CN105540571A - A preparing method of an aqueous stable graphene dispersion liquid - Google Patents
A preparing method of an aqueous stable graphene dispersion liquid Download PDFInfo
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- CN105540571A CN105540571A CN201510976285.7A CN201510976285A CN105540571A CN 105540571 A CN105540571 A CN 105540571A CN 201510976285 A CN201510976285 A CN 201510976285A CN 105540571 A CN105540571 A CN 105540571A
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Abstract
A preparing method of an aqueous stable graphene dispersion liquid is provided. The method includes (1) a step of adding a dispersing agent into water, and performing magnetic stirring for 2-3 min until dispersion is uniform with the mass volume ratio of the dispersing agent to the water being 0.5-5:10-100 g/mL, and (2) a step of adding graphene into the prepared dispersing solution with the mass volume ratio of the graphene to the water in the step (1) being 0.1:10-100 g/mL, performing magnetic stirring for 2-3 min and performing ultrasonic dispersion for 1-10 h to obtain the aqueous stable graphene dispersion liquid high in dispersity. Concentrated acids and other strong oxidants are not adopted for oxidation of the graphene in a preparing process of the method. The method brings no loss to physical and chemical properties of the graphene and does not produce waste polluting the environment.
Description
Technical field
The invention belongs to the technical field of Graphite Powder 99, be specially a kind of preparation method of Graphene water-based stable dispersions.
Background technology
Graphene, it is that carbon atom is with sp
2the two-dimensional atomic crystal of monoatomic thickness that hydridization connects, by one deck intensive, the carbon atom be wrapped in honeycomb crystal lattice forms, and is two-dimensional material the thinnest in the world, its thickness is only 0.35nm.This special construction has contained the abundant and physical phenomenon of novelty, makes Graphene show many excellent properties.(specific surface area of single-layer graphene can reach 2630m to superhigh specific surface area in theory
2/ g), electrology characteristic free from worldly cares and electron transport ability, uncertain curved characteristic and impenetrability, (intensity of Graphene is the highest in test material to mechanical property, reach 130GPa, more than 100 times of steel), thermomechanical property, specific conductivity all differ from traditional material, be a kind of type material and become rapidly the up-and-coming youngster of Material Field, producing far-reaching influence in many scientific domains.
The same with other nano materials many as carbon nanotube, due to the Van der Waals force between graphene layer, single-layer graphene can be reunited again for graphite, therefore Graphene reunion is a thorny problem of application process.At present, solved the problem of Graphene reunion by chemical process and thermal expansion-reduction method, at graphene film surface adsorption some other molecules and polymkeric substance, utilize self repulsion to reach the effect of dispersion.
The patent delivered, such as: the patent No. is " a kind of method of modifying of graphene oxide " proposition water reducer modified graphene oxide of CN201510261567, although demonstrate water reducer have modifying function to graphene oxide, but surface of graphene oxide contains the hydrophilic functional groups such as great amount of hydroxy group (-OH), carboxyl (-COOH), epoxy group(ing) (-O-), the dispersion of accelerating oxidation Graphene.The patent No. to be " a kind of preparation method of high concentration graphene dispersion liquid " of CN104692374A and the patent No. be CN104495826A " single-layer graphene dispersion liquid and preparation method thereof " is all oxidized Graphene with strong oxidizers such as concentrated acids, destroy the original structure of Graphene, its physical and chemical performance is made to have certain loss, and in preparation process, produce a large amount of waste liquid, extremely unfriendly to environment.The present invention is " a kind of preparation method of Graphene water-based stable dispersions ", because graphenic surface is only containing hydrophilic functional groups such as minute quantity hydroxyl (-OH), carboxyl (-COOH), epoxy group(ing) (-O-), dispersion difficulty is larger, but dispersing technology is simple, process period is short, and time stability is high, for commercialization Graphene, have more application prospect, also more economically.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Graphene water-based stable dispersions, to solve the employing concentrated acid that exists in prior art and other strong oxidizers carry out pre-treatment to Graphene, cause and the physical and chemical performance of Graphene is caused damage, produce the problem of waste environment being had to any pollution.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for Graphene water-based stable dispersions, step is as follows:
(1) be added to the water by dispersion agent, magnetic agitation 2-3min is until be uniformly dispersed, and wherein, the mass volume ratio of dispersion agent and water is 0.5-5:10-100g/mL;
(2) Graphene is joined in the dispersion liquid prepared, wherein, the mass volume ratio of the water in Graphene and step (1) is 0.1:10-100g/mL, then magnetic agitation 2-3min, ultrasonic disperse 1-10h, obtains the stable Graphene aqueous liquid dispersion of polymolecularity.
In described step (1), before dispersion agent is added to the water, be first added to the water by polycarboxylate water-reducer, magnetic agitation 1-2min, wherein, the mass volume ratio of polycarboxylate water-reducer and water is 0.1-1:10-100g/mL; Carry out the step adding dispersion agent subsequently again.
