CN109273134A - With preparing graphite alkene and graphene composite conductor - Google Patents
With preparing graphite alkene and graphene composite conductor Download PDFInfo
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- CN109273134A CN109273134A CN201710585623.3A CN201710585623A CN109273134A CN 109273134 A CN109273134 A CN 109273134A CN 201710585623 A CN201710585623 A CN 201710585623A CN 109273134 A CN109273134 A CN 109273134A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
Abstract
A kind of method manufacturing graphene joint product is provided, this method, which passes through, is formed in the initial composite structure comprising graphite in compression support construction, the compression support structure configuration is graphite to be maintained in compression support construction during mechanically deform, and apply the iteration mechanically deform process comprising multiple mechanically deform iteration to initial composite structure.Each iteration uses forming process, is configured as applying to composite construction horizontal and vertical power to compress the graphite in compression support construction, so that graphite densifies in compression support construction.Enough iteration are carried out to shear graphene layer from the graphite particle of graphite in compression support construction to provide graphene joint product.Graphene can also be extracted from graphene composite structure using being further processed.
Description
Technical field
Technical field of the invention is to produce graphene from graphite.Application of the invention is for producing for electric conductor
Graphene, for example, integrated circuit provide lead, electric wire for electronic equipment, cable, transmission line, motor and transformer.
Background technique
Known graphene has ideal electric conductivity.As the composition of compound between graphite layers, graphene is that have six
The carbon monoatomic layer of prismatic crystal lattice, an atom forms a vertex in lattice.Since with this atomic structure, graphene has
Many unique characteristics.At room temperature, it has very strong, the highest known conductivity with natural materials.This is because
Each carbon atom shares 6 electronics, and internal layer has 2, and outer layer has 4.In most of situation, this 4 outer-shell electrons can be used for
Chemical bonding, but in graphene, each atom is connected on 3 other carbon atoms on tow -dimensions atom layer, is released
Available 1 electronics is conducted for electronics in three-dimensional.The moveable electronics of these height is located above and below graphene layer.
In the band structure of graphene, linear dirac (Dirac) disperse at K point leads to zero effective mass of electronics, to overcome
Phon scattering simultaneously leads to significant electron mobility 200000cm2/ Vs is 10 in room temperature carrier density12/cm2.Graphene
The corresponding resistor rate of layer is 10-6Ω cm less than the resistivity of silver, and is also known minimum at room temperature.Particularly, stone
Black alkene can carry the current density than copper as high 6 orders of magnitude of electric conductor, and weight is also lighter than aluminium by about 40%.It can also be with
Heat is effectively conducted, and almost transparent.However, being industrial application and most of graphenes for producing are powder shapes
Formula has chip shape or form of film on substrate.The covalency of carbon key means that graphene platelet is difficult to connect on a large scale
With molding to form product.
Another obstacle that graphene conductor is widely used is limited availability phase with graphene on a commercial scale
It closes.Although there is presently no in such a way that low cost is repeatable there are many known method for producing graphene
Large-scale production includes the methods availalbe of the high quality material of original or approximate original graphite alkene.
Graphene can be removed by the micromechanics of the pyrolytic graphite of high-sequential, epitaxial growth, chemical vapor deposition, electricity
The also original manufacture of chemical stripping and graphene oxide.First three methods, which can produce, has opposite perfect structure and superiority
The graphene of energy, but output is very limited.
Graphene oxide can be used cheap graphite as raw material by cost-effective chemical method with high yield
Production.However, the graphene oxide routinely produced has many chemistry and fault of construction.Similarly, this also occurs in electrification
In the graphene for learning removing.Although the reduction treatment of graphene oxide can partly restore the structure and property of graphene,
But all defects can not be removed.Different reduction processes may also lead to the heterogeneity of the GO (rGO) of reduction.Therefore,
The problem of this technology is that the quality of the graphene layer generated is alterable height (for certain methods) and shows low at present
In the characteristic of the other methods such as theoretical potential of the original graphite alkene of mechanical stripping production.
