CN102701197A - Preparation method of soluble graphite oxide powder - Google Patents
Preparation method of soluble graphite oxide powder Download PDFInfo
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- CN102701197A CN102701197A CN2012102154240A CN201210215424A CN102701197A CN 102701197 A CN102701197 A CN 102701197A CN 2012102154240 A CN2012102154240 A CN 2012102154240A CN 201210215424 A CN201210215424 A CN 201210215424A CN 102701197 A CN102701197 A CN 102701197A
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Abstract
The invention discloses a preparation method of soluble graphite oxide powder, comprising the following steps of: (1) preparing a soluble graphite oxide by the strong oxidant oxidization method; (2) diluting the soluble graphite oxide to 1:100-1:1000 by distillation water: firstly ultrasonic-dispensing for 10-50min, and then, mechanically blending for 20-60min; (3) spry drying: firstly regulating the air temperature of the material inlet of a spray drier to 140 DEG C-200 DEG C, regulating the flow of a peristaltic pump to 300-1000mL/h and the frequency of a fan to 30Hz-100Hz, pre-spraying distillation water for 5min-10min, and then, spray drying the graphite oxide solution to obtain graphite oxide particles; and (4) drying for 2h-24h under the vacuum condition at room temperature, and obtaining the soluble graphite oxide powder. The preparation method provided by the invention has the characteristics of short preparation cycle and high efficiency. The obtained powdery soluble graphite oxide is more liable to dissolve into water and organic solvents compared with other graphite oxides, and simultaneously, is also uniform in size.
Description
Technical field
The present invention relates to a kind of preparation method of graphite oxide powder, especially a kind of preparation method of solubility graphite oxide powder.
Background technology
Graphene is the novel two-dimensional nano material with an atomic thickness, receives much attention in recent years.It is reported that its Young's modulus is 1,100 GPa, stress-at-break is 125 GPa, and thermal conductivity is 5,000 Wm
-1K
-1, charge carrier mobility is 200,000 cm
2V
-1S
-1, specific surface area is 2,630 m
2g
-1Therefore its theory and experimental result thereof show that all the graphene film of individual layer two dimension is the maximum material of finding so far of mechanical strength.In addition, this type type material has high specific conductivity, thermal conductivity, flintiness and high aspect ratio.Therefore, it is with a wide range of applications in fields such as transistor, ultracapacitor, strongtheners.
And graphite oxide has been widely used in preparing cheap Graphene and functionalization graphene as the intermediate product of " redox chemistry method " preparation Graphene.But after oxidation, hydrolysis, adopt the traditional drying method to prepare the pulverulent solids that graphite oxide is difficult to obtain favorable solubility, the solvability of product in water or in the organic solvent is relatively poor, has brought difficulty to subsequent applications.Therefore, need a kind of method for preparing solubility graphite oxide powder of design.
Summary of the invention
Goal of the invention of the present invention provides a kind of method for preparing the graphite oxide powder, obtains all reasonable graphite oxide powder of solvability in water and organic solvent to adopt simple and easy to do method.
For reaching the foregoing invention purpose, the technical scheme that the present invention adopts is: a kind of preparation method of solubility graphite oxide powder comprises the following steps:
(1) adopts SODIUMNITRATE, the vitriol oil, strong oxidizer as the intercalation oxygenant, Graphite Powder 99 is handled, obtain water miscible graphite oxide; Said strong oxidizer is selected from the mixture of potassium permanganate and concentrated nitric acid;
(2) graphite oxide that step (1) is obtained is used distilled water diluting, and the mass ratio of graphite oxide and zero(ppm) water is 1: 100～1: 1000, carries out ultra-sonic dispersion earlier 10～50 minutes, and mechanical stirring is 20～60 minutes again, obtains the homodisperse graphite oxide aqueous solution;
(3) the graphite oxide aqueous solution after step (2) dilution is carried out spraying drying, method is that the opening for feed wind-warm syndrome of at first regulating spray-drier is 140～200 ℃; The peristaltic pump flow is 300～1000mL/h; The blower fan frequency is 30～100Hz, sprayed in advance 5～10 minutes with zero(ppm) water, and then the graphite oxide aqueous solution is carried out spraying drying; Obtain the graphite oxide particle, in this process, the graphite oxide aqueous solution is continued to stir with mechanical stirring;
(4) the graphite oxide particle that step (3) is obtained is put in the vacuum drying oven, and drying is 2～24 hours under the room temperature, obtains solubility graphite oxide powder.
