CN103723709A - Preparation method of aqueous single-layer graphene solution - Google Patents
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Abstract
The invention discloses a preparation method of an aqueous single-layer graphene solution. According to the method, natural graphite, calcium nitrate, potassium nitrate, concentrated sulfuric acid and potassium permanganate are mixed and processed to obtain a graphite oxide solution, and after the graphite oxide solution is prepared into an aqueous single-layer graphene oxide solution, a reducing agent is added for a reaction, and the aqueous single-layer graphene solution is obtained. According to the method, the aqueous single-layer graphene solution with high single layer rate, strong compositing feature and uniform dispersion is prepared finally after multiple times of ultrasonic stripping.
Description
Technical field
The present invention relates to Graphene technical field, particularly a kind of preparation method of mono-layer graphite aqueous solution.
Background technology
Graphene is a kind of two dimensional surface material, it by carbon atom according to sp
2become key to form stable honey comb structure, there is the performances such as stable Colloidal particles and excellent electricity, calorifics, mechanics, in various fields such as unicircuit of future generation, energy storage material, flexible display material, bio-pharmaceuticals, aerospace, environment-friendly materials, thermally conductive material, High Strength Steels, having broad application prospects, is impact and the strategic novel material that leads new round Industrial Revolution.Therefore urgently seek a kind of method of preparing in a large number Graphene.
Prior art discloses the preparation method of graphite alkene, comprise graphite oxide reduction method, micromechanics stripping method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process etc., wherein, micromechanics stripping method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process all have complex process, high in cost of production shortcoming, and the graphite oxide reduction rule with the advantage such as with low cost, can quantifying standby, method is simple becomes study hotspot.Graphite oxide reduction method conventionally, first by graphite oxidation and peel off into graphene oxide, restores and obtains Graphene, wherein, and by graphite oxidation and peel off that to obtain graphene oxide be committed step.
Prior art, by method of reducing, makes graphene oxide deoxidation obtain Graphene, thereby the conductivity of graphene oxide is enlarged markedly, but individual layer rate is low, reduce not thoroughly, in Graphene, the ratio of carbon and oxygen element is little, electric property is poor, has greatly affected the widespread popularity of Graphene.The graphite suspension that the former graphene solution preparation method based on Hydrogen bromide reduction obtains after fully reacting with potassium permanganate can not be dispersed in water fully, although the graphene aqueous solution obtaining can be used for multiple industrial use, but cannot guarantee more than 98%, to make mono-layer graphite aqueous solution.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of mono-layer graphite aqueous solution, make can make graphite be well dispersed in water in preparing mono-layer graphite aqueous solution process, prepare the graphene aqueous solution of high individual layer rate.
The present invention is achieved by the following technical solutions:
A preparation method for mono-layer graphite aqueous solution, carries out according to following steps:
(1) natural graphite powder is joined in the mixture of nitrocalcite and saltpetre, drip wherein deionized water, stir, hierarchy of control temperature is 0 ~ 5 ℃, slowly drip the vitriol oil that mass concentration is 98%, fully stir also hierarchy of control temperature and be no more than 15 ℃, dropwise and continue to stir, when system temperature is down to 8 ~ 12 ℃, slowly add potassium permanganate, and hierarchy of control temperature is no more than 15 ℃, continue to stir and make it fully react 30min ~ 12h, obtain graphite oxide solution; Wherein the mass ratio of nitrocalcite and saltpetre is 1:1 ~ 1:5, and the mass ratio of the mixture of natural graphite powder and nitrocalcite and saltpetre is 1:0.1 ~ 1:1;
(2) graphite oxide solution step (1) being obtained is carried out suction filtration, the filter cake obtaining is that 2% dilute hydrochloric acid washs at the temperature of 30 ~ 35 ℃ by mass concentration, after washing, with deionized water, be washed till neutrality, the filter cake that washing suction filtration is crossed is dispersed in deionized water, dispersion concentration is 10 ~ 1000mg/L, through ultrasonic peeling off, obtains aqueous solution of single-layer grapheme oxide;
(3) in aqueous solution of single-layer grapheme oxide, add reductive agent reaction and obtain mono-layer graphite aqueous solution.
