CN101948108B - Preparation method of oxidized graphite paper - Google Patents
Preparation method of oxidized graphite paper Download PDFInfo
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- CN101948108B CN101948108B CN2010102991087A CN201010299108A CN101948108B CN 101948108 B CN101948108 B CN 101948108B CN 2010102991087 A CN2010102991087 A CN 2010102991087A CN 201010299108 A CN201010299108 A CN 201010299108A CN 101948108 B CN101948108 B CN 101948108B
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Abstract
The invention relates to an optimized preparation method of oxidized graphite paper, belonging to the technical field of nanomaterials. The preparation method comprises the following steps: preparing graphene oxide by adopting hydrogen peroxide; then, adding a glutaric dialdehyde solution into the suspension of the graphene oxide; and casting and drying on a substrate after stirring to obtain the oxidized graphite paper with enhanced mechanical properties. The method of the invention is simple and easy, is suitable for large-scale preparation, and can realize large-scale preparation of the oxidized graphite paper. By adding a small amount of cross-linking agent, the obtained oxidized graphite paper with enhanced mechanical properties has regular structure, uniform height and enough mechanical strength.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is a kind of optimization preparation method of graphite oxide paper.
Background technology
Graphene is as closely arranging the two-dimentional atomic crystal material that constitutes by the monolayer carbon atom, because its unique quantum effect and excellent electricity, calorifics and mechanical property; At the nanometer electronic device and the unicircuit in future, flexible electronic device, novel electron devices such as ultra-high sensitive senser element; Matrix material; Solar cell, super capacitor, aspects such as hydrogen storage material are with a wide range of applications.In graphene preparation method, chemical dispersion method prepares Graphene, with respect to physical method, because it has the productive rate height, and the simple and lower-cost advantage of preparation method, therefore, this method has become a hot topic of Graphene preparation.
Adopt chemical process with the flaky graphite oxidation; The graphite oxide that obtains can be in water and organic solvent homodisperse; Further can prepare graphite oxide paper,, nf membrane, ultracapacitor, bury aspects such as battery and be with a wide range of applications at matrix material.People such as Rodney S Ruoff write articles the 448th volume 457～460 pages of the 26th phases on Nature, the graphite oxide paper that utilizes the method for filtration under diminished pressure to obtain having considerable intensity.In order further to improve the intensity of graphite oxide paper, people such as Rodney S Ruoff write articles 572～578 pages of the 2nd the 3rd phases of volume on ACS Nano, adopt divalent-metal ion to realize the mechanics of graphite oxide paper is strengthened.
Yet the graphite oxide paper that the method for employing filtration under diminished pressure obtains is not suitable for suitability for industrialized production, is necessary to seek simple method, realizes the mass preparation of graphite oxide paper.Although people such as Titelman GI the 43rd volume on Carbon is write articles for 641～649 pages, the graphene oxide dispersion liquid can become the graphite oxide film by dried coating film, and the preparation that complete big area self-supporting has the graphite oxide paper of considerable intensity does not simultaneously appear in the newspapers.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of optimization preparation method of graphite oxide paper is provided; Adopt special base material,, can realize the mass preparation of graphite oxide paper graphite oxide dispersion liquid casting film-forming; Through adding a spot of linking agent, can realize that the mechanics of graphite oxide paper strengthens.This method is simple, is suitable for mass preparation, and can design the graphite oxide paper of different thickness, size and dimension as required, and resulting mechanics enhanced graphite oxide paper has compound with regular structure, highly even and enough physical strength.
The present invention realizes through following technical scheme; After the present invention adopts ydrogen peroxide 50 to prepare graphene oxide; Add glutaraldehyde solution in the suspension-s with graphene oxide, curtain coating is dry in substrate after stirring, and obtains mechanical property enhanced graphite oxide paper.
Described graphene oxide prepares in the following manner: after frozen water and graphite suspension are carried out the quencher reaction; Slowly add aqueous hydrogen peroxide solution and obtain glassy yellow graphene oxide suspension-s; Carry out pickling and drying successively through after filtering the tawny filter cake, obtain the graphene oxide solid.
The mass percent concentration of described ydrogen peroxide 50 is 30%;
Described pickling and drying are meant: adopting mass percent is that 3% Hydrogen chloride repetitive scrubbing is to the no SO of filtrating
4 2-Exist, and then be washed till the no Cl of filtrating with deionized water
-Exist, 40 ℃ of vacuum-drying 24h in vacuum drying oven obtain the graphene oxide solid then.
