CN106947119A - The composite of large-area graphene - Google Patents
The composite of large-area graphene Download PDFInfo
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- CN106947119A CN106947119A CN201710061806.5A CN201710061806A CN106947119A CN 106947119 A CN106947119 A CN 106947119A CN 201710061806 A CN201710061806 A CN 201710061806A CN 106947119 A CN106947119 A CN 106947119A
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- Prior art keywords
- graphene
- composite
- area graphene
- area
- matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention discloses a kind of composite of large-area graphene, including：One matrix；One graphene layer, including a plurality of large-area graphenes for being scattered in the matrix, the number of plies of the large-area graphene are less than 20 layers and with diameters of the La between 1 μm to 1000 μm, and the La is by a value obtained by Raman spectrum.The graphene content needed for the composite is compound in effective reduction by the selection large-area graphene, and then reduces the composite material defect Probability.
Description
Technical field
The present invention relates to a kind of composite, the composite that espespecially a kind of utilization large-area graphene is blended.
Background technology
Graphene is a kind of flat film for being made up of hexangle type honeycomb lattice with SP2 hybridized orbits carbon atom, is mesh
Most thin on former world is also most hard Nanometer material.Because the resistivity of graphene is low, and it is almost transparent, it is expected to use
In developing thinner, the conductive faster electronic component of speed to apply in the fields such as semiconductor, panel or battery.
Even if there is many expectations, also competitively input graphene is studied and is actively laid out, but graphite at this stage for international big factory
Alkene technology also fails to be widely applied, obvious to also have many technical problems to exist at present：Either graphene in itself or
Improved on formula, have more preferably effect when being applied to composite to make graphene.
The content of the invention
In order to reach above-mentioned purpose, an aspect of the invention provides a kind of composite of large-area graphene, including：One
Matrix；One large-area graphene, is scattered in the matrix, the number of plies of the large-area graphene be less than 20 layers and with a La between
Diameter between 1 μm to 1000 μm, the La is by a value obtained by Raman spectrum.
The present invention simultaneously provides a kind of preparation method of the composite of large-area graphene, and it has area big by compound
And the graphene of more perfect graphene planes, to be obviously improved the physico-chemical property of the composite.The large-area graphene
The preparation method of composite include：A high-graphitized graphite flake is provided to be dispersed to a solvent to form a solution；Profit
The high-graphitized graphite flake is set to be separated into a large area graphite in the solution with a dispersant or a ultrasonic vibrating method
The number of plies of alkene, the wherein large-area graphene is less than 20 layers and with diameters of the La between 1 μm to 1000 μm, and the La is
One value obtained by Raman spectrum；And mix the solution with a matrix to form a composite.
Graphene composite material in known techniques be by graphene with multilayer mode storehouse, but due between graphene layer only
Weak bond power with Fan get Wa Li (van der Waals'forces), thus graphene with multilayer mode storehouse when, actually instead
And easily cause the graphene layer in the composite to turn into defect, and the composite in the present invention passes through from above-mentioned by height
The large-area graphene prepared by graphited graphite flake is spent, is extended along bed-plate dimension direction (La) rather than by the graphene layer
Storehouse, thus the graphene content being compound in needed for the composite is efficiently reduced, reduce the composite material defect and occur machine
Rate.
Brief description of the drawings
Fig. 1 forms high-graphitized graphene dispersion for the present invention in the schematic diagram of graphene layer；
Fig. 2 is the first embodiment of composite of the present invention and the tensile strength figure of comparative example；
Wherein, 10, composite；101st, large-area graphene；102nd, matrix.
Embodiment
Below, collocation schema is described in detail the present invention.
Fig. 1 is refer to, is a kind of composite 10 of large-area graphene, it is characterised in that including：One matrix 102；One
Large-area graphene 101, is scattered in the matrix 102, and the number of plies of the large-area graphene 101 is less than 20 layers and is situated between with a La
Diameter between 1 μm to 1000 μm, the La is by a value obtained by Raman spectrum.
In the present embodiment, the number of plies of the large-area graphene is between 1 to 20 layer, preferably 1 to 10 layer, is more preferably
1 to 5 layer, and the most preferably large-area graphene of individual layer.
The preparation method of the composite of large-area graphene, it has area big and more perfect graphene by compound
The graphene of plane, to be obviously improved the physico-chemical property of the composite.The preparation of the composite of the large-area graphene
Method includes：A high-graphitized graphite flake is provided to be dispersed to a solvent to form a solution；Surpass using a dispersant or one
Sound wave concussion method makes the high-graphitized graphite flake be separated into a large-area graphene in the solution, wherein the large area stone
The number of plies of black alkene is less than 20 layers and with diameters of the La between 1 μm to 1000 μm, and the La is obtained by one by Raman spectrum
The value obtained；And mix the solution with a matrix to form a composite.To make the composite that there is preferable machinery
Laminated structure graphene in intensity, the present invention preferably from the perfect hex crystal of tool, the high-graphitized graphite flake is one
Product obtained by molten carbon deposition method and with 0.8 to 1.0, preferably 0.9 to 1.0, more preferably 1.0 degree of graphitization, and
The large-area graphene as obtained by the high-graphitized graphite flake is scattered, the thickness of its simple layer between 0.3 nm to 1.5 how
Between rice.