In the preceding text, the vitriol oil is used to increase the oxidisability of strong oxidizer simultaneously on the one hand as solvent.The graphite oxide size that step (1) obtains is being carried out step (2) before generally greater than 2 μ m, can its quality purity reached more than 99% through filtering, washing.Step (4) is further removed the water in the graphite oxide through vacuum-drying.
In the technique scheme, in the step (1), press mass ratio, Graphite Powder 99: SODIUMNITRATE: the vitriol oil: strong oxidizer is 1: (0.8～1.2): (30～70): (3～10); Add 100～300 times the water that is equivalent to the Graphite Powder 99 quality in the reaction system; After reaction finished, product filtered and water is washed till neutrality.
In the technique scheme, in the said step (2), the optimum quality ratio of graphite oxide and zero(ppm) water is 1: 500.
In the technique scheme, the particle diameter of final product solubility graphite oxide powder is 0.1～2 μ m.
The solubleness of final product solubility graphite oxide powder in water is higher than 5 mg/mL; Solubleness in organic solvent is higher than 1 mg/mL.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
1. the present invention utilizes spray drying method for preparation graphite oxide powder, and method is simple, and preparation cycle is short, and efficient is high; The solvability of the solubility graphite oxide powder that obtains in water and in the organic solvent is high, and solubleness is greater than 5 mg/mL in water, and solubleness is greater than 1 mg/mL in organic solvent;
2. the pulverous graphite oxide of present method is dissolved in the water with respect to other graphite oxides more easily, and the powder size does not evenly contain any additives simultaneously, and purity surpasses 99%;
3. the graphite oxide diameter of particle of the present invention's acquisition is little, and specific surface area is big, more is prone to participate in chemical reaction.
Description of drawings
Accompanying drawing 1 is the process flow sheet of the embodiment of the invention one;
Accompanying drawing 2 is photos of the raw material Graphite Powder 99 of preparation graphite oxide in the embodiment of the invention one;
Accompanying drawing 3 is spongy sample photos that water soluble oxidized graphite obtains with freeze-drying in the Comparative Examples one;
Accompanying drawing 4 is bulk sample photos that water soluble oxidized graphite obtains with boulton process in the Comparative Examples two;
Accompanying drawing 5 is photos of the graphite oxide powder for preparing in the embodiment of the invention one;
Accompanying drawing 6 is that the graphite oxide powder of preparation in the embodiment of the invention one is dissolved in the photo in the water;
Accompanying drawing 7 is that the graphite oxide powder of preparation in the embodiment of the invention one is dissolved in the photo in the organic solvent;
Accompanying drawing 8 is uv-absorbing spectrograms of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 9 is Raman spectrums of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 10 is ir spectras of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 11 is X-ray diffractograms of the graphite oxide powder of preparation in the embodiment of the invention one.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment one: a kind of preparation method of solubility graphite oxide powder, its technology is referring to shown in the accompanying drawing 1.Concrete operations are following:
Pre-oxidation treatment: with 2.5 kg Graphite Powder 99s and 2 kg NaNO
3Be mixed in the 500 L water and the 80 L vitriol oils, with 4.5 kg KMnO
4With concentrated nitric acid oxidation 5 days, product filtered and washes with big water gaging and obtains graphite oxide;
Secondary oxidative treatments: wherein 200 gram graphite oxides mix with 20 kilograms of zero(ppm) water; Graphite oxide is irregular blocks of solid, earlier with ultra-sonic dispersion 20 minutes (ultrasonic frequency is 20KHz-30KHz, below identical); Stirred 20 minutes with mechanical stirrer then, obtain the graphite oxide aqueous solution.Next with spray-drier the graphite oxide aqueous solution is carried out spraying drying; Elder generation is adjusted to 160 ℃ with the inlet wind-warm syndrome of spray-drier before dry; The blower fan frequency adjustment is to 40Hz, and the peristaltic pump amount is 400mL/h, still need constantly carry out mechanical stirring to the graphite oxide aqueous solution in the whole process; The graphite oxide powder that obtains after the spraying drying is put into vacuum drying oven, and vacuum-drying is 4 hours under the normal temperature, can obtain title product graphite oxide powder.
