CN104445162A - Graphene oxide aqueous solution and graphene oxide thin film as well as preparation method of graphene oxide thin film - Google Patents
Graphene oxide aqueous solution and graphene oxide thin film as well as preparation method of graphene oxide thin film Download PDFInfo
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Abstract
The invention discloses a method for preparing graphene oxide aqueous solution and a method for preparing a graphene oxide thin film and the graphene thin film. The method comprises the steps of preparing graphene oxide hydrosol by using a Hummers process; calculating the mass of hydrosol; adding water and acid or alkali to prepare the graphene oxide aqueous solution with controlled concentration and pH value; preparing the graphene oxide thin film by using the graphene oxide aqueous solution in a gas-liquid interface self-assembly method; performing HI reduction on the graphene oxide thin film to prepare the graphene thin film. According to the method provided by the invention, the graphene oxide aqueous solution with high stability and controlled property can be prepared, the complete graphene oxide thin film with high light transmission, high mechanical property and large area can be prepared in a controlled form, and the graphene thin film with high conductivity and high mechanical property can be prepared in a controlled form.
Description
Technical field
The present invention relates to grapheme material technical field, be specifically related to a kind ofly prepare the method for graphene oxide water solution and a kind of method preparing graphene oxide film and graphene film.
Background technology
Day by day exhausted along with fossil oil, the environmental consciousness of people strengthens day by day, more urgent to the demand of the renewable environmentally friendly energy, and the solar cell with characteristics such as efficient, convenient, safety, environmental protection is subject to the favor of people day by day.Along with the propelling of thin film technique, all kinds of solar film battery is just becoming the focus of scientific research.Graphene relies on the electroconductibility of its excellence and physical strength, almost completely transparent and possess the advantages such as Hall effect, becomes star's material of solar film battery.
Grapheme material poorly water-soluble, is unfavorable for assembling film forming.Therefore, people often adopt graphene oxide water solution first to assemble graphene oxide film, then are reduced by graphene oxide film, can obtain graphene film.Prepare in the actual production process of graphene oxide film at employing liquid-gas interface self-assembly method, adopt the aqueous solution of graphene oxide powder preparation, time usually owing to boiling falls short of and can not form big area, continuous print, complete graphene oxide film, when big area, continuous print, complete graphene oxide film can be formed, there is again graphene oxide film blocked up, the problem that transparence is low.
As can be seen here, in order to obtain the graphene film that good conductivity, transparence are high, can be used for solar film battery field, and a kind of preparation method of big area, continuous, complete graphene oxide film and graphene film and compound method of its graphene oxide water solution adopted of being formed is provided, seem particularly important.
Summary of the invention
Of the present inventionly be that providing a kind of forms the preparation method of big area, continuous, complete graphene oxide film and graphene film and the compound method of its graphene oxide water solution adopted.
In order to reach above object, the compound method of graphene oxide water solution provided by the invention is: the first step, adopts hummers legal system for graphene oxide; Second step, centrifuge washing is 3-7 to the pH value of graphene oxide supernatant, collects the lower floor's graphene oxide after centrifuge washing, obtains graphene oxide precipitation; 3rd step, puts into container, according to graphene oxide by graphene oxide precipitation: the volume ratio of water is that the ratio of (1:1) ~ (1:1.5) adds water, stir evenly, centrifugal, removing bottom sediment thing, obtains good stability, the graphene oxide water-sol that concentration is large; 4th step, extracts the graphene oxide water-sol of certain volume, dries, calculates the mass concentration of the graphene oxide water-sol; 5th step, adds water, stirs evenly in the graphene oxide water-sol, is diluted to the concentration of needs, then adds acid or alkali, regulates the pH value of graphene oxide water solution, namely obtains the graphene oxide water solution that character is controlled.When second step centrifuge washing, the rotating speed of whizzer is preferably 3000-4000rpm, and when the 3rd step is centrifugal, the rotating speed of whizzer is preferably 500-1000rpm.Described acid is preferably HCl, H
2sO
4, described alkali is preferably KOH, NaOH.
The preparation method of graphene oxide film provided by the invention is: the above-mentioned graphene oxide water solution prepared is put into an open container, described open container is put into water-bath, adopts liquid-gas interface self-assembly method to form one deck graphene oxide film in solution surface.Further, adopt PET to be picked up by the graphene oxide film of described solution surface, dry.The concentration of the described graphene oxide water solution prepared is 0.2-2g/L, is preferably 0.5g/L-1g/L.The pH value of the described graphene oxide water solution prepared is 2-12, is preferably 3-7.The time that described liquid-gas interface self-assembly method prepares graphene oxide film is 1-300min, is preferably 2-60min.
The preparation method of graphene film provided by the invention is, by the above-mentioned graphene oxide film prepared, reduces in the HI that submerges, i.e. obtained graphene film.The mass percent of described HI is 45%-60%.
