CN106968128B - A kind of soft graphite alkenyl extrusion coating paper and preparation method thereof - Google Patents
A kind of soft graphite alkenyl extrusion coating paper and preparation method thereof Download PDFInfo
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- CN106968128B CN106968128B CN201710235829.3A CN201710235829A CN106968128B CN 106968128 B CN106968128 B CN 106968128B CN 201710235829 A CN201710235829 A CN 201710235829A CN 106968128 B CN106968128 B CN 106968128B
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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
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- 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
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/18—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylonitriles
-
- 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
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/24—Polyesters
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A kind of soft graphite alkenyl extrusion coating paper, including macromolecular fibre skeleton and graphene base body, the ratio I of D peak intensity and G peak intensity of the soft graphite alkenyl extrusion coating paper in Raman spectrumD/IGValue is less than or equal to 0.05；And graphene base body forms the hasp structure of interpenetrating networks with macromolecular fibre skeleton；Its preparation method includes：The macromolecular fibre skeleton prepared is taken to be placed on miillpore filter, graphene oxide dispersion is poured into above macromolecular fibre skeleton again and carries out decompression suction filtration, then filtered hydrogel block will be depressurized and obtain graphene oxide/macromolecular fibre extrusion coating paper through liquid phase volatilization self assembly, reduced again, high temperature induction graphitization obtains product.The soft graphite alkenyl extrusion coating paper that the present invention is prepared can be applied in transversal radiator is prepared, and show more excellent mechanical performance, conductive and heat conduction and heat radiation performance.
Description
Technical field
The invention belongs to high-performance special paper product field, and in particular to a kind of macromolecular fibre and graphene composite material
And preparation method thereof.
Background technology
The demand for development electronics of technology and the power of opto-electronic device such as information, communication and regenerative resource storage in recent years
Density is persistently lifted, thus the high efficiency and heat radiation of these devices become one it is main the problem of.High efficiency and heat radiation, it is to determine modern electricity
Son, photoelectron and photonic device Performance And Reliability deciding factor, especially for three dimensional integrated circuits of future generation and
For ultrafast high power density transistor device, this demand is more prominent.Due to the heat-sinking capability deficiency of elemental device unit
And causing its temperature control to fail, some new Heat Conduction Materials, mainly including heat-conducting interface material and transversal radiator etc. becomes this
The more promising critical elements of a little systems.
Transversal radiator is widely used in various commercial portable electric appts, such as mobile phone, tablet personal computer, luminous
Diode (LED) light fixture etc..Transversal radiator is usually paper-like, possesses thermal conductivity factor in high face, places it in part
Thermal source substrate can realize effective radiating.Typically the flexible graphite paper of commercial paper-like transversal radiator and graphitization polyamides are sub-
Amine (PI) paper.Graphene paper and graphitization PI paper have suitable heat conductivity, and graphite paper then takes second place, but graphene paper sexual valence
Than higher, and the thickness of graphene paper is controllable, such as adjustable from hundreds of nanometers to hundreds of microns.Therefore, graphene paper is one
The more high performance-price ratio parallel heat sinks of commercial application prospect.
However, existing graphene paper heat conductivility and flexibility all need further to improve to meet high power density electronics member device
The high speed development requirement of part.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
It is kind flexible, thickness is controllable, high heat conduction radiating, the soft graphite alkenyl extrusion coating paper of high strength, it is soft to correspondingly provide this
The preparation method and application of the graphene-based extrusion coating paper of property.
In order to solve the above technical problems, technical scheme proposed by the present invention is a kind of soft graphite alkenyl extrusion coating paper, it is described
Soft graphite alkenyl extrusion coating paper includes macromolecular fibre skeleton and graphene base body, the graphite of the soft graphite alkenyl extrusion coating paper
Fault of construction is few, and the graphite-structure defect is embodied in D of the soft graphite alkenyl extrusion coating paper in Raman spectrum less
The ratio I of peak intensity and G peak intensitiesD/IGValue is less than or equal to 0.05；And graphene base body is formed mutually with macromolecular fibre skeleton
Wear the hasp structure of network.
The said goods scheme provided by the invention had both maintained the nanoscale effect of graphene, and improved production well
Product mechanical strength and thermal conductivity.
Above-mentioned soft graphite alkenyl extrusion coating paper, it is preferred that the thickness control of the soft graphite alkenyl extrusion coating paper is micro-
Meter level or grade, thickness are controllable, can be as thin as several microns, also can be thick to more than several millimeters, and macromolecular fibre skeleton is thick
Spend controllable.It is furthermore preferred that the graphene base body and the mass ratio of macromolecular fibre skeleton are controlled in 5~11 ︰ 1.
