CN106006608B - A kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques - Google Patents
A kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques Download PDFInfo
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- CN106006608B CN106006608B CN201610315885.3A CN201610315885A CN106006608B CN 106006608 B CN106006608 B CN 106006608B CN 201610315885 A CN201610315885 A CN 201610315885A CN 106006608 B CN106006608 B CN 106006608B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/06—Graphene nanoribbons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
A kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques, the present invention relates to the use of the method that 3D printing technique prepares fiber, the present invention is to solve existing graphene fiber processing method complex process, the production cycle length technical problem.This method：First, graphene nanobelt is prepared by multi-walled carbon nanotube；2nd, graphene nanobelt is dispersed in high purity deionized water and obtains printing solution, then the printer through 3D liquid printers nozzle printing into the coagulating bath of ethyl acetate, after solidification, take out drying, obtain graphene nanobelt fiber.This method technique is simple, and precision is high, and shape and size will be changed and adjusted, can industrialized production, the tensile strength of prepared graphene nanobelt fiber reaches 90~100MPa, while the fiber has higher flexibility, available for fields such as energy storage device, photovoltaic device, sensors.
Description
Technical field
The method that 3D printing technique prepares fiber is the present invention relates to the use of, belongs to 3D printing preparation field.
Background technology
Graphene nanobelt is defined as width and is less than 10nm graphene, while keeps length-width ratio to be more than 10, and it compares
Graphene possesses more flexible adjustable property and bigger application value.Graphene nanobelt has because of its special single layer structure
High mechanical properties, elasticity, thermal conductivity and outstanding electron mobility rapidly become the popular words of physics, chemistry and materialogy
Topic, has started researcher to its property and the research boom of application.To make full use of the premium properties of graphene, by graphene
It is to have very much actual application value that nanobelt, which is prepared into macroscopic material, and graphene nanobelt is assembled into film and block structure,
It can be applied to ultracapacitor, bury the field of functional materials such as ion battery, energy catalysis.Domestic Zhejiang University's height is superfine at present
Through by modified graphene oxide, graphene oxide fiber is made using wet spinning.Therefore in order to successfully prepare graphene
Nanobelt fiber provides a good reference function.But the processing technology that these methods prepare graphene fiber is complicated, raw
Cycle length is produced, therefore the method for more easily preparing multi-functional graphene nanobelt fiber turns into the focus of research.
The content of the invention
The present invention is to solve existing graphene fiber processing method complex process, the production cycle length technology ask
Topic, and a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques is provided.
The method for preparing graphene nanobelt fiber using 3D solution printing techniques of the present invention, is carried out according to the following steps：
First, multi-walled carbon nanotube is put into the concentrated sulfuric acid and the mixed solution of concentrated phosphoric acid, adds potassium permanganate, be in temperature
Reaction is 1~5 hour under conditions of 55~80 DEG C, after reaction terminates, adds the ice water solution containing hydrogen peroxide and is diluted,
Then make separation of solid and liquid with supercentrifuge, extract solids；Again solids with hydrochloric acid solution, deionized water filter clearly
Neutrality is washed till, is dried in vacuo, obtains graphene nanobelt；
2nd, by graphene nanobelt quality and high purity deionized water volume ratio (5~20) mg：1mL ratio, will
The graphene nanobelt that step 1 obtains is dispersed in high purity deionized water, obtains graphene nanobelt printing solution；By graphite
Alkene nanobelt printing solution is transferred in the printer of 3D liquid printers, by the shape and size of default fiber, will be printed
Solution is printed to through the spout of printer in the coagulating bath of ethyl acetate and after 0.5~1h of holding, taking-up is dried, and in an oven
80~90 DEG C of drying, obtain graphene nanobelt fiber.
Multi-walled carbon nanotube is used potassium permanganate in CNT by the present invention in the concentrated sulfuric acid and the mixed solution of concentrated phosphoric acid
Oxidation stripping is carried out at the defects of surface, obtains graphene nanobelt, then printing solution is made in graphene nanobelt, utilizes 3D
RP technique is printed, by the shape of default graphene nanobelt fiber, 3D liquid printer is carried out laterally and longitudinally
Movement, printing solution is printed to and is molded in the coagulating bath of ethyl acetate, prepare it is different stacking shapes fibers, obtain stone
Black alkene nanobelt fiber.The graphene nanobelt of various concentrations is prepared by adjusting in printing solution graphene nanobelt content
Fiber, so as to obtain diameter difference, the electric conductivity graphene nanobelt fiber different with intensity.This method technique is simple, precision
Height, shape and size will be changed and adjusted, can industrialized production, the tensile strength 90 of prepared graphene nanobelt fiber~
100MPa, while the fiber has higher flexibility, available for fields such as energy storage device, photovoltaic device, sensors.