The graphene oxide water solution that the present invention obtains is light yellow or brown color, the graphene oxide water solution obtained relative to graphene oxide powder preparation of light color, and adopt the graphene oxide water solution pH value for preparing of the present invention and concentration controlled, stability is high, and static two days still without Precipitation.The graphene oxide film transparency that the present invention obtains is high, and area is large, continuous, complete, mechanicalness strong, and the graphene film transparency that the present invention obtains is high, and area is large, continuous, complete, good conductivity, mechanicalness are strong.
Accompanying drawing illustrates:
Fig. 1 is production scheme of the present invention.
Specific embodiment:
Below the specific embodiment of the present invention is described in detail.
Embodiment 1:
Adopt Hummers legal system for graphene oxide: to claim 8g Graphite Powder 99 and 5g NaNO
3be placed in dry beaker, be placed in ice-water bath, add the vitriol oil of 200mL, open whipping appts.Claim 32g KMnO
4slowly add in above-mentioned mixed solution, control temperature of reaction lower than 10 DEG C, reaction 1h.Then after reacting 1h at being transferred to 35 DEG C, more slowly add 300mL water, water-bath temperature is set simultaneously and is 98 DEG C and controls temperature of reaction in beaker, lower than 100 DEG C, to keep 98 DEG C of isothermal reaction 3h.Reaction product is transferred to 1000mL large beaker, adds the dilution of 600mL water and stir evenly, pour 40mL H subsequently into
2o
2(30%) stir evenly, while hot suction filtration, then use the HCl of 5%, water washing graphene oxide respectively.
Preparation graphene oxide water solution: above-mentioned graphene oxide is put into centrifuge tube, and add water centrifuge washing, centrifugal rotational speed controls at 4000rpm, until centrifuged supernatant pH value is 5.Then remove supernatant, take out the lower floor's graphene oxide after centrifuge washing, obtain graphene oxide precipitation.According to graphene oxide: the volume ratio of water is that 1:1 adds water in graphene oxide, stirs evenly.Recentrifuge, centrifugal rotational speed is 500rpm, removing bottom sediment thing, obtains good stability, the graphene oxide water-sol that concentration is large.Extract the graphene oxide water-sol of certain volume, dry, the mass concentration calculating the graphene oxide water-sol is 4mg/mL.In the graphene oxide water-sol, add the mass concentration that water is diluted to graphene oxide is 1mg/mL.In the graphene oxide water solution of 1mg/mL, add KOH, also can be NaOH, adjust ph to 7, namely obtains that pH value is 7, mass concentration is the graphene oxide water solution of 1mg/mL.
Prepare graphene oxide film: be 7 by above-mentioned pH value, mass concentration is the beaker that the graphene oxide water solution of 1mg/mL puts into 100mL, then described beaker is put into the water-bath of 80 DEG C, water bath time 2min.Graphene oxide water solution surface in beaker forms the graphene oxide film of the very thin yellow of one deck, by PET film, described graphene oxide film is pulled out, namely the graphene oxide film that obtained transparence is high, the transparence of described graphene oxide film is up to 96%.
Prepare graphene film: the massfraction that submerged by above-mentioned graphene oxide film is in the HI aqueous solution of 55%, takes out, namely obtains transparence high, the graphene film of good conductivity after 1min.The transparence of described graphene film is 94%, and square resistance is 6K Ω/sq.
Embodiment 2
The preparation of graphene oxide water solution: as embodiment 1 adopts Hummers legal system for graphene oxide.Then above-mentioned filter cake is put into centrifuge tube, add water centrifuge washing, centrifugal rotational speed controls at 3000rpm, until centrifuged supernatant pH value is 4.Then remove supernatant, take out the lower floor's graphene oxide after centrifuge washing, according to graphene oxide: the volume ratio of water is that 1:1.5 adds water, stirs evenly.Recentrifuge, centrifugal rotational speed is 1000rpm, removing bottom sediment thing, obtains good stability, the graphene oxide water-sol that concentration is large.Extract the graphene oxide water-sol of certain volume, dry, the mass concentration calculating the graphene oxide water-sol is 2.8mg/mL.In the graphene oxide water-sol, add the mass concentration that water is diluted to graphene oxide is 0.5mg/mL.In the graphene oxide water solution of 0.5mg/mL, add HCl, also can be H
2sO
4, adjust ph to 3, namely obtains that pH value is 3, mass concentration is the graphene oxide water solution of 0.5mg/mL.
Prepare graphene oxide film: be 3 by above-mentioned pH value, mass concentration is the beaker that the graphene oxide water solution of 0.5mg/mL puts into 100mL, then described beaker is put into the water-bath of 90 DEG C, water bath time 6min.Graphene oxide water solution surface in beaker forms the graphene oxide film of the very thin yellow of one deck, by PET film, described graphene oxide film is pulled out, namely the graphene oxide film that obtained transparence is high, the transparence of described graphene oxide film is up to 93.2%.