Up to the present, the graphene of mechanical stripping production shows best physical property, regardless of for producing graphite
How is the particular technique of alkene.Lift-off technology separates single-layer or multi-layer graphene from graphite.Graphite has the planar structure of stratiform,
It is made of multiple individual graphene layers.Carbon atom is divided into the honeycomb crystal lattice of 0.142nm between being distributed in, between plane
Distance is 0.335nm.Atom in plane is with Covalent bonding together (sp2), only there are four three sites in current potential binding site
Bonding.4th electronics planar free migration, makes graphite.Combination between layer is by weak Van der Waals force knot
It closes.Sp in graphite2It is bonded bonded energy very strong, and that there is about 284.4eV, and the removing of interlayer can reduce four numbers
Magnitude (42.6meV), so that graphite linings be allowed to separate.The graphene produced using mechanical stripping technology is of high quality, can be with
Produce original or approximate original graphene.Up to the present, mechanical stripping is to be known to production without the original graphene of substrate
Unique technical.But the yield of mechanical stripping technology is very low.For other graphene production technologies, impurity (such as oxygen, nitrogen,
Organic group etc.) and graphene between interaction lead to the reduction of the free electron on graphene surface.These impurity bases
Group can also be used as scattering center, to influence the mobility of free electron on surface, so as to cause more much lower than original graphite alkene
Conductivity.Chemical vapor deposition can produce single layer original graphite alkene, as the coating on substrate.However, using this skill
Art realizes that high purity graphite alkene may be at high cost and low yield.
Need one kind that the method that high-quality graphene includes original or approximate original graphite alkene can be mass produced, with full
The demand of foot industry and research circle.
Summary of the invention
A method of manufacture graphene joint product, comprising the following steps:
The initial composite structure comprising graphite is formed in compression support construction, the compression support construction is used in machinery
Graphite is maintained in compression support construction during deformation, and
Iteration mechanically deform process including multiple mechanically deform iteration is applied to initial composite structure, each iteration includes
Forming process is configured to apply horizontal and vertical power to composite construction to compress the graphite in compression support construction, and its
The iteration of middle forming process leads to the graphite densification in compression support construction, and carries out enough iteration to tie from compression support
The graphite grains of graphite shear graphene layer in structure, to provide graphene joint product.
The embodiment of iteration mechanically deform process may include the first stage, wherein the iteration mechanically deform of composite construction
Lead to compress the graphite particle densification in support construction.
In one embodiment, the first stage is characterized in that increasing graphite density to inhibition by horizontal and vertical power
The density for further rotating movement of graphite particle leads to the compression of graphite particle and redirects.
75% can be greater than by inhibiting the further rotation of density of graphite particle.
The embodiment of iteration mechanically deform process may include second stage, and wherein iteration mechanically deform causes from graphite
Particle shears graphite linings.
It can have the shear component for being parallel to graphite basal plane by the pressure that forming process applies, it is sufficient to cause due to stone
The bulk density of black particle and the shearing of the basal plane along some graphite particles.For example, being enough to generate by what shear component generated
Energy along basal plane shearing can be greater than 42.6meV.
In some embodiments, the friction in the first stage and second stage between graphite particle and support construction
Power can cause to shear in some graphite particles for being parallel to the frictional force of graphite basal plane.
In some embodiments, this method can have transition stage, and wherein graphite linings redirecting and shear all
Occur.
In some embodiments, forming process is drawing process.In such an embodiment, compression support construction can
To include the pipe formed by Stretch material, graphite is placed in the pipe for drawing process.Some embodiments of tube material
Including metal or polymer material.
In some alternative embodiments, forming process is the operation of rolling.In such an embodiment, initial composite knot
Structure can be the laminar structure including alternate substrate and graphite linings, and wherein substrate layer, which provides, keeps the compression of graphite to support knot
Structure.Some embodiments of substrate include metal or polymer.
In some embodiments, this method further includes the steps that periodically measuring the conductivity of composite construction with determination
Transforming degree of the graphite to graphene in composite construction.
In some embodiments, this method further includes the post-processing step from compression support construction separation graphene.
In some embodiments, post-processing step includes dissolution compression support construction material to extract graphene.
In some embodiments that compression support construction is laminar structure, post-processing step may include supporting compression
Structural stratification is to extract graphene.
Detailed description of the invention
Fig. 1 shows graphite lattice structure.
Fig. 2 is that the graphite of embodiment according to the present invention is converted into the high level flow chart of graphene process.
Fig. 3 schematically shows the powder casing process principle for production sample Al packet multifibres graphite core.
Fig. 4 is for sample Al/ graphite composite material to be pulled to φ 1.00mm from φ 8.00mm, and deformation rate is about 12%
Drawing die size table.
Fig. 5 schematically shows the size relationship thread between core number and the internal diameter of metal sleeve.
Fig. 6 schematically shows the arrangement for the Al/ graphite compound wire being filled into Al pipe, and quantitative relation formula is
1+6n, wherein n=1,2,3,4 ...
Fig. 7 schematically shows the power generated in drawing process.
Fig. 8 a schematically shows the graphene removed from graphite particle, and wherein basal plane is parallel to draw direction.
Fig. 8 b, which is schematically shown, (to be had random in the initial stage of drawing process by the graphite particle of frictional force drives
Orientation) rotation.
Fig. 9 a schematically shows the power being applied in graphite particle in the initial stage of drawing process.