Brief description of the drawings
Fig. 1 is the 3D printer schematic diagram used in experiment 1；Wherein 1 is underframe, and 2 be guide rail, and 3 be coagulating bath box, 4
To move up and down support, 5 is move left and right support, and 6 be printer, and 7 be shower nozzle；
Fig. 2 is macroscopical digital photo of graphene nanobelt printing solution prepared by 1 step 2 of experiment；
Fig. 3 is macroscopical digital photo of graphene nanobelt fiber prepared by experiment 1；
Fig. 4 is the elongation at break of graphene nanobelt fiber and the graph of relation of tensile strength of experiment 1；
Fig. 5 is the surface scan electron microscope of the graphene nanobelt fiber of preparation prepared by experiment 1；
Fig. 6 is the profile scanning electron microscope of the graphene fiber of preparation prepared by experiment 1；
Fig. 7 is the surface scan electron microscope of the graphene nanobelt fiber of preparation prepared by experiment 2；
Fig. 8 is the surface scan electron microscope of the graphene nanobelt fiber of preparation prepared by experiment 3.
Embodiment
Embodiment one:The side that graphene nanobelt fiber is prepared using 3D solution printing techniques of present embodiment
Method, carry out according to the following steps：
First, multi-walled carbon nanotube is put into the concentrated sulfuric acid and the mixed solution of concentrated phosphoric acid, adds potassium permanganate, be in temperature
Reaction is 1~5 hour under conditions of 55~80 DEG C, after reaction terminates, adds the ice water solution containing hydrogen peroxide and is diluted,
Then make separation of solid and liquid with supercentrifuge, extract solids；Solids is carried out with hydrochloric acid, deionized water again to filter cleaning extremely
Neutrality, vacuum drying, obtains graphene nanobelt；
2nd, by graphene nanobelt quality and high purity deionized water volume ratio (5~20) mg：1mL ratio, will
The graphene nanobelt that step 1 obtains is dispersed in high purity deionized water, obtains graphene nanobelt printing solution；By graphite
Alkene nanobelt printing solution is transferred in the printer of 3D liquid printers, by the shape and size of default fiber, will be printed
Solution is printed to through the spout of printer in the coagulating bath of ethyl acetate and after 0.5~1h of holding, taking-up is dried, and in an oven
80~90 DEG C of drying, obtain graphene nanobelt fiber.
Embodiment two：Present embodiment and the concentrated sulfuric acid in step 1 unlike embodiment one and dense phosphorus
The mixed solution of acid be by the concentrated sulfuric acid that mass percentage concentration is 98% be 85% with mass percentage concentration phosphoric acid by volume
For (9~10)：1 is formulated；It is other identical with embodiment one.
Embodiment three：Present embodiment in the step 1 unlike embodiment one or two more wall carbon receive
The mass ratio of mitron and potassium permanganate is 1:(5~6).It is other identical with embodiment one or two.
Embodiment four：Peroxide in step 1 unlike one of present embodiment and embodiment one to three
The mass percentage concentration for changing hydrogen is 0.1~10%.It is other identical with one of embodiment one to three.
Embodiment five：Hydrochloric acid in step 1 unlike one of present embodiment and embodiment one to four
The mass percentage concentration concentration of solution is 1~15%.It is other identical with one of embodiment one to four.
Embodiment six：Disperse in step 2 unlike one of present embodiment and embodiment one to five
Method be ultrasonic disperse, the time of ultrasonic disperse is 5h~8h；It is other identical with one of embodiment one to five.
Embodiment seven：Disperse in step 2 unlike one of present embodiment and embodiment one to five
Method be magnetic agitation, the time of magnetic agitation is 24~48h；It is other identical with one of embodiment one to five.
Embodiment eight：Printed in step 2 unlike one of present embodiment and embodiment one to seven
The print speed of solution is 5~10mL/h；It is other identical with one of embodiment one to seven.