Prepare graphene film: the massfraction that submerged by above-mentioned graphene oxide film is in the HI aqueous solution of 55%, takes out, namely obtains transparence high, the graphene film of good conductivity after 1min.The transparence of described graphene film is 85%, and square resistance is 3.6K Ω/sq.
Embodiment 3
The preparation of the graphene oxide water solution of different pH value: as embodiment 1 prepares the graphene oxide water solution that graphene oxide mass concentration is 1mg/mL, adopt HCl or KOH adjust ph to be 2,3,5,7,9,11,12, the mass concentration that namely obtained pH value is different is the graphene oxide water solution of 1mg/mL.
The preparation of the graphene oxide film of different pH value: the beaker above-mentioned graphene oxide water solution being put into 100mL, then puts into the water-bath of 80 DEG C, water bath time 60min by described beaker.Graphene oxide water solution surface in beaker forms the graphene oxide film of the very thin yellow of one deck, by PET film, described graphene oxide film is pulled out, namely the graphene oxide film that obtained transparence is high, described graphene oxide film as shown in table 1 in the transparence at 650nm place.
The different pH value of table 1 obtains the transparence of graphene oxide film
| PH value | 2 | 3 | 5 | 7 | 9 | 11 | 12 |
| Transparence (%) | 58.2 | 60.1 | 55.5 | 47.3 | 29.8 | 25.6 | 22.7 |
The preparation of the graphene film of different pH value: the massfraction that submerged by above-mentioned graphene oxide film is in the HI aqueous solution of 55%, takes out after 10min, namely obtain having metalluster, the graphene film of good conductivity.The square resistance of described graphene film is as shown in table 2.
The square resistance of the graphene film of the different pH value of table 2
| PH value | 2 | 3 | 5 | 7 | 9 | 11 | 12 |
| Square resistance (Ω/sq) | 29.3 | 26.6 | 28.4 | 56.7 | 122 | 194 | 300 |
Embodiment 4:
The preparation of graphene oxide water solution: as embodiment 1 adopts Hummers legal system for graphene oxide.Then above-mentioned filter cake is put into centrifuge tube, add water centrifuge washing, centrifugal rotational speed controls at 4000rpm, until centrifuged supernatant pH value is 3.Then remove supernatant, take out the lower floor's graphene oxide after centrifuge washing, according to graphene oxide: the volume ratio of water is that 1:1.5 adds water, stirs evenly.Recentrifuge, centrifugal rotational speed is 500rpm, removing bottom sediment thing, obtains good stability, the graphene oxide water-sol that concentration is large.Extract the graphene oxide water-sol of certain volume, dry, the mass concentration calculating the graphene oxide water-sol is 3.6mg/mL.In the graphene oxide water-sol, add the mass concentration that water is diluted to graphene oxide is 2mg/mL.In the graphene oxide water solution of 2mg/mL, add HCl, adjust ph to 3, namely obtain that pH value is 3, mass concentration is the graphene oxide water solution of 2mg/mL.
Prepare graphene oxide film: be 3 by above-mentioned pH value, mass concentration is the beaker that the graphene oxide water solution of 2mg/mL puts into 100mL, then described beaker is put into the water-bath of 70 DEG C, water bath time 300min.Graphene oxide water solution surface in beaker forms the graphene oxide film of one deck yellow, by PET film, described graphene oxide film is pulled out, the i.e. graphene oxide film of obtained good mechanical property, the mechanical strength value of described graphene oxide film is in table 3.
Prepare graphene film: the massfraction that submerged by above-mentioned graphene oxide film is in the HI aqueous solution of 47%, takes out after 300min, namely obtain that physical strength is high, the graphene film of good conductivity.Described Graphene square resistance is 30.4 Ω/sq, and the mechanical strength value of described graphene film is in table 3.
The physical strength of table 3 graphene oxide and graphene film
Adopt method provided by the invention, the graphene oxide water solution that good stability, concentration and pH value are controlled can be obtained, controllably can prepare the graphene oxide film that light transmission is good, mechanicalness is strong, large-area, complete, controllably can prepare the graphene film that light transmission is good, electroconductibility is excellent, mechanicalness is strong, large-area, complete.
