CN104129779A - Preparation method of graphene-containing nano paper - Google Patents
Preparation method of graphene-containing nano paper Download PDFInfo
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- CN104129779A CN104129779A CN201410298555.9A CN201410298555A CN104129779A CN 104129779 A CN104129779 A CN 104129779A CN 201410298555 A CN201410298555 A CN 201410298555A CN 104129779 A CN104129779 A CN 104129779A
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Abstract
The invention relates to a preparation method of graphene-containing nano paper, and the preparation method is specifically as follows: A. preparing a graphene oxide dispersion liquid; B. adding a stabilizer into the graphene oxide dispersion liquid, then adding a reductant for reduction of graphene oxide for preparation of a stable aqueous graphene dispersion liquid; C. preparing carbon nanotubes; D. separating the carbon nanotubes to obtain a metallic carbon nanotube dispersion liquid, then adding an oxidant for partial oxidation of the metallic carbon nanotubes; E. using a microfiltration membrane for filtration of the graphene dispersion liquid to obtain a graphene film; and filtering the partially oxidized metallic carbon nanotube dispersion liquid to obtain a graphene film deposited with the carbon nanotubes; F. repeating the above step E to obtain multilayer-alternately deposited graphene-carbon nanotube films deposited on the microfiltration membrane; and G. carbonizing the multilayer films deposited on the microfiltration membrane to obtain the graphene-containing nano paper.
Description
Technical field
The present invention relates to a kind of method of preparing rice paper, be specifically related to a kind of method of the nanometer paper of preparing graphene-containing.
Background technology
Nano-carbon material, comprises two-dimentional Graphene (GS) or graphene oxide (GO), and the carbon nanotube (CNTs) of one dimension all belongs to the new lover of Tan Xi family.Their discovery has all produced far-reaching influence to whole scientific circles, and wherein Graphene obtained Nobel Prize in physics in 2010.These nano-carbon materials are outstanding significant advantage at aspects such as mechanics, optics, electronics.As carbon nanotube has 1-dimention nano hollow structure, high length-diameter ratio, very good mechanical properties and conductivity; Graphene is that thickness only has single or several atoms, and size but can reach several even two-dimensional nano films of tens microns, good conductivity, and physical strength is high; These carbon nanomaterials are synthesizing the matrix material of high mechanical strength and high conductivity, are having many potential using values as aspects such as storage hydrogen and energy storage material, sensor and catalytic materials.
Carbon paper is very extensive in the application of field of batteries, but, these materials are prepared based on macroscopic material, its performance is limited, be difficult to meet more and more harsher demand, and the conductivity excellence of Graphene especially receives publicity in the application in the fields such as battery, if Graphene is prepared into carbon paper for fields such as batteries, be conducive to undoubtedly improve its performance.
Summary of the invention
The present invention overcomes the deficiency that prior art exists, and a kind of preparation method of the nanometer paper that contains Graphene is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A. prepare the dispersion liquid of graphene oxide;
B. in the dispersion liquid of above-mentioned graphene oxide, add stablizer, then add reductive agent redox graphene, prepare stable watersoluble plumbago alkene dispersion liquid;
C. prepare carbon nanotube;
D. separating carbon nano-tube obtains the dispersion liquid of metallic carbon nanotubes, then, adds this metallic carbon nanotubes of oxygenant partial oxidation;
E. obtain graphene film by micro-filtrate membrane filtration graphene dispersing solution; Then the dispersion liquid of the metallic carbon nanotubes of filtration fraction oxidation, obtains depositing it on the graphene film by carbon nanotube;
F. repeat above-mentioned steps E, obtain being deposited on the graphene-carbon nano tube film of the multilayer alternating deposit in microfiltration membrane;
G. the above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
Further, in the application, stablizer can be alkali, or tensio-active agent.
Further, described alkali is ammoniacal liquor, sodium hydroxide, or potassium hydroxide.Preferably ammoniacal liquor.
Further, described tensio-active agent is alkyl quaternary ammonium salts or sodium polystyrene sulfonate.
Further, described separating carbon nano-tube comprises that the mode of use gel absorption separates.
Further, described oxygenant is nitric acid or potassium permanganate or hydrogen peroxide.
The application has utilized the dimensional properties of low dimension carbon nanomaterial, with and the character of high conduction, be prepared into the nanometer paper that contains Graphene, Graphene is sprawled in the plane, and carbon nano tube surface is through partial oxidation, contain the oxy radicals such as hydroxyl, the oxy radical on itself and Graphene surface forms a large amount of hydrogen bonds in dry carbonization process or dehydration forms oxo bridge, promote the combination of carbon nanotube and Graphene, again by the process of alternating deposit, the effect that makes carbon nanotube serve as fiber, has played the effect that this nanometer paper toughness that contains Graphene is improved.