Fig. 9 b is schematically shown to be applied in graphite particle in the stage for the drawing process for realizing strong mechanically deform
Power.
Fig. 9 c schematically shows the power that the later stage in drawing process is applied in graphite particle, such as covers in Al
It is hardened in the case where strong mechanically deform.
Figure 10 schematically shows how graphite plate is separated by mechanically deform.
Figure 11 a shows the cross section shapes of the single graphite core of Al packet.
Figure 11 b shows the cross section shapes of the Al packet multifibres graphite core with 7 silks.
Figure 11 c shows the cross section shapes of the Al packet multifibres graphite core with 49 silks.
The electric current that Figure 12 a shows the resistivity measured from pure Al and Al packet monofilament, 7 multifibres and 49 multifibres graphite cores relies on
Property.
The electric current that Figure 12 b shows the temperature measured from pure Al and Al packet monofilament, 7 multifibres and 49 multifibres graphite cores relies on
Property.
Figure 13 schematically shows the principle for producing original graphite alkene using continuous mechanically deform using rolling.
Specific embodiment
Embodiments of the present invention provide it is a kind of using mechanically deform make graphene layer from be maintained at compression support construction in
Graphite particle removing method.Mechanically deform process uses multiple mechanically deform iteration so as to compress the graphite in support construction
Crystal grain densification, this is first stage mechanically deform, and shears graphite linings in compression support construction from graphite particle
Graphene is formed, this is second stage mechanically deform.Graphene in compression support construction may be used as composite graphite alkene product.
Graphene is separated from compression support construction to recycle graphene alternatively, other operation stages can be used.Compression support knot
Structure, which can be, any type of structure of graphite is kept during mechanically deform, and deform during mechanically deform
Mechanically deform power is transmitted to graphite particle.Such as in one embodiment, compression support construction is pipe, in pipe wire drawing or
Graphite can be filled for powder casing in extrusion process.In other embodiments, compression support construction can be lamination knot
Structure, container or honeycomb can keep graphite particle at it during compacting, the operation of rolling or punched mechanically deform
In.
Compression support construction can be made of any material that permanent mechanical deforms.For example, for drawing process, compression branch
Support structure can be aluminum pipe or copper pipe.Alternatively, this can be made of polymer or any other materials for being suitable for stretching or squeezing out.
Similarly, suitable for keeping graphite during mechanically deform and any material of mechanically deform being kept to can be used for such as rolling, punching
Pressure, the processes such as compacting.In some embodiments, compressible support construction material can be based on the compound production of final use graphene
The material requirements of the property of product (such as electric conductor) and deformation technique to be used selects.In other embodiments, may be used
Compression support construction material property can be selected needed for the post-processing based on graphene composite structure.In an embodiment party
In formula, required property can be the solubility that graphene is recycled for post-processing.In other embodiments, post-processing can
To include the support construction material suitable for other production processes for producing other products and selection.
Graphite is the form that crystalline carbon naturally occurs and most stable of carbon form.Graphite can also be synthesized.Graphite is rich
It is rich and can be commercially available in a variety of forms, such as powder, thin slice or solid bar, item or ingot bar.As described above and Fig. 1 institute
Show, graphite 100 has the planar structure of stratiform, is made of multiple single graphene layers 110,112,114.Carbon atom is disposed in
In honeycomb crystal lattice, it is divided into 0.142nm therebetween, is divided into 0.335nm between plane 110,112,114.In plane 110,112,114
130 covalent bonding (sp of atom2) 135, only there are three bondings in four current potential binding sites.4th electronics planar from
By migrating, make graphite.110,112,114 monoatomic layer is with bonding force bonding (or holding) between pattern ylid Chuihua molecule, such as Fig. 1
It is middle to be indicated with line 140.Sp in graphite2Bonding is very strong, and the combination energy with about 284.4eV, and the removing energy of interlayer
Low four orders of magnitude (42.6meV), so that graphite linings 110,112,114 be allowed to separate or slide over each other.Embodiment utilizes stone
This property of ink, and apply the enough power for being parallel to graphite layer plane using mechanically deform process to cause dividing for layer
From.
Fig. 2 is the high level flow chart from the method 200 of graphite manufacture graphene.This method includes initial step 210, shape
At including in the initial composite structure for compressing the graphite in supporting structure, compression supporting structure is configured to will during mechanically deform
Graphite is maintained in compression support construction.Then, the iteration machine including multiple mechanically deform iteration is applied to initial composite structure
Tool deformation process 220, each iteration include forming process, which is configured as applying to composite construction horizontal and vertical
Power is to compress the graphite in compression support construction, and wherein the iteration of forming process leads to the densification for compressing the graphite in support construction
Change 222 and carry out enough iteration so that from compression support construction in graphite graphite particle shear 225 graphene layers from
And provide graphene joint product 230.Graphene composite structure 230 can be the shape for some applications from the output of the technique
Formula, such as graphene composite conductor.However, it is possible to execute optional step 240 to separate graphene with compression support construction
To extract graphene.