Claims (10)
1. a compound method for graphene oxide water solution, comprises the following steps:
The first step, adopts hummers legal system for graphene oxide;
Second step, centrifuge washing is 3-7 to the pH value of graphene oxide supernatant, collects the lower floor's graphene oxide after centrifuge washing, obtains graphene oxide precipitation;
3rd step, puts into container, according to graphene oxide by graphene oxide precipitation: the volume ratio of water is that the ratio of (1:1) ~ (1:1.5) adds water, stir evenly, centrifugal, removing bottom sediment thing, obtains good stability, the graphene oxide water-sol that concentration is large;
4th step, extracts the graphene oxide water-sol of certain volume, dries, calculates the mass concentration of the graphene oxide water-sol;
5th step, adds water, stirs evenly in the graphene oxide water-sol, is diluted to the concentration of needs, then adds acid or alkali, regulates the pH value of graphene oxide water solution, namely obtains the graphene oxide water solution that character is controlled.
2. the compound method of graphene oxide water solution according to claim 1, is characterized in that: when described second step centrifuge washing, the rotating speed of whizzer is 3000-4000rpm, and when described 3rd step is centrifugal, the rotating speed of whizzer is 500-1000rpm.
3. the compound method of graphene oxide water solution according to claim 1, is characterized in that: described acid is HCl or H
2sO
4, described alkali is KOH or NaOH.
4. a preparation method for graphene oxide film, comprises the following steps:
Adopt the compound method preparation graphene oxide water solution of graphene oxide water solution according to claim 1;
The graphene oxide water solution prepared is put into an open container, described open container is put into water-bath, adopt liquid-gas interface self-assembly method to form one deck graphene oxide film in solution surface.
5. the preparation method of graphene oxide film according to claim 4, is characterized in that: also comprise and adopt PET to be picked up by the graphene oxide film of described solution surface, dry.
6. the preparation method of graphene oxide film according to claim 4, is characterized in that: described in the concentration of graphene oxide water solution for preparing be 0.2-2g/L.
7. the preparation method of graphene oxide film according to claim 4, is characterized in that: described in the pH value of graphene oxide water solution for preparing be 2-12.
8. the preparation method of graphene oxide film according to claim 4, is characterized in that: the time that described liquid-gas interface self-assembly method prepares graphene oxide film is 1-300min.
9. a preparation method for graphene film, comprises the following steps:
The preparation method of graphene oxide film according to claim 4 is adopted to prepare graphene oxide film;
Described graphene oxide film is submerged in HI and reduce, be i.e. obtained graphene film.
10. the preparation method of graphene film according to claim 9, is characterized in that: the mass percent of described HI is 45%-60%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554007A (en) * | 2015-09-16 | 2017-04-05 | 中国科学院金属研究所 | A kind of method of microwave reduction graphene oxide film |
| CN113184838A (en) * | 2021-05-19 | 2021-07-30 | 重庆交通大学 | Preparation method of functionalized graphene material |
| CN113816367A (en) * | 2021-10-13 | 2021-12-21 | 北京化工大学 | Graphene oxide film and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
| CN101734654A (en) * | 2009-12-23 | 2010-06-16 | 天津大学 | Transparent graphene oxide film and method for regulating transmittance |
| CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
| CN103723709A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of aqueous single-layer graphene solution |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN104003380A (en) * | 2014-06-09 | 2014-08-27 | 黑龙江奥星能源科技有限公司 | Preparation method of ultra-thin graphite paper and graphene oxide composited film |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
-
2014
- 2014-11-12 CN CN201410636894.3A patent/CN104445162A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559944A (en) * | 2009-05-27 | 2009-10-21 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
| CN101734654A (en) * | 2009-12-23 | 2010-06-16 | 天津大学 | Transparent graphene oxide film and method for regulating transmittance |
| CN102887508A (en) * | 2012-09-28 | 2013-01-23 | 上海理工大学 | Method for preparing high-strength graphite oxide aerogel |
| CN103723709A (en) * | 2013-11-22 | 2014-04-16 | 盐城纳新天地新材料科技有限公司 | Preparation method of aqueous single-layer graphene solution |
| CN103787317A (en) * | 2014-01-02 | 2014-05-14 | 上海应用技术学院 | Preparation method of graphene oxide dispersion liquid |
| CN104030275A (en) * | 2014-05-30 | 2014-09-10 | 上海应用技术学院 | Preparation method of reduction graphene oxide heat-conducting film |
| CN104003380A (en) * | 2014-06-09 | 2014-08-27 | 黑龙江奥星能源科技有限公司 | Preparation method of ultra-thin graphite paper and graphene oxide composited film |
Non-Patent Citations (1)
| Title |
|---|
| CHENGMENG CHEN ET AL.: "Self-assembled Free–Standing Graphite Oxide membrane", 《ADVANCED MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554007A (en) * | 2015-09-16 | 2017-04-05 | 中国科学院金属研究所 | A kind of method of microwave reduction graphene oxide film |
| CN113184838A (en) * | 2021-05-19 | 2021-07-30 | 重庆交通大学 | Preparation method of functionalized graphene material |
| CN113816367A (en) * | 2021-10-13 | 2021-12-21 | 北京化工大学 | Graphene oxide film and preparation method thereof |
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