Embodiment
Below in conjunction with specific examples, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Use improved Kazakhstan Moss method to prepare graphene oxide, obtain the dispersion liquid of graphene oxide, wherein add 25% ammoniacal liquor, add-on is that every g graphene oxide is approximately 5-25g, then adds stoichiometric hydrazine hydrate, ultrasonic reduction.
Any means is prepared carbon nanotube, be distributed in deionized water, ratio is 1g carbon nanotube 20ml deionized water, ultrasonic dispersion, this dispersion liquid, by being filled with the separator column of sepharose, after separating for several times, is selected to filtrate, add the oxygenant nitric acid (mass concentration is 30%) of the every g carbon nanotube of 0.05g, ultrasonic.
Select high molecule microfilter membrane, approximately 0.2 micron, aperture, diameter 5mm, makes graphene dispersing solution filter deposition on microfiltration membrane surface, and then deposited gold attribute carbon nano tube dispersion liquid, makes it be deposited on the surface of graphene film.
Repeat above-mentioned deposition step, obtain the film of plane SH wave, thickness 200nm, it is pointed out that thickness is to select as required.
The above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
Embodiment 2
Use improved Kazakhstan Moss method to prepare graphene oxide, obtain the dispersion liquid of graphene oxide, wherein add 25% sodium hydroxide, add-on is that every g graphene oxide is approximately 5-20g sodium hydroxide solution, then adds stoichiometric hydrazine hydrate, ultrasonic reduction.
Any means is prepared carbon nanotube, be distributed in deionized water, ratio is 1g carbon nanotube 20ml deionized water, ultrasonic dispersion, this dispersion liquid, by being filled with the separator column of sepharose, after separating for several times, is selected to filtrate, add the oxidant potassium permanganate (solution that mass concentration is 10%) of the every g carbon nanotube of 0.05g, ultrasonic.
Select high molecule microfilter membrane, approximately 0.2 micron, aperture, diameter 5mm, makes graphene dispersing solution filter deposition on microfiltration membrane surface, and then deposited gold attribute carbon nano tube dispersion liquid, makes it be deposited on the surface of graphene film.
Repeat above-mentioned deposition step, obtain the film of plane SH wave, thickness 250nm.
The above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
Embodiment 3
Use improved Kazakhstan Moss method to prepare graphene oxide, obtain the dispersion liquid of graphene oxide, wherein add 25% potassium hydroxide, add-on is that every g graphene oxide is approximately 5-20g potassium hydroxide solution, then add stoichiometric sodium borohydride, ultrasonic reduction.
Any means is prepared carbon nanotube, be distributed in deionized water, ratio is 1g carbon nanotube 20ml deionized water, ultrasonic dispersion, this dispersion liquid, by being filled with the separator column of sepharose, after separating for several times, is selected to filtrate, add the oxidant potassium permanganate (solution that mass concentration is 10%) of the every g carbon nanotube of 0.05g, ultrasonic.
Select high molecule microfilter membrane, approximately 0.2 micron, aperture, diameter 5mm, makes graphene dispersing solution filter deposition on microfiltration membrane surface, and then deposited gold attribute carbon nano tube dispersion liquid, makes it be deposited on the surface of graphene film.
Repeat above-mentioned deposition step, obtain the film of plane SH wave, thickness 220nm.
The above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
Embodiment 4
Use improved Kazakhstan Moss method to prepare graphene oxide, obtain the dispersion liquid of graphene oxide, wherein add sodium polystyrene sulfonate (dredging molecular weight is 60000), add-on is that every g graphene oxide is approximately 9-15g, then add stoichiometric sodium borohydride, ultrasonic reduction.
Any means is prepared carbon nanotube, be distributed in deionized water, ratio is 1g carbon nanotube 20ml deionized water, ultrasonic dispersion, this dispersion liquid, by being filled with the separator column of sepharose, after separating for several times, is selected to filtrate, add the oxidant potassium permanganate (solution that mass concentration is 10%) of the every g carbon nanotube of 0.05g, ultrasonic.
Select high molecule microfilter membrane, approximately 0.2 micron, aperture, diameter 5mm, makes graphene dispersing solution filter deposition on microfiltration membrane surface, and then deposited gold attribute carbon nano tube dispersion liquid, makes it be deposited on the surface of graphene film.
Repeat above-mentioned deposition step, obtain the film of plane SH wave, thickness 200nm.
The above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a method of preparing the nanometer paper of graphene-containing, is characterized in that, concrete steps are:
A. prepare the dispersion liquid of graphene oxide;
B. in the dispersion liquid of above-mentioned graphene oxide, add stablizer, then add reductive agent redox graphene, prepare stable watersoluble plumbago alkene dispersion liquid;
C. prepare carbon nanotube;
D. separating carbon nano-tube obtains the dispersion liquid of metallic carbon nanotubes, then, adds this metallic carbon nanotubes of oxygenant partial oxidation;
E. obtain graphene film by micro-filtrate membrane filtration graphene dispersing solution; Then the dispersion liquid of the metallic carbon nanotubes of filtration fraction oxidation, obtains depositing it on the graphene film by carbon nanotube;
F. repeat above-mentioned steps E, obtain being deposited on the graphene-carbon nano tube film of the multilayer alternating deposit in microfiltration membrane;
G. the above-mentioned multilayer film being deposited in microfiltration membrane of carbonization, obtains the nanometer paper that contains Graphene.