The preparation method of described mono-layer graphite aqueous solution, can be according to adding the ratio of 0.01 ~ 0.5g reductive agent to add reductive agent in 1g graphite oxide aqueous solution in step (3), reduction reaction temperature can be 60 ~ 100 ℃, and the reaction times can be 10min ~ 24h, can be preferably 30min ~ 1h.
The preparation method of above-described mono-layer graphite aqueous solution, described reductive agent can be Hydrogen bromide.
The preparation method of described mono-layer graphite aqueous solution, in step (1), the amount of deionized water can be 10 ~ 50 times of natural graphite powder quality, the amount of the vitriol oil can be 1% ~ 50% of natural graphite powder quality, and the amount of potassium permanganate can be 0.5% ~ 20% of natural graphite powder quality.
The preparation method of described mono-layer graphite aqueous solution, it can be that ultrasonic described in step (2) peeled off under 40 ~ 80KHz ultrasonic for 2 ~ 10 times, and each ultrasonic time can be 30min ~ 2h, and the intermittent time can be 10min ~ 30min.
Reduction mechanism of the present invention is: Hydrogen bromide can effectively be realized the open loop of epoxy-functional on graphene oxide under low-temperature heat condition, make it be converted into oh group, utilize bromine atoms substituted hydroxy group simultaneously, thereby obtain bromination Graphene, again because interaction force between the carbon in bromine atoms and Graphene plane is less, in solution environmental, be attached to that bromine atoms in Graphene plane can be spontaneous from Graphene surface cancellation, and then realize the reduction of graphene oxide, the graphene solution obtaining.
Compared with prior art, the invention has the advantages that:
1, kind and the proportioning of interpolation oxygenant are more reasonable, select the nitrocalcite of specific proportioning and the mixture of saltpetre, and Graphite Powder 99 is fully oxidized, and are beneficial to graphite oxide and peel off into graphene oxide, graphite oxide are disperseed in deionized water more even;
2, graphite oxide is carried out to repeated ultrasonic operation, can significantly improve and obtain mono-layer graphite aqueous solution probability, individual layer rate reaches more than 99%, is conducive to the batch production of single-layer graphene;
3, use Hydrogen bromide as reductive agent, to equipment without particular requirement, toxicity is little, reductibility is strong, efficiency is high, is conducive to Graphene and fully reduces, the automatic cancellation of bromide anion after reaction, has no effect to Graphene quality, obtains high-quality Graphene.
Accompanying drawing explanation
Fig. 1 is Graphene atomic force microscope picture.
Fig. 2 is Graphene altitude distribution figure.
Fig. 3 is Graphene scanning electronic microscope schematic diagram.
Embodiment
Embodiment 1
(1) take 10g natural graphite powder, be placed in 1000ml reaction flask, add wherein 1g nitrocalcite and 5g saltpetre, after stirring, in reaction flask, slowly drip 120g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 2 g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 0.2g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 30 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/L graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 30min under 80KHz, and ultrasonic 30min again after 10min, repeats ultrasonic 5 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 0.3g Hydrogen bromide, stirring and control temperature of reaction system is 80 ℃, and isothermal reaction 10min makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.1%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.8-1.2nm.
Embodiment 2
(1) take 10g natural graphite powder, be placed in 1000ml reaction flask, add wherein 1g nitrocalcite and 4g saltpetre, after stirring, in reaction flask, slowly drip 100g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 0.5g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 0.05g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 31 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 40min under 80KHz, and ultrasonic 40min again after 20min, repeats ultrasonic 4 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 0.1g Hydrogen bromide, stirring and control temperature of reaction system is 70 ℃, and isothermal reaction 30min makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.2%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.6-1nm.
Embodiment 3
(1) take 10g natural graphite powder, be placed in 100ml reaction flask, add wherein 2g nitrocalcite and 4g saltpetre, after stirring, in reaction flask, slowly drip 200g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 1g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 2g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 30 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 50min under 70KHz, and ultrasonic 50min again after 25min, repeats ultrasonic 10 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 2g Hydrogen bromide, stirring and control temperature of reaction system is 60 ℃, and isothermal reaction 1h makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.4%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.5-0.8nm.
