CN109295796A - A kind of graphene oxide fibrous paper and preparation method thereof from fusion - Google Patents
A kind of graphene oxide fibrous paper and preparation method thereof from fusion Download PDFInfo
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- CN109295796A CN109295796A CN201811109163.8A CN201811109163A CN109295796A CN 109295796 A CN109295796 A CN 109295796A CN 201811109163 A CN201811109163 A CN 201811109163A CN 109295796 A CN109295796 A CN 109295796A
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- graphene oxide
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
- D21H13/50—Carbon fibres
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Abstract
The invention discloses a kind of graphene oxide fibrous papers and preparation method thereof from fusion, and different from the preparation method of conventional oxidation graphene film, which assembles using graphene oxide staple fiber as primitive by wet process fusion.Structural unit due to constituting membrane material is the one-dimensional graphene oxide fiber of diameter some tens of pm rather than the two dimensional oxidation graphene sheet layer of nanometer grade thickness, it is substantially shorter the molding time of fibrous paper, and obtains the performance close with the graphene oxide membrane of traditional handicraft preparation.Meanwhile by the control of the selection of ingredient and pretreating process to structural unit graphene oxide fiber and fusion degree, it can be achieved that the flexible design of the structure and function to fibrous paper, to expand the application field of this graphene oxide fibrous paper.
Description
Technical field
The present invention relates to graphene fiber and membrane materials, more particularly to one kind to be merged by graphene oxide fiber wet process
Graphene oxide paper and preparation method thereof.
Background technique
Graphene oxide is a kind of two-dimensional material of nanometer grade thickness, can be stably dispersed in aqueous solution isopolarity solution,
Therefore there is preferable film forming and machinability.The preparation of graphene oxide membrane reports (Dikin et by Ruoff et al. earliest
Al.Nature 2007,448:457-460), show preferable flexible and certain mechanical strength.With graphite in recent years
The deep development of alkene research field, graphene oxide/graphene film material are related as a kind of macroscopical assembly of important two dimension
Preparation method, structure optimization and functional application be one of the hot research direction in this field.Researchers have developed
Common graphene oxide membrane preparation means (the Li et al.Chemical such as suction filtration film forming, deposition film forming, spraying, dip-coating is gone out
Reviews 2015,115:7046-7117), however, conventional solution processing method uses the graphene dispersion of relatively low concentration
To obtain the uniform membrane material of property, therefore with the increase of film thickness, the period of film preparation is often up to a couple of days, restricts significantly liquid
The production efficiency of graphene oxide membrane.
It is the one dimension fibre shape macrostructure for assembling primitive that graphene oxide fiber, which is with graphene oxide layer, due to oxygen
The swelling character of graphite alkene fiber can further realize the wet process fusion assembling to fiber, obtain such as graphene fiber
The unique fiber package assembly such as non-woven fabrics (Nature Communications, 2016,13684).Based on this method, lead to
The control to fiber swelling and fusion degree is crossed, fine and close graphene oxide membrane material can be obtained, and greatly shorten oxidation
The preparation process of graphene film.Before merging to obtain the work of film by fiber wet process and it is not found in report.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide it is a kind of by the fusion of graphene oxide fiber wet process and
At graphene oxide membrane material and preparation method thereof.
The invention is realized by the following technical scheme: a kind of graphene oxide fibrous paper from fusion, which is characterized in that tool
There are the fibrous textures formed by graphene oxide staple fiber from fusion, the fusion method is wet process fusion.
A kind of preparation method of the graphene oxide fibrous paper from fusion, comprising the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion.
(2) obtained graphene oxide fiber is placed at room temperature for 12h or more, is subsequently placed in 40-60 DEG C of heating 3h.
(3) step 2 treated graphene oxide fiber immersion is made into its swelling in the solution, and is stirred using high speed shear
It mixes machine and fiber is blended into the staple fiber that length is 1-7mm, form the dispersion liquid of graphene oxide staple fiber.
(4) it is deposited on the graphene oxide fiber in dispersion liquid on filter membrane using vacuum filtration method, with doing for fiber
It is dry it to be made mutually to merge obtain graphene oxide fibrous paper.
Further, spinning solution is the aqueous solution or n,N-Dimethylformamide solution of graphene oxide.It is corresponding, it spins
The coagulating bath that silk process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
Further, the dispersion liquid of graphene oxide staple fiber includes water, ethyl alcohol, n,N-Dimethylformamide in step 3
Etc. the polar solvent that graphene oxide fiber can be made to generate swelling.
Further, the revolving speed of high shear agitation is 3000-8000rpm.