Iteration mechanically deform process 220 is by the successive ignition including at least one forming process.However, iteration mechanically deform
Process may be considered that including two Main Stages, it is characterized in that based on forming process to the physical influence of graphite particle, without
It is the property of forming process itself.In fact, identical forming process can be used for all iteration, such as pass through reality discussed below
Apply what example will become apparent.But the characteristics of we will discuss two Main Stages first.
222 period in the first stage, the graphite particle that the iteration mechanically deform of composite construction makes to compress in support construction cause
Densification.This stage increases the density of graphite.The stage is characterized in that increasing graphite density extremely by horizontal and vertical power
The density for further rotating movement for inhibiting graphite particle, leads to the compression of graphite particle and redirects.
During second stage 225, iteration mechanically deform causes to shear graphite linings from graphite grains.In the second stage
In, the pressure applied by forming process has the shear component for being parallel to graphite basal plane, it is sufficient to make some layers due to graphite
Grain bulk density and slided along the basal plane of some graphite grains.This may cause graphene layer from graphite particle removing or
Graphite particle is broken into smaller " lath " including multiple graphene layers by person.In the process stage that mechanically deform continues,
From graphite particle remove graphene and lath densification and redirect it can also happen that.
In addition, the frictional force between graphite particle and support construction is in some graphite during the first and second stages
It may cause shearing in grain, wherein frictional force is parallel to graphite basal plane.
It should be understood that redirecting and shearing the place all occurred it can also happen that transition stage in graphite linings.
Redirecting and shear the degree occurred in the iterative process of forming process can be according to the type of used forming process
Change with the geometry of composite construction.
This method is discussed in more detail now with reference to Samples EXAMPLE.The present inventor has invented in pipe manufacturing process
The middle method using powder manufacture graphene core conductor, such as International Patent Application PCT/AU2017/ in co-pending view
050309, priority date is described on April 7th, 2016 and laminar structure is such as in co-pending view submitted in 2016
Described on August 17, and the Australian Provisional Patent Application 2016903265 and 2017901290 on April 7th, 2017.
These production methods utilize traditional wire drawing and rolling manufacturing process and equipment.In the manufacturing process of graphene composite conductor,
Initial sample test is carried out using identical manufacturing equipment and manufacturing process to convert graphene for graphite.This sample production
The feasibility of the graphite production method is had been proven that with test, but this method should not be construed as limiting these technologies
- provide and apply any manufacturing method of iteration mechanically deform process of compression (transverse direction) and stretching (longitudinal direction) power and can be used in this
The production method of graphene.
First sample is manufactured using the drawing process for iteration mechanically deform, and the process is shown in FIG. 3.
In the sample making, inventor generates serious mechanically deform using known powder casing stretching technique to shell from graphite
From graphene layer.The graphite for entering this process can be bulk graphite or graphite powder.The advantages of using iteration mechanically deform
It is, method of the invention can be used known manufacturing technology and be implemented using the equipment of continuous treatment process, to realize
Efficiently batch production.Powder casing manufacturing technology is utilized in first experiment for verifying concept, as shown in Figure 3.First
It walks in (a), the high purity graphite powder 310 with 10nm to 500 μm of particle size is packed into aluminium (A1) pipe 320 to provide compression
Support construction 325.The outer diameter of Al pipe 120 is φ 8mm, and internal diameter is φ 4mm, length 1000mm.It should be noted that input material
The parameter of material and Al pipe is to can be used for the equipment of sample based on available material and the present inventor come selection, rather than any work
Skill requires or limitation.Rubble ink particle (> 200 μm) also can be used in this method or solid graphite stick is filled or plugged in pipe and carries out
Processing.The material of pipe can be metal (such as Al, Cu or Ag pipe etc.), polymer or other.Can be used any can deform
To generate the shell material of shearing force on graphite core.The outer diameter and inner diameter of pipe can be according to tube material and in material
The load capacity for generating the machine of mechanically deform changes in a wide range.According to the application of production material, pipe range can be from
Several millimeters are arrived several kms or longer.It should be understood that parameter such as tube material, pipe diameter and length may by it is selected at
The influence of shape process, and therefore will change within the scope of the invention very big.
Then, the composite material 325 of Al/ graphite-pipe is stretched to Al packet graphite core wire 330 using iteration drawing process, with
Form the Al/ graphite compound wire with graphite monofilament (graphite single).In the drawing process, Al pipe (having graphite core) is logical
It crosses one group of drawing die iteratively to stretch, drawing die diameter when stretching iteration every time reduces.