Described polycarboxylate water-reducer is German western card polycarboxylate water-reducer, and solid content is 40%.
Described dispersion agent is one or more in γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl triethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, γ-divinyl triammonium base oxypropyl trimethyl silane, 3-aminopropyl ortho-siliformic acid, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane.
Described Graphene is multi-layer graphene, and the number of plies is no more than 9 layers, and thickness is no more than 5nm.
Described ultrasonic disperse instrument used is Ultrasonic Cleaners, and power is 20-80KHz.
The concentration of the Graphene aqueous liquid dispersion adopting aforesaid method to prepare is 1 ~ 10mg/L.
The invention has the beneficial effects as follows: method of the present invention does not adopt concentrated acid and other strong oxidizers to carry out pre-treatment to Graphene, Graphene can keep its original atomic structure of carbon, surface can not a large amount of oxygen-containing functional group of grafting, once Graphene is oxidized to graphene oxide, the physical and chemical performance of Graphene will change, the performance utilized is weakened to have some to wish, and method of the present invention utilizes the hydrolysis properties of dispersion agent originally in water, graphenic surface is adsorbed on after dispersion agent hydrolysis, utilize electrostatic repulsion, Graphene is repelled mutually, thus reach the object of dispersion, can not cause damage to the physical and chemical performance of Graphene, Graphene is made to keep the performances such as the photoelectricity of its excellence.And the inventive method such as not to wash at the process, and the dispersion agent also toxicological harmless of use, can not waste resource and not produce waste environment being had to any pollution.Preparation process described in method of the present invention only needs two steps, and instrument is simple, and preparation technology is simple, and easy to operate, Graphene is good dispersity in water, and stability is high.
Accompanying drawing explanation
Fig. 1 is that the Graphene SEM in embodiment 1 before dispersion schemes;
Fig. 2 is that the Graphene TEM in embodiment 1 after dispersion schemes;
Fig. 3 is Graphene and the Graphene XRD figure before disperseing after the dispersion of embodiment 1.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
In following embodiment, polycarboxylate water-reducer is purchased from Germany's west card, and solid content is 40%; The instrument of ultrasonic disperse adopts Ultrasonic Cleaners, and power is 20-80KHz.
Embodiment 1
(1) add in 100mL water by the polycarboxylate water-reducer of 0.1g, magnetic agitation 1-2min, add 0.5g γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 1h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
As can be seen from Figure 1 Graphene is due to the spontaneous reunion of Van der Waals force of self, causes in use disperseing uneven, falls flat.
As can be seen from Figure 2 Graphene presents multi-layer transparent state, illustrates that dispersion effect is obvious.
As Fig. 3, stronger diffraction peak is there is in Graphene about 2 θ=11 °, Graphene after dispersant does not have diffraction peak to occur, in complete amorphous state, this is due to after dispersion agent hydrolysis, be adsorbed on graphenic surface, Graphene is made to reach the object of dispersion by Coulomb repulsion, on the other hand, hydrophilic radical ionization on dispersion agent is adsorbed on graphenic surface, hydrophobic group aligns at interface, under ultrasonic effect, Graphene is being repelled each other, simultaneously, dispersion agent used is high molecular polymer, molecular chain length is longer, further increase Graphene distance between layers, promote the dispersion of Graphene.
Embodiment 2
(1) add in 10mL water by the polycarboxylate water-reducer of 1g, magnetic agitation 1-2min, add 5gN-β-aminoethyl-γ-aminopropyl triethoxysilane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 10h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 3
(1) add in 40mL water by the polycarboxylate water-reducer of 0.25g, magnetic agitation 1-2min, add 1.25g γ-divinyl triammonium base oxypropyl trimethyl silane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 2.5h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 4
(1) add in 50mL water by the polycarboxylate water-reducer of 0.2g, magnetic agitation 1-2min, add 1g3-aminopropyl ortho-siliformic acid, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 2h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 5
(1) add in 80ml water by the polycarboxylate water-reducer of 0.125g, magnetic agitation 1-2min, add 0.625g3-urea propyl trimethoxy silicane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 1.5h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 6
(1) by 0.5g γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane adds in 100mL water, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 1h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 7
(1) by 5g γ-divinyl triammonium base oxypropyl trimethyl silane adds in 10mL water, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 10h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 8
(1) add in 40mL water by 1.25gN-β-aminoethyl-γ-aminopropyl triethoxysilane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 2.5h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 9
(1) add in 50mL water by 1g3-urea propyl-triethoxysilicane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 2h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
Embodiment 10
(1) add in 80mL water by 0.625g3-urea propyl trimethoxy silicane, magnetic agitation 2-3min is until be uniformly dispersed;
(2) 0.1g Graphene is joined in the dispersion liquid prepared, magnetic agitation 2-3min, ultrasonic disperse 1.5h, obtain the stable Graphene aqueous liquid dispersion of polymolecularity.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. a preparation method for Graphene water-based stable dispersions, is characterized in that: step is as follows:
(1) be added to the water by dispersion agent, magnetic agitation 2-3min is until be uniformly dispersed, and wherein, the mass volume ratio of dispersion agent and water is 0.5-5:10-100g/mL;
(2) Graphene is joined in the dispersion liquid prepared, wherein, the mass volume ratio of the water in Graphene and step (1) is 0.1:10-100g/mL, then magnetic agitation 2-3min, ultrasonic disperse 1-10h, obtains the stable Graphene aqueous liquid dispersion of polymolecularity.
