric conductivity.The predominantly organic tool of preparation method of Graphene is peeled off at present, chemical vapour deposition technique, liquid phase method, chemistry redox method etc..But most preparation method is relatively costly, productivity is relatively low and limits the large-scale application of Graphene, and Hummers method is a kind of method succinctly preparing Graphene easily, its low cost, productivity is high, therefore, for the commercial Application of Graphene, Hummers method is a kind of the most attractive method preparing Graphene, has had the company utilizing this kind of method to carry out volume production Graphene.But in the preparation process of this kind of method, the dispersibility of graphite oxide is uneven, it is easy to reunite.And the Graphene itself preparing gained has defect and specific surface area is less, aperture structure is unfavorable for the ion migration in lithium ion battery and ultracapacitor.
Summary of the invention
It is an object of the invention to prepare Graphene itself for Hummers method and there is defect and the less deficiency of specific surface area, provide the preparation method of a kind of micropore Graphene and the prepared Graphene with relatively multi-cellular structure, thus improve specific surface area and the electric conductivity of Graphene further.
The present invention realizes the technical scheme that above-mentioned purpose used:
The preparation method of a kind of micropore Graphene, comprises the following steps:
The first step, utilizes the dispersion liquid of the graphite oxide of high degree of dispersion prepared by Hummers method, and concentration is 3-5
mg/mL.；
Second step, joins polyvinylpyrrolidone (PVP) in the dispersion liquid of graphite oxide, supersound process after the dissolving that stirs, and then dries up to obtain dusty material under natural environment；
3rd step, the powder mull of gained is uniform, be placed on high-temperature roasting in inert atmosphere, micropore Graphene.
The preparation method of described micropore Graphene, it is characterized in that, the dispersion solution preparing step of described graphite oxide: first sodium nitrate, crystalline flake graphite and concentrated sulphuric acid are joined in beaker and stir, then under condition of ice bath, add a certain amount of potassium permanganate, until after potassium permanganate addition terminates, continue to stir at normal temperatures, the temperature of ice bath controls at 0-5 DEG C, add dilute sulfuric acid after stirring certain time and hydrogen peroxide continues to stir, it is eventually adding buffer solution, after standing a period of time, it is centrifuged washing.Washing uses distilled water to carry out repeatedly centrifuge washing, surveying pH value until stopping centrifuge washing when supernatant PH is 7, being poured out by the solution washed, i.e. can get the dispersion liquid of finely dispersed graphite oxide from centrifuge tube, and concentration is about 3-5 mg/mL.
The preparation method of described micropore Graphene, is characterized in that, described buffer solution be dilute sulfuric acid and hydrogen peroxide mixed solution, the mass ratio of concentrated sulphuric acid, hydrogen peroxide and distilled water is 1:3:30.
The rotating speed of described centrifuge washing is 1000 ~ 8000 rpm/min.
The dispersion liquid of described graphite oxide is to take the upper strata expansion solutions of gained after centrifuge washing, is got rid of by lower sediment thing, and solution concentration is the dispersion liquid of the homodisperse graphite oxide of 2-5 mg/mL.
The running parameter of described supersound process: operating frequency is 40 ~ 100 KHz, ultrasonic power 120 W, ultrasonic time 30 min-2 h.
The consumption of polyvinylpyrrolidone (PVP) is in graphite oxide mass-dispersion liquid 1/2-2 times of graphite oxide quality.
Inert atmosphere refers under nitrogen atmosphere, and the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
Beneficial effect:
1 can be good at combining with the oxy radical in graphite oxide due to polyvinylpyrrolidone (PVP), further increases the dispersibility of graphite oxide.And polyvinylpyrrolidone (PVP) can decompose completely at about 400 DEG C, by specific surface area and the graph of pore diameter distribution of grapheme material, it can be seen that grapheme material specific surface area prepared by this kind of method is up to 450 m2 g-1, there is higher specific surface area and even aperture distribution, micropore be distributed in about 0.4 nm.Something which increases electric conductivity and the electron mobility of grapheme material.
2, owing to containing nitrogen element in polyvinylpyrrolidone (PVP), when pyrolytic, most nitrogen element is attached to graphenic surface, this electric conductivity also further increasing grapheme material and high rate performance.
3, polyvinylpyrrolidone (PVP) is nontoxic and can be good at being dissolved in water, and therefore this kind of preparation method is with low cost, and technique is relatively simple, is suitable for industrialized production.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the grapheme material using the art of this patent to prepare.
Fig. 2 is the specific surface area figure of the grapheme material using the art of this patent to prepare
Fig. 3 is the graph of pore diameter distribution of the grapheme material using the art of this patent to prepare.
Detailed description of the invention
The preparation method of a kind of micropore Graphene, comprises the following steps:
The first step, utilizes the dispersion liquid of the graphite oxide of high degree of dispersion prepared by Hummers method, and concentration is 3-5
mg/mL.；
Second step, joins polyvinylpyrrolidone (PVP) in the dispersion liquid of graphite oxide, supersound process after the dissolving that stirs, and then dries up to obtain dusty material under natural environment；
3rd step, the powder mull of gained is uniform, be placed on high-temperature roasting in inert atmosphere, micropore Graphene.