In embodiment sample, it is φ 1.24mm that the initial Al packet graphite composite structure that diameter is φ 8mm, which is pulled to diameter,
Graphite core wire.Then monofilament Al/ graphite compound wire is cut into length is seven pieces of 1200mm.Together by these line tyings
340, wherein a line surrounds (as shown in Figure 5) by other six lines, being inserted into outer diameter is φ 8mm, and internal diameter is φ 4mm, long
Degree is in another aluminum pipe 342 of 1000mm, for further stretching.For sample making, the step is necessary, because
Limitation-minimum diameter of stretcher is φ 1mm.It should be appreciated that the outer diameter of compound wire depends on answering for manufacturing Al/ graphite
Close the internal diameter of the pipe of the multifibres core of conducting wire and by the quantity of the silk core manufactured.For example, there are 7 graphite silk cores in order to manufacture
Al/ graphite compound wire, the outer diameter of Al pipe is φ 8mm, and internal diameter is φ 4mm, and theoretically the diameter of conducting wire should be φ 1.33mm,
Based on arrangement shown in fig. 5.However, it also depends on available drawing die sometimes.On the one hand, the diameter of conducting wire is necessarily less than
Theoretical size, so as to easily will be in 7 line insertion tubes of manufacture.It is close to be desirable for increasing close to the line of theoretical diameter accumulation
Degree.Fig. 4 shows the table of stretching die, and inventor can be used for drawing the material that outer diameter is φ 8mm to φ 1mm in sample making
It stretches.Obviously, the die size of 1.34mm is more than threshold size, and next useful size is φ 1.24mm.Therefore, in sample reality
It applies in example, has manufactured the Al/ graphite compound wire that the outer diameter with graphite monofilament (graphite single) is φ 1.24mm.
Above-mentioned technique is repeated, Al/ graphite multiple tube is drawn into the conducting wire that diameter is φ 1.24mm, being formed has more than 7
The Al/ graphite compound wire of silk graphite.This process can be repeated to be formed and have 49 (72)、343(73)、2401(74)、16,
807(75)、117,649(76)、823,543(77)、5,764,801(78) root multifibres graphite Al/ graphite compound wire etc..Or
The quantity of person, multifibres graphite can be respectively 19,37,61 etc. using index, such as based on geometry shown in fig. 6, can
To be 19,361 (192)、6859(193)、130,321(194) etc., the specification depending on product.It should be understood that above
The arrangement of the multifibres core of discussion is one embodiment of powder sleeve technology, and the arrangement (that is, core and accumulation arrangement) can be with
Change between the embodiments, and does not need to follow discussed above.The important feature of the process is to make the graphite containing supporting mechanism
Extreme mechanical deformation lead to the shearing of graphite particle.
During stretching, as shown in fig. 7, being applied to three power F on conducting wire 770 there are drawing die 710p720, Fc
730 and Fb740, wherein Fd750 be tractive force, Fc730 be pressure, is applied to for mold 710 perpendicular to drawing force 750
On conducting wire 770.Fp720 be the frictional force that drawing die 710 is applied on conducting wire 770.Fd750 are drawing forces and are equal to Fb
740.In these power, Fb740 be the pulling force and F of elongate material 760c730 be pressure.Fc730 perpendicular to pipe 760 or conducting wire
770 surface, to reduce the diameter of material.
In the initial stage of drawing process, since the plastic deformation ability of Al is far longer than graphite, so mechanically deform master
Occur in Al set.Therefore, the flowing of Al leads to frictional force F in drawing processfBe applied on graphite wicking surface-by the stream of aluminium
It is dynamic to cause frictional force generation during stretching between the inner surface of aluminium set and the outer edge of graphite core.In mechanically deform process
Initial stage, pressure FcEffect mainly increase core in graphite bulk density.For example, in Samples EXAMPLE, stone
The initial bulk density at ink powder end is about 45%, allow initial mechanical deform (stretchings) iteration during powdered graphite particle show
Write movement.This movement and compression in earlier iterations the result is that increase powdered graphite bulk density.
As described above, in the first phase, FcFunction be mainly improve graphite core density, by squeeze Al pipe in
Absolutely empty is reduced the cross-sectional area of Al/ graphite composite material.In this stage, with FfIt compares, compared with the influence of frictional force,
Due to the movement of lower bulk density and particle, FcPower to single graphite particle is unconspicuous.In early stage, due to
In graphite grains (crystal) two different influences may occur for frictional force.Firstly, when graphite grains be aligned so that
It obtains basal plane and is parallel to FfDirection when, due to frictional force Ff, the top graphene layer of particular graphite particle can be removed directly.