Further, this method further includes that the graphene oxide fibrous paper after drying is restored to obtain graphene fibre
Tie up paper.Restoring method is that reduction or 100- are carried out using chemical reducing agents such as hydroiodic acid, hydrazine hydrate, Vitamin C, sodium borohydrides
3000 DEG C of thermal reductions.
Compared with the prior art, the present invention has the following beneficial effects:
(1) graphene oxide fibrous paper is assembled by graphene oxide fiber fusion, reduces the process of solvent removal,
Therefore the preparation efficiency of graphene oxide membrane is substantially increased.
(2) preparation method is simply controllable, and the fusion degree of fiber, and then realization pair can be controlled by the pretreatment to fiber
The design of structure, density and the mechanical property of graphene oxide fibrous paper etc..
(3) ingredient of graphene oxide fiber and micro-structure directly determine the ingredient and micro-structure of fibrous paper, therefore can be
It realizes during preparing raw material graphene oxide fiber to the functionalized design of product graphene oxide fibrous paper, makes it in function
Energy devices field has broad application prospects.
Detailed description of the invention
Fig. 1 is the microscopic appearance from fusion fibrous paper that graphene oxide fiber obtains after different condition pre-processes,
Pretreatment temperature be respectively 40 DEG C of (a), (b) 60 DEG C, (c) 80 DEG C.
Specific embodiment
Present invention utilizes the hydrophily of graphene oxide and the swelling characters of graphene oxide fiber.Graphene oxide is fine
Dimension can be such that the fibre structure of script Close stack softens after being swollen in polarity good solvent, have certain deformability.When molten
Swollen graphene oxide fiber accumulations together after, can under the booster action of vacuum filtration fast eliminating adsorb solvent, and
Make fibre deformation, be bonded to each other, forms fine and close filter cake, while realizing interface by interactions such as hydrogen bond, Van der Waals forces
Combining closely between graphene oxide layer obtains graphene oxide fiber so that fusion behavior is come from performance after being completely dried
Paper.
Graphene oxide fiber is pre-processed by using different heating temperature, the hydrophily of fiber can be significantly changed
And Swelling Capacity, the fusion degree of graphene oxide fiber is then influenced, realizes the essence to graphene oxide fibrous paper micro-structure
Really control.As shown in Figure 1, the fusion degree of graphene oxide fiber declines, in product fibrous paper with the raising for the treatment of temperature
Porosity increase.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment, all belong to the scope of protection of the present invention.
Embodiment 1:
(1) using concentration for 5mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, ethyl acetate is
Coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h, then 40 DEG C at a temperature of heat 3h.
(3) pretreated graphene oxide fiber is impregnated 10min or more in aqueous solution is swollen it sufficiently, then
Fibre cutting is obtained by the aqueous dispersions of graphene oxide staple fiber (1-7mm) with 3000rpm revolving speed using high-speed shearing machine.
(4) graphene oxide staple fiber dispersion liquid is filtered by vacuum, it is made to be deposited on filter membrane and dry.
By above step, the obtained graphene oxide fibrous paper of fusion certainly is in the oxidation macroscopically obtained with conventional method
Graphene film indifference, mechanical strength about 82MPa, density about 1.1g/cm3.In microstructure, less obvious threadiness is formed
Texture makes fibrous paper have certain structure designability.
Embodiment 2:
(1) using concentration for 5mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, ethyl acetate is
Coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h, then 60 DEG C at a temperature of heat 3h.
(3) pretreated graphene oxide fiber is impregnated 10min or more in aqueous solution is swollen it sufficiently, then
Fibre cutting is obtained by the aqueous dispersions of graphene oxide staple fiber (1-7mm) with 3000rpm revolving speed using high-speed shearing machine.
(4) graphene oxide staple fiber dispersion liquid is filtered by vacuum, it is made to be deposited on filter membrane and dry.
By above step, the obtained graphene oxide fibrous paper of fusion certainly is in the oxidation macroscopically obtained with conventional method
Graphene film indifference, fibrous paper mechanical strength about 55MPa, density about 1.0g/cm3.In microstructure, fusion degree is reduced,
Obvious fibrous textures are formed, are conducive to carry out functionalized design to fibrous paper.
Embodiment 3:
Step 1,3,4 with embodiment 1, and 80 DEG C of pretreatment graphene oxide fibers are used in step 2.
By above step, obtained fusion graphene oxide fibrous paper certainly is in the macroscopically visible non-uniform thickness of naked eyes
Distribution, tensile strength about 10MPa, density about 0.8g/cm3.In microstructure, fusion degree further declines, fibrous web-like knot
Structure is obvious, and porosity rises.
Embodiment 4:
(1) using concentration for 5mg/mL graphene oxide/aqueous solution as spinning solution, calcium chloride/water/alcohol mixeding liquid (matter
Amount is than 20:300:100) it is that coagulating bath carries out continuous wet spinning.