Above-mentioned " degree of graphitization " means the ratio of graphite.The theory of distance between graphene planes (graphene plane)
It is worth for 3.354 angstroms (angstrom), therefore when degree of graphitization is 1, refers to that graphene storehouse is the closest, its graphite plane
Spacing (d (0002)) is 3.354 angstroms.Degree of graphitization (G) can be calculated by following formula 1：
Formula 1G=(3.440-d (0002))/(3.440-3.354)
Accordingly, higher degree of graphitization corresponds to larger crystal size, is the hex crystal plane by graphene
The bottom surface direction size (La) of structure and the size of stack layer (Lc) are determined.Therefore, it is however generally that, it is high-graphitized to refer to
Degree of graphitization is more than or equal to 0.8.
When choosing is with the above-mentioned large-area graphene as obtained by high-graphitized graphite flake is scattered, it is compound in this and answered
Content needed for condensation material can be reduced preferably, in a such as aspect of the invention, and the content of the large-area graphene can account for this and answer
The 0.01wt% of condensation material gross weight to 20wt%, is preferably then 0.01wt% to 10wt%.
In the present invention, the large-area graphene can be according to the one of required and various materials matrix composites, such as present invention
In aspect, the matrix can be at least one be selected from by plastic cement, rubber, staple fibre, natural fiber, ceramic material, metal material or
It combines constituted group, but the present invention is not limited thereto.Furthermore, in order to more improve the mechanical property of the composite,
The composite more may include an additive, the additive can at least one be selected from by organic material, metal material, ceramic material,
Or it combines constituted group；In the present invention an aspect in, can select an organic crosslinking agent, with strengthen those graphenes with
Adhesion between matrix.In the present invention, be not limited as the plastic cement species of matrix, can be thermoplastics type's plastic cement, such as polyethylene,
Polyvinyl alcohol, polypropylene, polyester, polyamide, makrolon, polytetrafluoroethylene (PTFE), polyacrylonitrile, polyethylene ethylene alcohol copolymer and
Its analog；The species of rubber is also unrestricted, for example, can be natural rubber, vulcanization rubber or synthetic rubber.
In addition to the above-mentioned adhesion strengthened in the way of additive between the two, more can by one heat treatment or one chemistry at
Manage to improve the affinity between the large-area graphene and the matrix.In the aspect of the present invention, the large-area graphene can
First handled through empty burning method, to increase the surface roughness of the graphene layer, improve its affinity between matrix；And in the present invention
Another aspect in, then the large-area graphene can be handled with thermal oxidation method, chemical oxidization method or chemical doping method.It is specific next
Say, the large-area graphene handled through thermal oxidation method or chemical oxidization method, it is in can produce C=in hex crystal planar structure
O, COOH ,-OH or C-O-C contain oxygen functional group；And through the large-area graphene of chemical doping method processing, its hex crystal is put down
Part carbon atom in the structure of face is then replaced by Group IIIA or VA races element.Above-mentioned processing can make the large-area graphene surface
With functional group, and then improve the bond strength and compatibility between its matrix between matrix.
Above-mentioned prepared composite, according to selected matrix, the difference of additive, can be applied to pressure-sensing
Device, surface acoustic wave filter, resonator, thermal grease, printed circuit board (PCB), conducting resinl, transparency electrode, UV lasers, light emitting diode,
Liquid crystal display, solar cell, transistor, capacitor, DNA chip or its combination, the invention is not limited in this.
Supplementary notes, " bottom surface direction size (La, based plane) " herein refers to by single atomic layer structure
Into graphene hex crystal planar structure size；" interplanar spacing (d (0002)) " refers to the side of single-layer graphene layer stack
To, wherein, spacing refers to the distance for the graphene hex crystal interplanar that single atomic layer is constituted.
On the preparation method of composite of the present invention, one is dispersed to there is provided a high-graphitized graphite flake first molten
Agent is to form a solution；The high-graphitized graphene is set to divide in the solution using a dispersant or a ultrasonic vibrating method
Dissipate for a large-area graphene, wherein the number of plies of the large-area graphene is less than 20 layers and with a La between 1 μm to 1000 μm
Between diameter, the La is by a value obtained by Raman spectrum；And the solution is mixed with a matrix answered with forming one
Condensation material.
It will further be illustrated below by embodiment, the right embodiment is only made for convenience of description, and be not intended to limitation originally
Invention.
First embodiment
It is to select a natural rubber as a matrix in first embodiment of the invention, and the large-area graphene is molten
In ethyl acetate, it is sufficiently mixed so that a solution is made, wherein, the high-graphitized large-area graphene and the natural rubber
Weight ratio be 1：99.Treat after the completion of above-mentioned steps, directly the natural rubber can be vulcanized and dry formation one containing plural number
The composite of individual large-area graphene.