As shown in Fig. 8 a, wherein frictional force 810 is parallel with basal plane 820, and frictional force may be enough two layers that overcomes graphite lattice structure
830, the weak Van der Waals force key between 840 causes one layer 840 to shear and separate from another layer 830.
Second, as shown in Figure 8 b, for the particle that basal plane 820 is not aligned with the direction of frictional force 810 (random orientation), only
There is the component of frictional force parallel with basal plane.The component of frictional force is generally insufficient to overcome the weak model moral in early stage process
Hua Jian.However, frictional force can lead to the rotation of particle 850 to redirect graphite particle, and it can be realized the accumulation of raising
Density.
Fig. 9 a to 9c illustrates in greater detail the power in graphite particle, and stone is discussed in the case where deformation process continues
Behavior of black particle under conditions of increasing density and compression.Fig. 9 a, which is shown, is applied to graphite particle in initial stage processing
On power.As discussed above, at this stage, due to the relative motion of the crystal grain in pipe, pressure becomes unobvious.Frictional force Ff
910 have the apparent component F perpendicular to basal plane 920tWith the apparent component F for being parallel to basal plane 920s940.With perpendicular to graphite
The F of basal planet930 compare, the shearing force F generated by frictions940 play prior effect in determining particle's behavior.This is
Because of the sp in graphite layer plane2Van der Waals force of the carbon key (284.8eV) of hydridization than graphite layers (removing can be 42.6meV)
High four orders of magnitude.In process segment early stage, when the force component 940 being applied in graphite basal plane 920 (a-b plane) is not big enough
When, the graphite particle with random orientation cannot be by FsAnd FtIt destroys.However, frictional force can drive these particles, (set interface is attached
(as shown in Figure 8 b) closely) is rotated, until the basal plane or layer plane of these graphite particles are parallel to frictional force FfDirection.Such as Fig. 8 a
It is shown, when basal plane 820 is parallel with frictional force, become shearing force Fs=Ff, and rub as caused by further drawing process
Power can lead to top graphene layer and remove from the graphite particle of these good alignments, as shown in Figure 8 a.
With the increase (due to lasting mechanically deform) of graphite density, the movement of graphite particle/crystal is suppressed.Inhibit
The further rotation of density of graphite particle is in the range of > 75%.Once the movement of graphite particle is suppressed, then pressure Fc 730
And frictional force 910 becomes significant.As shown in figure 9b, in the higher mechanically deform stage, graphite core is applied in the deformation of Al set
The frictional force increased.Particle rotation is limited by neighboring particles.In this case, most of Fc 730 is transferred to specifically
F is used as in graphite particlec'950, two force components can be divided into, be parallel to the shearing force of the basal plane plane of graphite particle
Fs'960 and the basal plane perpendicular to graphite particle power Ft'970.The force component in each direction depends on the orientation of particle.Frictional force
Shear component with pressure is superposition (Fs+Fs'), and can become large enough to make ultra-thin piece of graphite to slide, sometimes
It is the graphene layer sliding in graphite grains, as shown in figure 9b.
In some cases-for example lasting mechanically deform-processing hardening is likely to reduced the flowing in set, causes to rub
The reduction of power, makes pinch effect occupy an leading position.As is shown in fig. 9 c, wherein prime move is pressure F to one embodiment of this pointc
950.Pressure 950 has the shearing force component F for the basal plane for being parallel to graphite particles'960, and perpendicular to the basal plane of graphite particle
Force component Ft'970, and sufficiently large shearing force component will overcome the Van der Waals force of interlayer, and particle is caused to peel off or be broken into
Piece including several layers of graphenes, then by further mechanically deform iteration, piece is broken into single graphene layer.By shearing force point
What amount generated be enough the to destroy energy that is bonded between pattern ylid Chuihua molecule is in the range of > 42.6meV.
Further decrease (or the thickness as caused by rolling reduces) of the cross-sectional area of Al/ graphite composite material makes removing
Ultra-thin piece or graphene layer rotation, so that their basal plane is close to the interface between parallel Al and graphite core.Subsequent stretching
Or roll milling technology further removes multi-layer graphene at single-layer graphene.This generation is compound in the Al/ graphite with multifibres core
In the mechanically deform of material.Figure 10 is the schematic diagram for showing graphite flake and how being divided by mechanically deform.It should be understood that machine
Tool deformation can mainly utilize compressor mechanical deformation process, such as punching press or weight.It is real using the technique for such as stretching or rolling
Existing flowing effect may be advantageous the quick densifying during early stage processes, this is because high frictional force is helped
Help graphite particle redirect and the shearing of the early stage of interface between sheath and graphite.However, due to densifying
The relative motion of period particle still generates some flowings and friction effect during punching press or weight.It is envisioned that
The embodiment of this method can mainly utilize compressor mechanical deformation process.Alternatively, the deformation for causing flowing effect can be used
The combination of process (such as rolling or stretching) and mainly compressor mechanical deformation process.