The dispersion solution preparing step of described graphite oxide: first sodium nitrate, crystalline flake graphite and concentrated sulphuric acid are joined in beaker and stir, then under condition of ice bath, add a certain amount of potassium permanganate, until after potassium permanganate addition terminates, continue to stir at normal temperatures, the temperature of ice bath controls at 0-5 DEG C, adds dilute sulfuric acid and hydrogen peroxide continues to stir, be eventually adding buffer solution after stirring certain time, after standing a period of time, it is centrifuged washing.Washing uses distilled water to carry out repeatedly centrifuge washing, surveying pH value until stopping centrifuge washing when supernatant PH is 7, being poured out by the solution washed, i.e. can get the dispersion liquid of finely dispersed graphite oxide from centrifuge tube, and concentration is about 3-5 mg/mL.
The preparation method of described micropore Graphene, is characterized in that, described buffer solution be dilute sulfuric acid and hydrogen peroxide mixed solution, the mass ratio of concentrated sulphuric acid, hydrogen peroxide and distilled water is 1:3:30.
The rotating speed of described centrifuge washing is 1000 ~ 8000 rpm/min.
The dispersion liquid of described graphite oxide is to take the upper strata expansion solutions of gained after centrifuge washing, is got rid of by lower sediment thing, and solution concentration is the dispersion liquid of the homodisperse graphite oxide of 2-5 mg/mL.
The running parameter of described supersound process: operating frequency is 40 ~ 100 KHz, ultrasonic power 120 W, ultrasonic time 30 min-2 h.
The consumption of polyvinylpyrrolidone (PVP) is in graphite oxide mass-dispersion liquid 1/2-2 times of graphite oxide quality.
Inert atmosphere refers under nitrogen atmosphere, and the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
Embodiment 1:
Mainly in combination with concrete case study on implementation, the preparation method of Graphene is described in further detail below.The present embodiment is implemented under premised on technical solution of the present invention, gives detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
A kind of method preparing micropore Graphene of the present invention, it is characterised in that be achieved by the steps of:
Embodiment 1:
(1) weigh crystalline flake graphite 5 g, sodium nitrate 4.0 g to put in reactor；
(2) 172.2 are measured
The concentrated sulphuric acid of mL joins in reactor, stirs one day.Weigh 22.5
G potassium permanganate joins in reactor, adds stirring under condition of ice bath.
(3) sulfuric acid solution 500 mL preparing 5 wt% joins in reactor, stirs 2 h.It is subsequently adding the hydrogen peroxide solution of 50 mL, stirs 2 h.
(4) preparation concentrated sulphuric acid and the mixed solution of hydrogen peroxide, as the buffer solution of graphite oxide, be centrifuged washing, finally with distilled water wash, until supernatant PH is 7.
(5) dispersion liquid of the graphite oxide of centrifugal gained, concentration 2 mg/mL.Measure 100 mL graphite oxide dispersion.
(6) weigh in the dispersion liquid that polyvinylpyrrolidone (PVP) 0.1 g joins graphite oxide, after stirring and dissolving, ultrasonic disperse 30
min。
(7) mixed liquor placement being dried at room temperature for, ground by the mixture of gained and exist, carry out high-temperature roasting the most under nitrogen atmosphere, the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
The specific surface area of the Graphene preparing gained reaches 442.9 m2 g-1, micropore is uniformly distributed, and layered structure is preferable, reunites the most in a large number.
Embodiment 2:
(1) preparation of graphite oxide: with the preparation of graphite oxide in example one；
(2) dispersion liquid of the graphite oxide of centrifugal gained, measures 100 mL graphite oxide dispersion.
(3) weigh in the dispersion liquid that polyvinylpyrrolidone (PVP) 0.3 g joins graphite oxide, after stirring and dissolving, ultrasonic disperse 60
min。
(4) mixed liquor placement being dried at room temperature for, ground by the mixture of gained and exist, carry out high-temperature roasting the most under nitrogen atmosphere, the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
The specific surface area of the Graphene preparing gained reaches 452.6 m2 g-1, micropore is uniformly distributed, and layered structure is preferable, and a large amount of reunions are together.
Embodiment 3:
(1) preparation of graphite oxide: with the preparation of graphite oxide in example one；
(2) dispersion liquid of the graphite oxide of centrifugal gained, measures 100 mL graphite oxide dispersion.
(3) weigh in the dispersion liquid that polyvinylpyrrolidone (PVP) 0.4 g joins graphite oxide, after stirring and dissolving, ultrasonic disperse 90
min。
(4) mixed liquor placement being dried at room temperature for, ground by the mixture of gained, carry out high-temperature roasting the most under nitrogen atmosphere, the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
The specific surface area of the Graphene preparing gained reaches 450.2 m2 g-1, micropore is uniformly distributed, and layered structure is preferable, reunites the most in a large number.