Referring to table 1, be the ultimate analysis data of the graphite oxide powder of preparation in the embodiment of the invention one; Can find out that from table 1 product of embodiment one is compared on elementary composition with Comparative Examples two with Comparative Examples one does not have notable difference, what obtain is degree of oxidation graphite oxide preferably.
Table 1. ultimate analysis data
| Sample | N/% | C/% | H/% | O/% |
| Embodiment one: spraying drying graphite oxide powder | 0.132 | 42.31 | 3.002 | 54.556 |
| Comparative Examples one: block graphite oxide | 0.117 | 41.77 | 3.011 | 55.112 |
| Comparative Examples two: vacuum-drying graphite oxide | 0.102 | 43.21 | 3.071 | 53.617 |
Referring to accompanying drawing 2, be the photo that present embodiment prepares the raw material Graphite Powder 99 of graphite oxide;
Accompanying drawing 5 is photos of the graphite oxide powder for preparing in the embodiment of the invention one;
Accompanying drawing 6 is that the graphite oxide powder of preparation in the embodiment of the invention one is dissolved in the photo in the water;
Accompanying drawing 7 is that the graphite oxide powder of preparation in the embodiment of the invention one is dissolved in the photo in the organic solvent;
Accompanying drawing 8 is uv-absorbing spectrograms of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 9 is Raman spectrums of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 10 is ir spectras of the graphite oxide powder of preparation in the embodiment of the invention one;
Accompanying drawing 11 is X-ray diffractograms of the graphite oxide powder of preparation in the embodiment of the invention one.
Comparative Examples one:
With 2.5 kg Graphite Powder 99s and 2.5 kg NaNO
3Be mixed in the 500 L water and the 100 L vitriol oils, use KMnO
4And concentrated nitric acid oxidation, promptly obtain the solubility graphite oxide;
Will be wherein 100 gram solubility graphite oxides dry under freeze drier after with liquid nitrogen freezing, freeze drier is provided with temperature and be-50 ℃, vacuum tightness is 0.04 Mpa, drying can obtain cryodesiccated Vandyke brown bulk oxidation graphite solid in 10 days.
Referring to accompanying drawing 3, be the spongy sample photo that water soluble oxidized graphite obtains with freeze-drying in the Comparative Examples one.
Comparative Examples two:
With 2.5 kg Graphite Powder 99s and 2.5 kg NaNO
3Be mixed in the 500 L water and the 100 L vitriol oils, use KMnO
4And concentrated nitric acid oxidation, promptly obtain the solubility graphite oxide;
Wherein 100 gram solubility graphite oxides are dry with being placed in the vacuum drying oven, and oven temperature is 30 ℃, and vacuum tightness is 0.07 Mpa, can obtain vacuum drying black sheet oxidation graphite solid in dry 10 days.
Referring to accompanying drawing 4, be the bulk sample photo that water soluble oxidized graphite obtains with boulton process in the Comparative Examples two.
Embodiment two:
With 2 kg Graphite Powder 99s and 2 kg NaNO
3Be mixed in the 500 L water and the 50 L vitriol oils, with 10 kg KMnO
4With concentrated nitric acid oxidation 3 days, product filtered and washes with big water gaging and promptly obtains the solubility graphite oxide;
Wherein 100 gram graphite oxides mix with 10 kilograms of zero(ppm) water; Graphite oxide is near the black chip solid, earlier with ultra-sonic dispersion 20 minutes (ultrasonic frequency is 20KHz-30KHz, below identical); Stirred 20 minutes with mechanical stirrer then, obtain the graphite oxide aqueous solution.Next with spray-drier the graphite oxide aqueous solution is carried out spraying drying; Elder generation is adjusted to 180 ℃ with the inlet wind-warm syndrome of spray-drier before dry; The blower fan frequency adjustment is to 45Hz, and the peristaltic pump amount is 600mL/h, still need constantly carry out mechanical stirring to the graphite oxide aqueous solution in the whole process; The graphite oxide powder that spraying drying all obtains is put into vacuum drying oven, and vacuum-drying is 4 hours under the normal temperature, can obtain title product graphite oxide powder.