Described graphite suspension prepares in the following manner: at room temperature graphite is joined in the vitriol oil; After stirring, add SODIUMNITRATE, carry out processing under cooling after fully stirring 1h; Add potassium permanganate then in batches; Be heated to 35 ± 3 ℃ with water-bath at last, fully react and add mixture of ice and water quencher reaction behind the 2h, obtain the brown graphite suspension.
Described graphite is natural flaky graphite of 200～500 purposes or expanded graphite;
The described vitriol oil is that mass percent concentration is 98% the vitriol oil;
Described processing under cooling is treated to and places ice bath or cryosel bath to be cooled to 0 ℃ or following reaction vessel;
The described potassium permanganate that in batches adds is meant that the potassium permanganate amount of each adding is 2g～3g, and the timed interval that at every turn adds potassium permanganate is 20min, so that the temperature of reaction system remains on below 15 ℃.
The suspension-s of described graphene oxide is meant: graphene oxide is scattered in the water, and its concentration is 0.1mg/ml～5mg/ml.
Described substrate is tetrafluoroethylene, polycarbonate, Vilaterm, Vestolen PP 7052, polyimide, steel plate, PET, polyaryletherketone, SE, pvdf, urethane, POLYACTIC ACID, PS, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, ZGK 5, Mierocrystalline cellulose, rubber, PVK, mica, epoxy resin, resol, maleic resin or fluoro-resin;
Described curtain coating drying is meant: in temperature is 20 ℃～80 ℃ baking oven, and dry 6h～24h film forming.
The mass percentage concentration of described glutaraldehyde solution is 2%～100%.
The quality percentage composition of described LUTARALDEHYDE is 0.1%～5%;
The described reaction times is 10min～2h.
Compared with prior art, the invention has the advantages that and adopt special substrate, realize the mass preparation of graphite oxide paper adopting glutaraldehyde as cross linker simultaneously, realize that the mechanics of graphite oxide paper strengthens through the method for casting film-forming.
Description of drawings
Fig. 1 is the inventive method synoptic diagram.
Fig. 2 is the graphite oxide synoptic diagram;
Wherein: Fig. 2 a is the graphite oxide atomic force micrograph, and Fig. 2 b is graphite oxide altitude distribution figure, and Fig. 2 c is the electron scanning micrograph of graphite oxide.
Fig. 3 is the sem photograph of graphite oxide paper xsect.
Fig. 4 is the stress-strain curve diagram of graphite oxide paper.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
As shown in Figure 1, the large-scale producing method of the described graphite oxide paper of present embodiment may further comprise the steps:
The first step, at room temperature joins the natural flaky graphite of 10g 500 purposes in the 1000mL flask, mechanical stirring evenly after, add 5g SODIUMNITRATE; Continue to stir 1h, ice bath is cooled to 0 ℃, then; In 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not to be higher than 15 ℃, remove ice bath; With heating in water bath temperature of reaction system is risen to 35 ± 3 ℃, fully stirring reaction is 2 hours, obtains the brown graphite suspension.
Second step, the frozen water of 500mL is added quencher reaction in the flask, slowly add mass percent concentration subsequently and be 30% aqueous hydrogen peroxide solution 35mL, obtain glassy yellow graphene oxide suspension-s.
The 3rd the step, with the graphite oxide suspension filtered, obtain the tawny filter cake.Using mass percentage concentration is that 3% dilute hydrochloric acid solution washing is until the no SO of filtrating
4 2-Exist, and then be washed till the no Cl of filtrating with deionized water
-Exist, resulting filter cake places 40 ℃ of vacuum-drying 24h of vacuum drying oven, obtains the graphene oxide solid.
The 4th goes on foot, graphene oxide is scattered in the water, forms the dispersion liquid of 0.5mg/ml, prolongs film forming at tetrafluoroethylene substrate upper reaches, behind 60 ℃ of heat treated 24h, peels off and can obtain graphite oxide paper.
As shown in Figure 1, the mechanics Enhancement Method of the described graphite oxide paper of present embodiment may further comprise the steps:
The first step, at room temperature joins the natural flaky graphite of 10g 500 purposes in the 1000mL flask, mechanical stirring evenly after, add 5g SODIUMNITRATE; Continue to stir 1h, ice bath is cooled to 0 ℃, then; In 5h, add 30g potassium permanganate in batches, keep temperature of reaction system not to be higher than 15 ℃, remove ice bath; With heating in water bath temperature of reaction system is risen to 35 ± 3 ℃, fully stirring reaction is 2 hours, obtains the brown graphite suspension.