Second embodiment
In the second embodiment of the present invention, its preparation flow is roughly the same with first embodiment, institute's difference be in by
In matrix be a polyvinyl acrylic copolymer.Therefore, the large-area graphene used in this embodiment passes through a thermal oxide
Processing makes its surface have epoxy radicals (- C-O-C-) to improve the affinity between the large-area graphene and matrix.Then, when this
When a little large-area graphenes containing epoxy radicals are mixed with the matrix that polyvinyl acrylic copolymer is constituted, you can pass through matrix
Carboxyl (- COOH) and the large-area graphene epoxy radicals (- C-O-C-) formation covalent bond to improve affinity between the two,
And then lift the mechanical strength of the composite；Accordingly, the present embodiment is to prepare to complete a composite, wherein, the large area
It is to form covalently bonded more to enter with carboxyl via epoxy radicals between the matrix that graphene and polyvinyl acrylic copolymer are constituted
One step lifts the mechanical strength of the composite.
3rd embodiment
The preparation flow of third embodiment of the invention is roughly the same with first embodiment, and institute's difference is in because matrix is
One polyvinyl alcohol, and the large-area graphene are its surface is produced hydroxyl (- OH) through a chemical oxidation treatment, therefore this
Embodiment is, using a diepoxyoctane as a crosslinking agent, and to make the large-area graphenes of those hydroxyls and the polyvinyl alcohol institute
The matrix of composition is combined, and then lifts the mechanical strength of the composite；Accordingly, the present embodiment is to prepare to complete a composite wood
Material, wherein, be between the large-area graphene and the matrix via the crosslinking agent be crosslinked the large-area graphene with by polyethylene
The matrix that alcohol is constituted, and further lift the mechanical strength of the composite.
Comparative example
The component content of comparative example of the present invention is roughly the same with first embodiment of the invention with preparation flow, is not existed together
It is graphene used in comparative example without dispersion steps；Therefore in the composite of comparative example, what those were not dispersed through
High-graphitized graphite flake is by a stack architecture and is scattered in the matrix that vulcanization rubber is constituted.
Fig. 2 is the first embodiment of composite of the present invention and the tensile strength figure of comparative example, wherein by being controlled in point
The dispersant and/or ultrasonic vibrating treatment time added during the high-graphitized large-area graphene are dissipated, adjustment should
Graphene is layered and the scattered situation in matrix.As shown in Fig. 2 when the number of plies of the large-area graphene is fewer, i.e. the big face
Product graphene spacing is bigger, and under same amount, the tensile strength of prepared composite is higher.Furthermore, even if the big face
The product graphene storehouse number of plies is identical, and the large-area graphene is disperseed in matrix when must be more uniform, prepared composite
Tensile strength is also higher.Therefore the big face of minor proportion can be used via the composite prepared by the method for the invention described above
Product graphene can obtain preferably mechanical strength.
Above-described embodiment is illustrated only for convenient explanation, and the interest field that the present invention is advocated certainly should be special to apply
It is defined described in sharp scope, rather than is only limitted to above-described embodiment.
Claims (7)
1. a kind of composite of large-area graphene, it is characterised in that including：
One matrix；
One large-area graphene, is scattered in the matrix, and the number of plies of the large-area graphene is less than 20 layers and with a La between 1
μm to the diameter between 1000 μm, the La is by a value obtained by Raman spectrum.
2. the composite of large-area graphene as claimed in claim 1, it is characterised in that the number of plies of the large-area graphene
Between 1 to 5 layer.
3. the composite of large-area graphene as claimed in claim 1, it is characterised in that utilize a dispersant or a Supersonic
Ripple concussion method disperses a high-graphitized graphite flake to obtain the large-area graphene.
4. the composite of large-area graphene as claimed in claim 3, it is characterised in that the degree of graphitization of the graphite flake
Between 0.8 to 1.0.
5. the composite of large-area graphene as claimed in claim 1, it is characterised in that the thickness of the large-area graphene
Between 0.3 nm between 1.5 nms.
6. the composite of large-area graphene as claimed in claim 1, it is characterised in that the large-area graphene compared to
The graphene composite material has one between 0.01wt.% to the percentage by weight between 20wt.%.
7. the composite of large-area graphene as claimed in claim 1, it is characterised in that the matrix be selected from by plastic cement,
Rubber, staple fibre, natural fiber, ceramic material, metal material or the constituted group of its combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710061806.5A CN106947119A (en) | 2017-01-26 | 2017-01-26 | The composite of large-area graphene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710061806.5A CN106947119A (en) | 2017-01-26 | 2017-01-26 | The composite of large-area graphene |
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| CN106947119A true CN106947119A (en) | 2017-07-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675259A (en) * | 2018-05-18 | 2018-10-19 | 中国电子科技集团公司第十三研究所 | Pressure sensor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663435A (en) * | 2012-09-12 | 2014-03-26 | 铼钻科技股份有限公司 | Graphene reinforced composite material |
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- 2017-01-26 CN CN201710061806.5A patent/CN106947119A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663435A (en) * | 2012-09-12 | 2014-03-26 | 铼钻科技股份有限公司 | Graphene reinforced composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675259A (en) * | 2018-05-18 | 2018-10-19 | 中国电子科技集团公司第十三研究所 | Pressure sensor |
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Application publication date: 20170714 |
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