2. the method for a kind of nanometer paper of preparing graphene-containing according to claim 1, is characterized in that, described stablizer can be alkali, or tensio-active agent.
3. the method for a kind of nanometer paper of preparing graphene-containing according to claim 2, is characterized in that, described alkali is ammoniacal liquor, sodium hydroxide, or potassium hydroxide.
4. the method for a kind of nanometer paper of preparing graphene-containing according to claim 2, is characterized in that, described alkali is ammoniacal liquor.
5. the method for a kind of nanometer paper of preparing graphene-containing according to claim 2, is characterized in that, described tensio-active agent is alkyl quaternary ammonium salts or sodium polystyrene sulfonate.
6. the method for a kind of nanometer paper of preparing graphene-containing according to claim 1, is characterized in that, described separating carbon nano-tube comprises that the mode of use gel absorption separates.
7. the method for a kind of nanometer paper of preparing graphene-containing according to claim 1, is characterized in that, described oxygenant is nitric acid or potassium permanganate or hydrogen peroxide.
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Cited By (8)
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| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN107024510A (en) * | 2017-05-22 | 2017-08-08 | 清华大学 | A kind of graphene test paper and its preparation and the liquid analysis method based on the test paper |
| CN107262078A (en) * | 2017-08-16 | 2017-10-20 | 刘胜 | A kind of graphene/silicon glue SPE material and its application |
| CN108559188A (en) * | 2018-05-10 | 2018-09-21 | 南通市第人民医院 | Base material for gestational diabetes mellitus blood sugar test paper |
| CN109132194A (en) * | 2018-08-31 | 2019-01-04 | 平湖市景兴包装材料有限公司 | A kind of package paper and preparation method thereof with sterilizing fresh-keeping function |
| CN110602934A (en) * | 2019-08-13 | 2019-12-20 | 深圳烯湾科技有限公司 | Electromagnetic shielding heat dissipation film and preparation method and application thereof |
| CN111732743A (en) * | 2020-06-10 | 2020-10-02 | 新材料与产业技术北京研究院 | Preparation method of carbon nanotube/graphene flexible film |
| CN112609469A (en) * | 2020-12-17 | 2021-04-06 | 广东金发科技有限公司 | Graphene melt-blown non-woven fabric and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106396680A (en) * | 2016-09-07 | 2017-02-15 | 南昌大学 | Preparation method of flexible ultrathin carbon nanotube paper |
| CN107024510A (en) * | 2017-05-22 | 2017-08-08 | 清华大学 | A kind of graphene test paper and its preparation and the liquid analysis method based on the test paper |
| CN107262078A (en) * | 2017-08-16 | 2017-10-20 | 刘胜 | A kind of graphene/silicon glue SPE material and its application |
| CN107262078B (en) * | 2017-08-16 | 2020-03-31 | 淄博海关综合技术服务中心 | Graphene/silica gel solid phase extraction material and application thereof |
| CN108559188A (en) * | 2018-05-10 | 2018-09-21 | 南通市第人民医院 | Base material for gestational diabetes mellitus blood sugar test paper |
| CN108559188B (en) * | 2018-05-10 | 2020-08-07 | 南通市第一人民医院 | Substrate for blood sugar test paper for gestational diabetes |
| CN109132194A (en) * | 2018-08-31 | 2019-01-04 | 平湖市景兴包装材料有限公司 | A kind of package paper and preparation method thereof with sterilizing fresh-keeping function |
| CN109132194B (en) * | 2018-08-31 | 2020-02-14 | 平湖市景兴包装材料有限公司 | Packaging paper with antibacterial and fresh-keeping functions and preparation method thereof |
| CN110602934A (en) * | 2019-08-13 | 2019-12-20 | 深圳烯湾科技有限公司 | Electromagnetic shielding heat dissipation film and preparation method and application thereof |
| CN111732743A (en) * | 2020-06-10 | 2020-10-02 | 新材料与产业技术北京研究院 | Preparation method of carbon nanotube/graphene flexible film |
| CN112609469A (en) * | 2020-12-17 | 2021-04-06 | 广东金发科技有限公司 | Graphene melt-blown non-woven fabric and preparation method thereof |
| CN112609469B (en) * | 2020-12-17 | 2022-06-07 | 广东金发科技有限公司 | Graphene melt-blown non-woven fabric and preparation method thereof |
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Application publication date: 20141105 |