Second step, the frozen water of 500mL is added quencher reaction in the flask, slowly add mass percent concentration subsequently and be 30% aqueous hydrogen peroxide solution 35mL, obtain glassy yellow graphene oxide suspension-s.
The 3rd the step, with the graphite oxide suspension filtered, obtain the tawny filter cake.Using mass percentage concentration is that 3% dilute hydrochloric acid solution washing is until the no SO of filtrating
4 2-Exist, and then be washed till the no Cl of filtrating with deionized water
-Exist, resulting filter cake places 40 ℃ of vacuum-drying 24h of vacuum drying oven, obtains the graphene oxide solid.
The 4th goes on foot, graphene oxide is scattered in the water; Form the dispersion liquid of 0.5mg/ml, adding quality percentage composition is 0.1% LUTARALDEHYDE, stirring reaction 1h; Prolong film forming at tetrafluoroethylene substrate upper reaches; Behind 60 ℃ of heat treated 24h, peel off and can obtain mechanical property enhanced graphite oxide paper, its mechanical property has improved 20%.
Step in the process that adds potassium permanganate, is reduced to cooling temperature-10 ℃ as implementing 1, and the mean sizes of resulting flake graphite alkene has increased by 50%.
Step such as embodiment 1, graphene oxide is scattered in the water, and the concentration that forms dispersion liquid becomes 5mg/ml by 0.5mg/ml, the mechanical properties decrease 20% of resulting graphite oxide paper.
Step such as embodiment 2 bring up to 1% with the quality percentage composition of LUTARALDEHYDE from 0.1%, and the mechanical property of resulting graphite oxide paper has improved 40%.
In the preparation process of graphene oxide, through adopting the method for potassium permanganate/vitriol oil intercalation oxidation, obtain can be in organic solvent individual layer dispersive graphene oxide sheet, help in reduction process, further obtaining dispersive Graphene in organic solvent.Utilize AFM and sem, the pattern of graphene oxide is characterized.The AFM picture of graphene oxide shows that mono-layer graphite oxide alkene is smooth and level and smooth, shown in the thickness chart 2b, is about 0.8～1.2nm shown in Fig. 2 a.The ESEM picture shows that graphene oxide is of a size of micron level shown in Fig. 2 c.
In the preparation process of graphite oxide paper,, come the thickness of controlled oxidation graphite paper through the concentration and the volume of controlled oxidation graphite suspension.Through the quality percentage composition and the reaction times of control LUTARALDEHYDE, come the mechanical strength of controlled oxidation graphite paper.
Claims (8)
1. the preparation method of a graphite oxide paper; It is characterized in that, after the employing ydrogen peroxide 50 prepares graphene oxide, add glutaraldehyde solution in the suspension-s with graphene oxide; Curtain coating is dry in substrate after stirring, and obtains mechanical property enhanced graphite oxide paper;
Graphene oxide prepares in the following manner: after frozen water and graphite suspension are carried out the quencher reaction; Slowly add aqueous hydrogen peroxide solution and obtain glassy yellow graphene oxide suspension-s; Carry out pickling and drying successively through after filtering the tawny filter cake, obtain the graphene oxide solid.
2. the preparation method of graphite oxide paper according to claim 1 is characterized in that, the mass percent concentration of described ydrogen peroxide 50 is 30%.
3. the preparation method of graphite oxide paper according to claim 1 is characterized in that, described pickling and drying are meant: adopting mass percent is that 3% Hydrogen chloride repetitive scrubbing is to the no SO of filtrating
4 2-Exist, and then be washed till the no Cl of filtrating with deionized water
-Exist, 40 ℃ of vacuum-drying 24h in vacuum drying oven obtain the graphene oxide solid then.
4. the preparation method of graphite oxide paper according to claim 1 is characterized in that, described graphite suspension prepares in the following manner: at room temperature graphite is joined in the vitriol oil; After stirring, add SODIUMNITRATE, carry out processing under cooling after fully stirring 1h; Add potassium permanganate then in batches; Be heated to 35 ± 3 ℃ with water-bath at last, fully react and add mixture of ice and water quencher reaction behind the 2h, obtain the brown graphite suspension.
5. the preparation method of graphite oxide paper according to claim 4; It is characterized in that; The described potassium permanganate that in batches adds is meant that the potassium permanganate amount of each adding is 2g～3g, and the timed interval that at every turn adds potassium permanganate is 20min, so that the temperature of reaction system remains on below 15 ℃.