Embodiment 4
(1) take 20g natural graphite powder, be placed in 100ml reaction flask, add wherein 2g nitrocalcite and 6g saltpetre, after stirring, in reaction flask, slowly drip 760g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 5g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 2g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 33 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 60min under 60KHz, and ultrasonic 60min again after 30min, repeats ultrasonic 3 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 5g Hydrogen bromide, stirring and control temperature of reaction system is 60 ℃, and isothermal reaction 12h makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.4%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.4-0.8nm.
Embodiment 5
(1) take 9g natural graphite powder, be placed in 100ml reaction flask, add wherein 3g nitrocalcite and 6g saltpetre, after stirring, in reaction flask, slowly drip 450g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 3g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 0.5g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 35 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 50min under 40KHz, and ultrasonic 50min again after 20min, repeats ultrasonic 4 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 3g Hydrogen bromide, stirring and control temperature of reaction system is 60 ℃, and isothermal reaction 24h makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.5%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.5-1nm.
Embodiment 6
(1) take 20g natural graphite powder, be placed in 100ml reaction flask, add wherein 3g nitrocalcite and 6g saltpetre, after stirring, in reaction flask, slowly drip 600g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, the mass concentration that slowly drips 0.2g in constant temperature downhill reaction bottle is 98% vitriol oil, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 1g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 35 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 2h under 40KHz, and ultrasonic 2h again after 30min, repeats ultrasonic 3 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 10g Hydrogen bromide, stirring and control temperature of reaction system is 80 ℃, and isothermal reaction 30min makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.2%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.6-1nm.
Embodiment 7
(1) take 10g natural graphite powder, be placed in 100ml reaction flask, add wherein 2g nitrocalcite and 8g saltpetre, after stirring, in reaction flask, slowly drip 100g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, in constant temperature downhill reaction bottle, slowly drip 98% vitriol oil that 5g mass concentration is, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 0.8g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 34 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 1h under 70KHz, and ultrasonic 1h again after 10min, repeats ultrasonic 5 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 3g Hydrogen bromide, stirring and control temperature of reaction system is 90 ℃, and isothermal reaction 40min makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.3%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.5-0.9nm.
Embodiment 8
(1) take 20g natural graphite powder, be placed in 100ml reaction flask, add wherein 3g nitrocalcite and 3g saltpetre, after stirring, in reaction flask, slowly drip 300g deionized water, and hierarchy of control temperature is 2 ± 1 ℃, in constant temperature downhill reaction bottle, slowly drip 98% vitriol oil that 6g mass concentration is, hierarchy of control temperature is no more than 15 ℃, continues to stir, when system temperature is down to 10 ℃, slowly add 3g potassium permanganate, constantly stir, control temperature of reaction and be no more than 15 ℃, after reaction 1h, will obtain graphite oxide solution.
(2) graphite oxide solution is carried out to suction filtration, the dilute hydrochloric acid that filter cake is 2% by mass concentration washs 3 times at 32 ℃, then uses deionized water wash 4 times, obtains graphite oxide filter cake; Configuration 100ml, the 25g/l graphite oxide aqueous solution, be placed in 250ml Erlenmeyer flask, ultrasonic 40min under 80KHz, and ultrasonic 40min again after 15min, repeats ultrasonic 4 times, obtains finely dispersed graphite oxide aqueous solution.
(3) Erlenmeyer flask is placed in to the water-bath heating in advance, adds 8g Hydrogen bromide, stirring and control temperature of reaction system is 100 ℃, and isothermal reaction 10min makes black mono-layer graphite aqueous solution, and recording individual layer rate is 99.1%.Through principle force microscope, measure, single-layer graphene layer is smooth and level and smooth, and thickness is about 0.8-1nm.