With following verification experimental verification beneficial effects of the present invention：
Experiment 1：The method for preparing graphene nanobelt fiber using 3D solution printing techniques of this experiment, according to the following steps
Carry out：
The first, 2g multi-walled carbon nanotubes are put into the concentrated sulfuric acid and 50mL matter for filling that 150mL mass percent concentrations are 98%
In the there-necked flask for measuring the mixed solution for the concentrated phosphoric acid that percent concentration is 85%, it is stirred 1 hour, there-necked flask is placed in ice bath
In, 10g potassium permanganate is slowly added to, it is less than 10 DEG C that temperature in there-necked flask is kept during potassium manganate is increased, in room temperature
Lower stirring 1 hour, reaction is 1 hour under conditions of being then heated to 70 DEG C in a water bath, after reaction terminates, by there-necked flask
Interior material pours into the deionized water of 1L mixture of ice and water and adds the permanganic acid that 5mL hydrogen peroxide does not consume to react
Potassium, then make separation of solid and liquid with supercentrifuge, extract solids；It is again 10t% with mass percentage concentration concentration by solids
Hydrochloric acid cleans 3 times, then it is neutral, the vacuum under 60 DEG C of temperature conditionss to carry out filtering cleaning to the pH value of filtrate with deionized water
Dry, obtain graphene nanobelt；
2nd, the graphene nanobelt that 200mg step 1 obtains is placed in 100mL beaker, add 20mL it is high-purity go from
Sub- water is made into the dispersion liquid that concentration is 10mg/mL, and beaker is put into ultrasonic pond and handles 5h, and it is molten to obtain graphene nanobelt printing
Liquid；Graphene nanobelt printing solution is transferred in the printer 6 of 3D liquid printers, the bore of shower nozzle 7 is 1mm, with printing
Speed is 10mL/h speed, by printing solution after shower nozzle 7 prints in the coagulating bath box 3 of ethyl acetate and keeps 0.5h,
Taking-up is dried, and 90 DEG C of drying in an oven, obtains graphene nanobelt fiber.
The schematic diagrames of the 3D liquid printers of this experiment as shown in figure 1,
The photo of the graphene nanobelt printing solution obtained in this test procedure two is as shown in Fig. 2 be homogeneous black
Solution.
The photomacrograph for the graphene nanobelt fiber that this experiment obtains is as shown in figure 3, the graphene nanobelt fiber chi
Very little uniformity, fiber softening.
Fig. 4 is the elongation at break of graphene nanobelt fiber and the relation curve of tensile strength that this experiment obtains, from
The tensile strength that Fig. 4 can be seen that the graphene nanobelt fiber of this experiment preparation is 95MPa.
The stereoscan photograph for the graphene nanobelt fiber that this experiment obtains is as shown in figure 5, the ESEM in section shines
Piece as shown in fig. 6, from fig. 5, it can be seen that the graphene nanobelt fiber printed under the concentration of this experiment it is a diameter of 110 micro-
The cylinder of rice, any surface finish of fiber, impulse- free robustness, from fig. 6, it can be seen that section is close, no cavity.
Experiment 2：The method for preparing graphene nanobelt fiber using 3D solution printing techniques of this experiment, according to the following steps
Carry out：
First, the preparation of graphene nanobelt is identical with the step of experiment 1 one.
2nd, the graphene nanobelt that 300mg step 1 obtains is placed in 100mL beaker, add 20mL it is high-purity go from
Sub- water is made into the dispersion liquid that concentration is 15mg/mL, and beaker is put into ultrasonic pond and handles 5h, and it is molten to obtain graphene nanobelt printing
Liquid；Graphene nanobelt spinning solution is transferred in the printer of 3D liquid printers, shower nozzle bore is 1mm, to print speed
The speed for 10mL/h is spent, after printing solution is printed in the coagulating bath of ethyl acetate and keep 0.5h, taking-up is dried, and
90 DEG C of drying, obtain graphene nanobelt fiber in baking oven.
The stereoscan photograph for the graphene nanobelt fiber that this experiment obtains was as shown in fig. 7, from figure 7 it can be seen that should
A diameter of 150 microns of cylinder of the graphene nanobelt fiber printed under concentration, any surface finish of fiber, impulse- free robustness.
Its tensile strength is 93MPa.
Experiment 3：The method for preparing graphene nanobelt fiber using 3D solution printing techniques of this experiment, according to the following steps
Carry out：
First, the preparation of graphene nanobelt is identical with the step of experiment 1 one.