(2) obtained graphene oxide fiber is being placed at room temperature for 12h, then 40 DEG C at a temperature of heat 3h.
(3) pretreated graphene oxide fiber is immersed in 15min or more in ethanol solution keeps it sufficiently molten
It is swollen, then high-speed shearing machine is used, by fibre cutting, to obtain the second of graphene oxide staple fiber (1-7mm) with 5000rpm revolving speed
Alcohol dispersion liquid.
(4) graphene oxide staple fiber dispersion liquid is filtered by vacuum, it is made to be deposited on filter membrane and dry.
By above step, what is obtained merges graphene oxide fibrous paper mechanical strength about 63MPa, density about 1.0g/ certainly
cm3.In microstructure, fibrous textures are formed.
Embodiment 5:
(1) using concentration for 8mg/mL graphene oxide/n,N-Dimethylformamide solution as spinning solution, wherein being added
The multi-walled carbon nanotube of 5wt% mass fraction, ethyl acetate are that coagulating bath carries out continuous wet spinning.
Step 2-4 uses hydrazine hydrate with embodiment 1, and to the graphene oxide after drying/carbon nano tube composite fibre paper
Carry out further electronation.
By above step, obtained fusion graphene/carbon nano-tube composite fibre paper mechanical strength about 78MPa certainly is close
Spend about 1.3g/cm3, conductivity about 303S/m.In microstructure, fibrous textures are formed.
Claims (6)
1. a kind of graphene oxide fibrous paper from fusion, which is characterized in that have by graphene oxide staple fiber from fusion and
The fibrous textures of formation, the fusion method are wet process fusion.
2. a kind of preparation method of the graphene oxide fibrous paper from fusion, which comprises the following steps:
(1) continuous wet spinning is carried out by spinning solution of graphene oxide dispersion.
(2) obtained graphene oxide fiber is placed at room temperature for 12h or more, is subsequently placed in 40-60 DEG C of heating 3h.
(3) step 2 treated graphene oxide fiber immersion is made into its swelling in the solution, and uses high shear homomixer
Fiber is blended into the staple fiber that length is 1-7mm, forms the dispersion liquid of graphene oxide staple fiber.
(4) it is deposited on the graphene oxide fiber in dispersion liquid on filter membrane using vacuum filtration method, as the drying of fiber is
It can be made mutually to merge and obtain graphene oxide fibrous paper.
3. according to the method described in claim 2, it is characterized in that, spinning solution is the aqueous solution or N of graphene oxide, N- diformazan
Base formamide solution.Corresponding, the coagulating bath that spinning process uses is calcium chloride/water/alcohol mixeding liquid or ethyl acetate.
4. according to the method described in claim 2, it is characterized in that, in step 3, the dispersion liquid of graphene oxide staple fiber includes
Water, ethyl alcohol, n,N-Dimethylformamide etc. can make graphene oxide fiber generate the polar solvent being swollen.
5. according to the method described in claim 2, it is characterized in that, the revolving speed of high shear agitation is 3000-8000rpm.
6. according to the method described in claim 2, it is characterized in that, this method further includes the graphene oxide fiber after drying
Paper is restored to obtain graphene fiber paper.Restoring method is to be changed using hydroiodic acid, hydrazine hydrate, Vitamin C, sodium borohydride etc.
It learns reducing agent and carries out reduction or 100-3000 DEG C of thermal reduction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647158A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Macroscopic quantity preparation method of graphene-based micron rod |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192201A (en) * | 2016-07-18 | 2016-12-07 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN106948165A (en) * | 2017-04-28 | 2017-07-14 | 浙江大学 | A kind of graphene fiber of fusion certainly and preparation method thereof |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
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2018
- 2018-09-21 CN CN201811109163.8A patent/CN109295796A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106192201A (en) * | 2016-07-18 | 2016-12-07 | 浙江大学 | A kind of graphene fiber non-woven fabrics and preparation method thereof |
| CN106948165A (en) * | 2017-04-28 | 2017-07-14 | 浙江大学 | A kind of graphene fiber of fusion certainly and preparation method thereof |
| CN107032343A (en) * | 2017-05-24 | 2017-08-11 | 北京服装学院 | The preparation method of wet spinning graphene oxide solution and graphene fiber |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112647158A (en) * | 2019-10-10 | 2021-04-13 | 中国科学技术大学 | Macroscopic quantity preparation method of graphene-based micron rod |
| CN112647158B (en) * | 2019-10-10 | 2023-08-29 | 中国科学技术大学 | Macroscopic quantity preparation method of graphene-based micro rod |
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