Figure 11 a to 11c shows the cross section shapes of sample Al/ graphite composite material, and wherein Figure 11 a shows monofilament core
Line, Figure 11 b are 7 cores, and Figure 11 c is 49 cores.The outer diameter of these compound wires is φ 1.00mm.Increasing is passed through for multifibres line
Add the silk number in compound wire, the diameter of graphite core is significantly reduced from 380 microns of monofilament.This process makes graphite particle
(crystal) is divided into many (including several layers of graphenes), is then ultimately formed by wire drawing or roll milling technology by mechanically deform
Monatomic graphene layer.In most cases, by increasing deformation rate, graphene layer covers the interface between graphite core from Al
Form and be aligned to the center of core.
In general, the resistivity of Al is 2.85 × 10-6Ω cm, and graphite is 2.5 × 10 along the resistivity of basal plane-4Ω·
Cm to 5.0 × 10-4Ω cm, perpendicular to the resistivity 3.0 of basal plane-1Ω cm to 5.0 × 10-1Ω·cm.For by have with
The graphite of the particle composition of machine orientation, average resistivity are 1.5 × 10-1Ω·cm.Five orders of magnitude higher than the resistivity of aluminium.
Therefore, the graphite core compound wire formed and adding graphite in Al pipe and stretching will be obtained with the pure Al line of resistivity ratio
Much higher compound wire.Although the mechanically deform being applied in monofilament Al/ graphite composite material on graphite core is quite strong,
The formation of graphene occurs over just in the thin layer of Al set lower section, and most of carbon core is still graphite.Such as the curve of Figure 12 a
Shown, compared with pure Al line, this phenomenon causes the resistivity of compound wire higher.For multifibres conducting wire, Al set is applied to stone
Mechanically deform on Mo Xin is serious.This causes graphite particle to be separated, rotates then removing to be formed in Al set lower section
The thick-layer of monatomic stratiform graphene.These graphene layers cover the interface arrangement between " graphite " core along Al.Further
Deformation causes the diameter of graphite core to be substantially reduced, to generate complete graphene core under ideal conditions.Figure 12 a draws pure Al
Conducting wire 1210,1220,7 1230 and 49 1240 aluminium/graphite compound wire resistivity of single.Figure 12 b depicts same set of
The temperature and current dependence of conducting wire.Figure 12 a is shown by by the graphite-filled 7- silk 1230 prepared into pure Al pipe and 49-
1240 compound wires have the DC resistivity lower than pure Al conducting wire 1210.Since graphite has the electricity than pure five orders of magnitude of Al high
Resistance rate, single graphite conducting wire 1220 show higher resistivity.These test results show that sample manufacture passes through serious machinery
Deformation forms graphene in Al/ graphite compound wire.Because more graphenes are since stronger mechanically deform is from graphite
Grain removing, so obtaining lower resistivity with the material with more multifibres prepared by powder sleeve technology.In addition to 49 multifibres
Except the mechanically deform degree of core is bigger, these cores also experienced more mechanically deform iteration.
This method can also include periodically measuring the conductivity of composite construction to determine in composite construction graphite to stone
The step of transforming degree of black alkene.This can provide a kind of for testing graphite to the simple and non-of graphene conversion realization degree
Destructive method.
As shown in figure 13, powder casing methods are similar to, it can also be effectively by the continuous mechanically deform that rolling generates
Graphite particle is removed, so that the graphene of high quality be mass produced.In this embodiment, initial composite structure be include hand over
The laminar structure of the substrate and graphite linings that replace, wherein substrate layer provides the compression support construction for keeping graphite.
Although embodiment discussed above forms compression support construction using aluminium, other metals or polymerization also can be used
Object material.
It should be appreciated that can choose mechanically deform process, so that this method provides the output that can be used as final product form
Joint product, such as low-resistivity conducting wire or conductive bar.
This method can also include the post-processing step from compression support construction separation graphene.Post-processing step can wrap
Dissolution compression support construction material is included to extract graphene.Such as in one embodiment, compression support construction is by polymer
Material is formed, and post-processing step may include dissolution polymer material.Then graphene can be extracted from solution, such as
By being centrifuged and drying.Alternatively, compression of metals support construction can also mechanically and/or chemically be removed to recycle graphene.
Alternatively, graphene can be extracted mechanically.For example, compressing the case where support construction is laminar structure
Under, post-processing may include making to compress support construction layering to extract graphene.
It will be appreciated by those skilled in the art that without departing from the spirit and scope of the present invention, can carry out
Many modifications.