Embodiment 4:
(1) preparation of graphite oxide: with the preparation of graphite oxide in example one；
(2) dispersion liquid of the graphite oxide of centrifugal gained, concentration 5 mg/mL.Measure 100 mL graphite oxide dispersion.
(3) weigh in the dispersion liquid that polyvinylpyrrolidone (PVP) 0.5 g joins graphite oxide, after stirring and dissolving, ultrasonic disperse 120
min。
(4) mixed liquor placement being dried at room temperature for, ground by the mixture of gained and exist, carry out high-temperature roasting the most under nitrogen atmosphere, the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
The specific surface area of the Graphene preparing gained reaches 449.1 m2 g-1, micropore is uniformly distributed, and layered structure is preferable, reunites the most in a large number.
In the present invention, the mass ratio of polyvinylpyrrolidone and graphite oxide is meeting the requirement of 1/2-2, and ultrasonic time is 30
The present invention can be realized in min-2 h；Do not enumerate case study on implementation.
The present invention is directed to the defect that the Graphene specific surface area utilizing Hummers method to prepare that illustrated in technical background is less, significantly improve this defect by adding polyvinylpyrrolidone (PVP).Polyvinylpyrrolidone (PVP) is nontoxic and can be good at being dissolved in water, and well links together with the oxygen-containing functional group in graphite oxide, it is possible to increase the dispersibility of graphite oxide.The addition of polyvinylpyrrolidone (PVP) not only greatly improves the specific surface area of Graphene, and also can draw Graphene micropore quantity showed increased prepared by this kind of method according to graph of pore diameter distribution, and pore-size distribution is 0.4
About nm, the grapheme material of microcellular structure, it is more beneficial for the migration of ion, charge and discharge process is not susceptible to structure change, so that the stability of lithium ion battery and ultracapacitor strengthens.Simultaneously, polyvinylpyrrolidone (PVP) has nitrogen-containing group, Graphene after high-temperature process also contains a small amount of nitrogen element, this also further increases the electric conductivity of Graphene, the Graphene prepared by doping polyvinylpyrrolidone (PVP), preparation technology is simple, easy to operate, has extraordinary application prospect in ultracapacitor and lithium ion battery.
Claims (8)
1. a preparation method for micropore Graphene, comprises the following steps:
The first step, utilizes the dispersion liquid of the graphite oxide of high degree of dispersion prepared by Hummers method, and concentration is 3-5 mg/mL；
Second step, joins polyvinylpyrrolidone (PVP) in the dispersion liquid of graphite oxide, supersound process after the dissolving that stirs, and then dries up to obtain dusty material under natural environment；
3rd step, the powder mull of gained is uniform, be placed on high-temperature roasting in inert atmosphere, micropore Graphene.
The preparation method of micropore Graphene the most according to claim 1, it is characterized in that, the dispersion solution preparing step of described graphite oxide: first by sodium nitrate, crystalline flake graphite and concentrated sulphuric acid join in beaker and stir, then under condition of ice bath, add a certain amount of potassium permanganate, until after potassium permanganate addition terminates, continue to stir at normal temperatures, the temperature of ice bath controls at 0-5 DEG C, add dilute sulfuric acid after stirring certain time and hydrogen peroxide continues to stir, it is eventually adding buffer solution, after standing a period of time, it is centrifuged washing, washing uses distilled water to carry out repeatedly centrifuge washing, survey
PH value is until the supernatant
Stopping centrifuge washing when pH is 7, poured out by the solution washed, i.e. can get the dispersion liquid of finely dispersed graphite oxide from centrifuge tube, concentration is 3-5 mg/mL.
The preparation method of micropore Graphene the most according to claim 2, is characterized in that, described buffer solution is the mixed solution of dilute sulfuric acid and hydrogen peroxide, and the mass ratio using concentrated sulphuric acid, hydrogen peroxide and distilled water is that 1:3:30 prepares.
The most according to claim 2, the preparation method of micropore Graphene, is characterized in that, the rotating speed of described centrifuge washing is 1000 ~ 8000 rpm/min.
The preparation method of micropore Graphene the most according to claim 2, it is characterized in that, the dispersion liquid of described graphite oxide is to take the upper strata expansion solutions of gained after centrifuge washing, is got rid of by lower sediment thing, and solution concentration is the dispersion liquid of the homodisperse graphite oxide of 3-5 mg/mL.
The most according to claim 1, the preparation method of micropore Graphene, is characterized in that, the running parameter of described supersound process: operating frequency is 40 ~ 100 KHz, ultrasonic power 120 W, ultrasonic time 30 min-2 h.
The most according to claim 1, the preparation method of micropore Graphene, is characterized in that, in the dispersion liquid that consumption is graphite oxide of polyvinylpyrrolidone (PVP) 1/2-2 times of graphite oxide quality.
The most according to claim 1, the preparation method of micropore Graphene, is characterized in that, inert atmosphere refers under nitrogen atmosphere, and the temperature of high-temperature roasting is 800 DEG C, and roasting time is 2 h, and programming rate is 5 DEG C/min.
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