2. the preparation method of Graphene water-based stable dispersions according to claim 1, it is characterized in that: in described step (1), before dispersion agent is added to the water, first polycarboxylate water-reducer is added to the water, magnetic agitation 1-2min, wherein, the mass volume ratio of polycarboxylate water-reducer and water is 0.1-1:10-100g/mL; Carry out the step adding dispersion agent subsequently again.
3. the preparation method of Graphene water-based stable dispersions according to claim 2, is characterized in that: described polycarboxylate water-reducer is German western card polycarboxylate water-reducer, and solid content is 40%.
4. the preparation method of Graphene water-based stable dispersions according to claim 1, is characterized in that: described dispersion agent is one or more in γ-divinyl triammonium base hydroxypropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl triethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxy dimethoxysilane, γ-divinyl triammonium base oxypropyl trimethyl silane, 3-aminopropyl ortho-siliformic acid, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane.
5. the preparation method of Graphene water-based stable dispersions according to claim 1, is characterized in that: described Graphene is multi-layer graphene, and the number of plies is no more than 9 layers, and thickness is no more than 5nm.
6. the preparation method of Graphene water-based stable dispersions according to claim 1, is characterized in that: described ultrasonic disperse instrument used is Ultrasonic Cleaners, and power is 20-80KHz.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106744900A (en) * | 2017-01-03 | 2017-05-31 | 江苏华生塑业有限公司 | A kind of preparation method of polymolecularity Graphene |
| CN107803121A (en) * | 2017-11-14 | 2018-03-16 | 湖南中大经纬地热开发科技有限公司 | A kind of nanofiber composite filtering film for water treatment and preparation method thereof |
| CN112591797A (en) * | 2020-12-23 | 2021-04-02 | 陕西科技大学 | High-concentration high-dispersibility ultrathin molybdenum disulfide dispersion liquid and preparation method thereof |
| CN116281985A (en) * | 2023-04-17 | 2023-06-23 | 湖北冶金地质研究所(中南冶金地质研究所) | Method for preparing high-dispersity graphene based on physical modification means |
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| CN103253656A (en) * | 2013-05-02 | 2013-08-21 | 南京科孚纳米技术有限公司 | Preparation method of graphene dispersion liquid |
| CN104772064A (en) * | 2015-03-31 | 2015-07-15 | 山东玉皇新能源科技有限公司 | Method for preparing grapheme dispersion liquid |
| CN104876204A (en) * | 2015-05-21 | 2015-09-02 | 东南大学 | Method for modifying graphene oxide |
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2015
- 2015-12-23 CN CN201510976285.7A patent/CN105540571A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253656A (en) * | 2013-05-02 | 2013-08-21 | 南京科孚纳米技术有限公司 | Preparation method of graphene dispersion liquid |
| CN104772064A (en) * | 2015-03-31 | 2015-07-15 | 山东玉皇新能源科技有限公司 | Method for preparing grapheme dispersion liquid |
| CN104876204A (en) * | 2015-05-21 | 2015-09-02 | 东南大学 | Method for modifying graphene oxide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744900A (en) * | 2017-01-03 | 2017-05-31 | 江苏华生塑业有限公司 | A kind of preparation method of polymolecularity Graphene |
| CN107803121A (en) * | 2017-11-14 | 2018-03-16 | 湖南中大经纬地热开发科技有限公司 | A kind of nanofiber composite filtering film for water treatment and preparation method thereof |
| CN107803121B (en) * | 2017-11-14 | 2019-11-19 | 湖南中大经纬地热开发科技有限公司 | A kind of nanofiber composite filtering film and preparation method thereof for water treatment |
| CN112591797A (en) * | 2020-12-23 | 2021-04-02 | 陕西科技大学 | High-concentration high-dispersibility ultrathin molybdenum disulfide dispersion liquid and preparation method thereof |
| CN116281985A (en) * | 2023-04-17 | 2023-06-23 | 湖北冶金地质研究所(中南冶金地质研究所) | Method for preparing high-dispersity graphene based on physical modification means |
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