6. the preparation method of graphite oxide paper according to claim 1 is characterized in that, the suspension-s of described graphene oxide is meant: graphene oxide is scattered in the water, and its concentration is 0.1mg/ml～5mg/ml.
7. the preparation method of graphite oxide paper according to claim 1; It is characterized in that described substrate is tetrafluoroethylene, polycarbonate, Vilaterm, Vestolen PP 7052, polyimide, steel plate, PET, polyaryletherketone, SE, pvdf, urethane, POLYACTIC ACID, PS, ABS resin, polyacrylonitrile, poly (arylene ether nitrile), polyethersulfone, ZGK 5, Mierocrystalline cellulose, rubber, PVK, mica, epoxy resin, resol, maleic resin or fluoro-resin.
8. the preparation method of graphite oxide paper according to claim 1 is characterized in that, the mass percentage concentration of described glutaraldehyde solution is 2%～100%.
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| GB201204170D0 (en) * | 2012-03-09 | 2012-04-25 | Bio Nano Consulting | Cross-linked graphene networks |
| GB201215766D0 (en) * | 2012-09-04 | 2012-10-17 | True 2 Materials | A novek method to create graphite oxide, graphene oxide and graphene freestanding sheets |
| CN103660484A (en) * | 2012-09-25 | 2014-03-26 | 绿晶能源股份有限公司 | Flexible graphite paper, and manufacturing method and thickening structure thereof |
| CN103779081A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene/graphene oxide thin film and preparation method thereof, and usage |
| CN103803533A (en) * | 2012-11-15 | 2014-05-21 | 福建省辉锐材料科技有限公司 | Preparation method of graphene |
| CN103265012B (en) * | 2013-04-26 | 2015-01-28 | 华中科技大学 | Methods for preparing large-area graphene film and large-area graphene composite films |
| CN103496690B (en) * | 2013-09-13 | 2015-12-23 | 山东聊城鲁西化工集团有限责任公司 | A kind of preparation method of graphene oxide |
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| CN104030280A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Preparation method of graphene paper |
| CN104163420B (en) * | 2014-07-25 | 2016-08-24 | 中国科学院深圳先进技术研究院 | Ag doping Graphene extrusion coating paper and preparation method thereof |
| CN104591162B (en) * | 2014-12-19 | 2017-01-11 | 东华大学 | Preparation method of multi-response graphene/graphite oxide film |
| CN104743549B (en) * | 2015-03-18 | 2017-01-11 | 浙江大学 | Non-layered cross-linked graphene oxide film as well as preparation method and application thereof |
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| CN107381551B (en) * | 2016-08-18 | 2020-09-04 | 成都中医药大学 | Manganese-embedded graphene and preparation method and application thereof |
| CN108625218A (en) * | 2017-03-17 | 2018-10-09 | 山东圣泉新材料股份有限公司 | A kind of graphene combined mica paper and preparation method thereof |
| CN107754786B (en) * | 2017-10-16 | 2020-06-16 | 广西大学 | By using KMnO4Method for improving electrocatalytic oxidation on direct oxidized graphite paper |
| CN108821263B (en) * | 2018-07-10 | 2020-02-07 | 杭州高烯科技有限公司 | High-strength graphene film and preparation method thereof |
| CN108966376B (en) * | 2018-07-10 | 2020-06-16 | 浙江大学 | Collapsible electric heat membrane device based on graphite alkene |
| CN110406213B (en) * | 2019-07-18 | 2021-07-27 | 柯林(福建)服饰有限公司 | Method for manufacturing antistatic, antibacterial, far infrared, moisture-absorbing and quick-drying down fabric |
| CN114059384B (en) * | 2020-08-01 | 2023-11-28 | 杭州特种纸业有限公司 | Nanometer air filter paper and preparation method thereof |
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| GB0516154D0 (en) * | 2005-08-05 | 2005-09-14 | Ntnu Technology Transfer As | Carbon membranes |
| US8182917B2 (en) * | 2008-03-20 | 2012-05-22 | The United States Of America, As Represented By The Secretary Of The Navy | Reduced graphene oxide film |
| CN101474898A (en) * | 2009-01-16 | 2009-07-08 | 南开大学 | Conductive carbon film based on graphene as well as preparation method and application |
| CN101559944B (en) * | 2009-05-27 | 2011-05-11 | 天津大学 | Conductive graphene film and self-assembly preparation method thereof |
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