Embodiment three:
With 2.5 kg Graphite Powder 99s and 2.5 kg NaNO
3Be mixed in the 500 L water and the 100 L vitriol oils, use KMnO
4And concentrated nitric acid oxidation, promptly obtain the solubility graphite oxide;
Wherein 300 gram graphite oxides mix with 50 kilograms of zero(ppm) water; Graphite oxide is a particle diameter greater than 10 microns particulate solid, earlier with ultra-sonic dispersion 50 minutes (ultrasonic frequency is 20KHz-30KHz, below identical); Stirred 90 minutes with mechanical stirrer then, obtain the graphite oxide aqueous solution.Next with spray-drier the graphite oxide aqueous solution is carried out spraying drying; Elder generation is adjusted to 190 ℃ with the inlet wind-warm syndrome of spray-drier before dry; The blower fan frequency adjustment is to 35Hz, and the peristaltic pump amount is 800mL/h, still need constantly carry out mechanical stirring to the graphite oxide aqueous solution in the whole process; The graphite oxide powder that spraying drying all obtains is put into vacuum drying oven, and vacuum-drying is 12 hours under the normal temperature, can obtain title product graphite oxide powder.
Claims (5)
1. the preparation method of a solubility graphite oxide powder is characterized in that, comprises the following steps:
(1) adopts SODIUMNITRATE, the vitriol oil, strong oxidizer as the intercalation oxygenant, Graphite Powder 99 is handled, obtain water miscible graphite oxide; Said strong oxidizer is the mixture of potassium permanganate and concentrated nitric acid;
(2) graphite oxide that step (1) is obtained is used distilled water diluting, and the mass ratio of graphite oxide and zero(ppm) water is 1: 100～1: 1000, carries out ultra-sonic dispersion earlier 10～50 minutes, and mechanical stirring is 20～60 minutes again, obtains the homodisperse graphite oxide aqueous solution;
(3) the graphite oxide aqueous solution after step (2) dilution is carried out spraying drying, method is that the opening for feed wind-warm syndrome of at first regulating spray-drier is 140～200 ℃; The peristaltic pump flow is 300～1000mL/h; The blower fan frequency is 30～100Hz, sprayed in advance 5～10 minutes with zero(ppm) water, and then the graphite oxide aqueous solution is carried out spraying drying; Obtain the graphite oxide particle, in this process, the graphite oxide aqueous solution is continued to stir with mechanical stirring;
(4) the graphite oxide particle that step (3) is obtained is put in the vacuum drying oven, and drying is 2～24 hours under the room temperature, obtains solubility graphite oxide powder.
2. the preparation method of solubility graphite oxide powder according to claim 1 is characterized in that: in the step (1), press mass ratio, Graphite Powder 99: SODIUMNITRATE: the vitriol oil: strong oxidizer is 1: (0.8～1.2): (30～70): (3～10); Add 100～300 times the water that is equivalent to the Graphite Powder 99 quality in the reaction system; After reaction finished, product filtered and water is washed till neutrality.
3. the preparation method of solubility graphite oxide powder according to claim 1 is characterized in that: the particle diameter of said solubility graphite oxide powder is 0.1～2 μ m.
4. the preparation method of solubility graphite oxide powder according to claim 1 is characterized in that: the solubleness of described solubility graphite oxide powder in water is higher than 5 mg/mL; Solubleness in organic solvent is higher than 1mg/mL.
5. the preparation method of solubility graphite oxide powder according to claim 1 is characterized in that: in the said step (2), the mass ratio of graphite oxide and zero(ppm) water is 1: 500.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110482540A (en) * | 2019-09-27 | 2019-11-22 | 常州汇墨新材料科技有限公司 | A kind of preparation method of the graphene oxide powder of good dispersion |
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| US20100056819A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Process for producing dispersible and conductive Nano Graphene Platelets from non-oxidized graphitic materials |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110482540A (en) * | 2019-09-27 | 2019-11-22 | 常州汇墨新材料科技有限公司 | A kind of preparation method of the graphene oxide powder of good dispersion |
| CN110482540B (en) * | 2019-09-27 | 2022-11-08 | 徐州汇墨新材料科技有限公司 | Preparation method of graphene oxide powder with good dispersibility |
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Application publication date: 20121003 |