In the description before claim and the present invention, except context is in addition because of language expression or necessary meaning requirement
Except, the variant of word " including (comprise) " or such as " including (comprises) " or " including (comprising) " are to wrap
The meaning included uses, that is, specifies the presence of the feature, but be not precluded in different embodiments of the invention and exist or add
Other feature.
It should be understood that the disclosure of referenced herein any prior art, the reference are not an admission that the disclosure
A part of general knowledge known in this field is constituted in Australia or any other country.
Claims (19)
1. a kind of method for manufacturing graphene joint product, comprising the following steps:
The initial composite structure comprising graphite is formed in compression support construction, the compression support construction is used in mechanically deform
Graphite is maintained in compression support construction by period, and
Iteration mechanically deform process including multiple mechanically deform iteration is applied to initial composite structure, each iteration includes forming
Process is configured to apply to composite construction horizontal and vertical power to compress the graphite in compression support construction, and wherein at
The iteration of shape process leads to the graphite densification in compression support construction, and carries out enough iteration out of compression support construction
The graphite particle of graphite shears graphene layer, to provide graphene composite material.
2. according to the method described in claim 1, wherein the iteration mechanically deform process includes the first stage, wherein described multiple
The iteration mechanically deform for closing structure leads to the densification for compressing the graphite particle in support construction.
3. according to the method described in claim 2, wherein the first stage is characterized in that increasing by horizontal and vertical power
Graphite density leads to the compression of graphite particle and redirects to the density for further rotating movement for inhibiting graphite particle.
4. according to the method described in claim 3, the density for wherein inhibiting the graphite particle to further rotate movement is greater than
75%.
5. according to the method described in claim 2, wherein the iteration mechanically deform process includes second stage, wherein described change
Cause to shear graphite linings from graphite particle for mechanically deform.
6. according to the method described in claim 5, it is characterized in that, can have by the pressure that the forming process applies flat
Row in the shear component of graphite basal plane, it is sufficient to lead to the bulk density due to graphite particle and along the basal plane of some graphite particles
Shearing.
7. according to the method described in claim 6, it is characterized in that being enough to cause some layers of edge by what the shear component generated
The energy of basal plane sliding can be greater than 42.6meV.
8. the method according to any one of claim 2 to 7, wherein in the first stage and second stage, it is described
Frictional force between graphite particle and the support construction can be in some graphite for being parallel to the frictional force of graphite basal plane
Cause to shear in particle.
9. according to the method described in claim 5, it is characterized in that, there is transition stage, wherein the again fixed of graphite linings occurs
To and shearing.
10. method according to any of the preceding claims, wherein the forming process is drawing process.
11. according to the method described in claim 10, wherein the compression support construction includes the pipe formed by Stretch material,
The graphite is placed in the pipe for drawing process.
12. according to the method for claim 11, wherein the tube material is metal or polymer material.
13. method according to any one of claim 1 to 9, wherein the forming process is the operation of rolling.
14. according to the method for claim 13, wherein the initial composite structure is to include alternate substrate and graphite linings
Laminar structure, wherein the substrate layer provides the compressible support construction for keeping the graphite.
15. according to the method for claim 14, wherein the baseplate material is metal or polymer.
16. method according to any of the preceding claims further includes periodically measuring leading for the composite construction
The step of electric rate is with the transforming degree of the graphite in the determination composite construction to graphene.
17. method according to any of the preceding claims further includes separating the stone from the compression support construction
The post-processing step of black alkene.
18. according to the method for claim 17, wherein the post-processing step includes dissolving the compression support construction material
Material is to extract the graphene.
19. according to the method for claim 17, wherein the compression support construction is laminar structure, and the post-processing
Step includes making the compression support construction layering to extract the graphene.
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| CN105417535A (en) * | 2015-12-29 | 2016-03-23 | 成都新柯力化工科技有限公司 | Method for preparing graphene material through stretching |
| US20160145108A1 (en) * | 2014-11-24 | 2016-05-26 | Taiwan Carbon Nanotube Technology Corporation | Method for manufacturing graphene platelets |
| CN106744879A (en) * | 2016-12-23 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of application of the method and Graphene that Graphene is peeled off based on draft flowing deformation |
| CN106898408A (en) * | 2017-01-23 | 2017-06-27 | 杭州电缆股份有限公司 | graphene-based electric conductor and preparation method thereof |
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| US20160145108A1 (en) * | 2014-11-24 | 2016-05-26 | Taiwan Carbon Nanotube Technology Corporation | Method for manufacturing graphene platelets |
| CN105417535A (en) * | 2015-12-29 | 2016-03-23 | 成都新柯力化工科技有限公司 | Method for preparing graphene material through stretching |
| CN106744879A (en) * | 2016-12-23 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of application of the method and Graphene that Graphene is peeled off based on draft flowing deformation |
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