2nd, the graphene nanobelt that 400mg step 1 obtains is placed in 100mL beaker, add 20mL it is high-purity go from
Sub- water is made into the dispersion liquid that concentration is 20mg/mL, and beaker is put into ultrasonic pond and handles 5h, and it is molten to obtain graphene nanobelt printing
Liquid；Graphene nanobelt spinning solution is transferred in the printer of 3D liquid printers, shower nozzle bore is 1mm, to print speed
The speed for 10mL/h is spent, after printing solution is printed in the coagulating bath of ethyl acetate and keep 0.5h, taking-up is dried, and
90 DEG C of drying, obtain graphene nanobelt fiber in baking oven,.
The stereoscan photograph for the graphene nanobelt fiber that this experiment obtains is as shown in figure 8, this is dense as can be seen from Figure 8
A diameter of 200 microns of cylinder of the graphene nanobelt fiber printed under degree, any surface finish of fiber, impulse- free robustness, tightly
It is close, no cavity.Its tensile strength is 96MPa.
Claims (7)
- A kind of 1. method for preparing graphene nanobelt fiber using 3D solution printing techniques, it is characterised in that this method is by following Step is carried out：First, multi-walled carbon nanotube is put into the concentrated sulfuric acid and the mixed solution of concentrated phosphoric acid, add potassium permanganate, temperature be 55~ Reaction is 1~5 hour under conditions of 80 DEG C, after reaction terminates, adds the ice water solution containing hydrogen peroxide and is diluted, then Make separation of solid and liquid with supercentrifuge, extract solids；Solids filter cleaning into hydrochloric acid, deionized water again Property, vacuum drying obtains graphene nanobelt；The mixed solution of the wherein concentrated sulfuric acid and concentrated phosphoric acid is to be by mass percentage concentration The phosphoric acid that 98% concentrated sulfuric acid is 85% with mass percentage concentration is (9~10) by volume：1 is formulated；2nd, by graphene nanobelt quality and high purity deionized water volume ratio (5~20) mg：1mL ratio, by step One obtained graphene nanobelt is dispersed in high purity deionized water, obtains graphene nanobelt printing solution；Graphene is received Rice is transferred to printing solution in the printer of 3D liquid printers, by the shape and size of default fiber, by printing solution Through the nozzle printing of printer into the coagulating bath of ethyl acetate and after keeping 0.5~1h, taking-up is dried, and in an oven 80~ 90 DEG C of drying, obtain graphene nanobelt fiber.
- 2. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its It is characterised by step 1 that the mass ratio of multi-walled carbon nanotube and potassium permanganate is 1:(5~6).
- 3. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its The mass percentage concentration for being characterised by hydrogen peroxide in step 1 is 0.1~10%.
- 4. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its The mass percentage concentration concentration for being characterised by hydrochloric acid solution in step 1 is 1~15%.
- 5. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its The method for being characterised by disperseing in step 2 is ultrasonic disperse, and the time of ultrasonic disperse is 5h~8h.
- 6. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its The method for being characterised by disperseing in step 2 is magnetic agitation, and the time of magnetic agitation is 24~48h.
- 7. a kind of method for preparing graphene nanobelt fiber using 3D solution printing techniques according to claim 1, its The print speed for being characterised by printing solution in step 2 is 5~10mL/h.
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| CN110823421A (en) * | 2019-11-18 | 2020-02-21 | 西南石油大学 | Method for preparing flexible piezoresistive shear force sensor by utilizing 3D printing |
| CN113388905B (en) * | 2021-06-15 | 2022-07-05 | 广西大学 | Self-crimping preparation method and application of hollow graphene fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036970A (en) * | 2014-05-29 | 2014-09-10 | 浙江大学 | Preparation method for flexible graphite fibre-based asymmetric super capacitor |
| CN105544017A (en) * | 2016-01-27 | 2016-05-04 | 浙江大学 | High-conductivity graphene fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036970A (en) * | 2014-05-29 | 2014-09-10 | 浙江大学 | Preparation method for flexible graphite fibre-based asymmetric super capacitor |
| CN105544017A (en) * | 2016-01-27 | 2016-05-04 | 浙江大学 | High-conductivity graphene fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Precise unzipping of flattened carbon nanotubes to regular grapheme nanoribbons by acid cutting along the folded edges;Yan-Ru Kang et al.;《Journal of Materials Chemistry》;20120622;第22卷;第16284页第2.2节 * |
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