The single-layer graphene respectively above embodiment being made carries out X x ray diffraction analysis x, Infrared spectroscopy, Raman spectrum analysis and X ray photoelectron spectroscopic analysis, and result shows, by method provided by the invention, has prepared single-layer graphene.
In the preparation process of Graphene, the reaction times lower than 30min time reduction not thorough, in solution, still have more graphene oxide; Reaction times surpass 1h on reducing degree without impact, and it is serious to be that product is reunited, so the Best Times of reduction reaction is 30min ~ 1h; The best proportioning of oxygenant nitrocalcite and saltpetre is 1:1 ~ 1:5, is greater than or less than this proportioning and makes graphite oxidation incomplete, contains the graphite that can not peel off in graphite oxide, affects the individual layer rate of graphene oxide, thereby affects the individual layer rate of Graphene.To embodiment 5, utilize atomic power electron microscope to observe, result as Fig. 1 be that Graphene principle force microscope picture and Fig. 2 are as shown in Graphene altitude distribution figure, with sem observation as shown in Figure 3, in embodiment 3 preparation Graphene pattern and structure characterize.Wherein as shown in Figure 1, show that single-layer graphene layer is smooth and level and smooth, thickness as shown in Figure 2, is about 0.5-1.0nm.Meanwhile, the scanning electron microscope diagram sheet of Graphene as shown in Figure 3, has further confirmed the thin layer pattern of Graphene.
Claims (6)
1. a preparation method for mono-layer graphite aqueous solution, is characterized in that, according to following steps, carries out:
(1) natural graphite powder is joined in the mixture of nitrocalcite and saltpetre, drip wherein deionized water, stir, hierarchy of control temperature is 0 ~ 5 ℃, slowly drip the vitriol oil that mass concentration is 98%, fully stir also hierarchy of control temperature and be no more than 15 ℃, dropwise and continue to stir, when system temperature is down to 8 ~ 12 ℃, slowly add potassium permanganate, and hierarchy of control temperature is no more than 15 ℃, continue to stir and make it fully react 30min ~ 12h, obtain graphite oxide solution; Wherein the mass ratio of nitrocalcite and saltpetre is 1:1 ~ 1:5, and the mass ratio of the mixture of natural graphite powder and nitrocalcite and saltpetre is 1:0.1 ~ 1:1;
(2) graphite oxide solution step (1) being obtained is carried out suction filtration, the filter cake obtaining is that 2% dilute hydrochloric acid washs at the temperature of 30 ~ 35 ℃ by mass concentration, after washing, with deionized water, be washed till neutrality, the filter cake that washing suction filtration is crossed is dispersed in deionized water, dispersion concentration is 10 ~ 1000mg/L, through ultrasonic peeling off, obtains aqueous solution of single-layer grapheme oxide;
(3) in aqueous solution of single-layer grapheme oxide, add reductive agent reaction and obtain mono-layer graphite aqueous solution.
2. the preparation method of mono-layer graphite aqueous solution according to claim 1, it is characterized in that, in step (3), according to adding the ratio of 0.01 ~ 0.5g reductive agent to add reductive agent in 1g graphite oxide aqueous solution, reduction reaction temperature is 60 ~ 100 ℃, and the reaction times is 10min ~ 24h.
3. the preparation method of mono-layer graphite aqueous solution according to claim 2, is characterized in that, the reaction times is 30min ~ 1h.
4. the preparation method of mono-layer graphite aqueous solution according to claim 1 and 2, is characterized in that, described reductive agent is Hydrogen bromide.
5. the preparation method of mono-layer graphite aqueous solution according to claim 1, it is characterized in that, the amount of the middle deionized water of step (1) is 10 ~ 50 times of natural graphite powder quality, the amount of the vitriol oil is 1% ~ 50% of natural graphite powder quality, and the amount of potassium permanganate is 0.5% ~ 20% of natural graphite powder quality.
6. the preparation method of mono-layer graphite aqueous solution according to claim 1, is characterized in that, ultrasonic described in step (2) peeled off as under 40 ~ 80KHz ultrasonic 2 ~ 10 times, and each ultrasonic time is 30min ~ 2h, and the intermittent time is 10min ~ 30min.
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