Above-mentioned soft graphite alkenyl extrusion coating paper, it is preferred that the thermal conductivity of the soft graphite alkenyl extrusion coating paper is in 950W/
More than mK, square resistance are 1 Ω/below sq, and tensile strength is in more than 28.0MPa.By performing GB/T457-2008 paper
Folding test method (MIT methods), 135 ° of folding angles, bending number is up to more than 100 times.
The characteristics of above-mentioned technical proposal of the present invention takes full advantage of macromolecular fibre skeleton and graphene base body each, system
Standby soft graphite alkenyl extrusion coating paper not only has excellent mechanical strength, due also to its skeleton structure, maintains graphene and receive
Metrical scale effect, so as to show excellent heat conduction and heat radiation performance.
Above-mentioned soft graphite alkenyl extrusion coating paper, it is preferred that selected macromolecular fibre skeleton is mainly fine by following macromolecule
Dimension is formed：It is fine to include polyimide fiber, polyester fiber, poly terephthalic acid p-phenylenediamine fiber (aramid fiber), polyvinyl alcohol
At least one of dimension, polyacrylonitrile fibre, wool, silk, linen-cotton.
Currently preferred macromolecular fibre not only has excellent mechanical property, and abundant surface-active functional group will
Its papermaking reinforcing material as graphene-based extrusion coating paper, the contact area with matrix can be increased, strengthen interfacial combined function.
But low conductivity, thermal conductivity caused by Polymer Materials ' Structure limit its application in heat conduction and heat radiation field, of the invention by it
Combined with graphene, graphitizing is induced using graphene, can solve difficult graphited problem well, so as to improve height
The electrical and thermal conductivity performance of molecular fiber composite.
The technical concept total as one, the present invention also provide a kind of preparation side of above-mentioned soft graphite alkenyl extrusion coating paper
Method, comprise the following steps：The macromolecular fibre skeleton prepared is taken to be placed on miillpore filter, then the graphite oxide that will have been configured
Alkene dispersion liquid pours into above macromolecular fibre skeleton and carries out decompression suction filtration, and will depressurize filtered hydrogel block can be transferred to
On smooth glass plate, graphene oxide/macromolecular fibre extrusion coating paper then is obtained through liquid phase volatilization self assembly, then is reduced,
Follow-up alternative compacting, high temperature induction graphitization obtain product.
Above-mentioned preparation method, it is preferred that by the macromolecular fibre slurry of preparation is filtered, can to obtain screen cloth shape more for drying
The macromolecular fibre skeleton in hole；
The macromolecular fibre slurry is mainly made up of macromolecular fibre, bonding agent, dispersant and deionized water, wherein high
Molecular fiber, bonding agent, the mass ratio of dispersant are the ︰ 0~5 of 0.05~10 ︰ 0~15；The macromolecular fibre, bonding agent, divide
The mass ratio control of the summation and deionized water of powder is 0.05~20 ︰ 100~5000.It is furthermore preferred that the bonding agent is poly-
One or more in the water soluble polymers such as vinyl alcohol, polyethylene glycol, hydroxymethyl cellulose, polyvinylpyrrolidone, or
For polymer fibrids, paper pulp wood pulp etc.；
The dispersant can be polyethylene glycol oxide, Tween-80, AEO, polyacrylamide, alginic acid
Sodium, natural gum, methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, potassium pyrophosphate, APES phosphate ester
At least one of salt；But preferably at least one of polyethylene glycol oxide, polyacrylamide, because its water-soluble and flocculability
It is more suitable for macromolecular fibre papermaking shaping, is more beneficial for optimizing the performance of macromolecular fibre skeleton.
Above-mentioned preparation method, it is preferred that the decompression, which filters, to be specifically referred to having completed the micro- of macromolecular fibre skeleton
Graphene oxide dispersion is added on the filter membrane of hole to be filtered by vacuum, and treats that graphene oxide dispersion free above filter cake will
When disappearance, vacuum system is turned off.
Above-mentioned preparation method, it is preferred that the graphene oxide in the graphene oxide dispersion is by wet chemistry method
It is made, the wet chemistry method includes electrochemical oxidation process, hummers methods, closed oxidizing process, improved hummers methods, obtained oxygen
Graphite alkene is configured to graphene oxide dispersion after washing and filtering, dialysis, ultrasound, the graphene oxide dispersion
Concentration control is 1-15mg/mL.
Above-mentioned preparation method, it is preferred that reduced to the macromolecular fibre and graphene oxide composite material
Method include the direct chemical reduction method of reducing agent, high-temperature heat treatment method, catalytic reduction method, electrochemical reducing, Microwave reduction method,
Solvothermal method etc., but the reduction particularly preferably uses high-temperature heat treatment method, and the high-temperature heat treatment method can be than routine
Induction graphitization, graphitization temperature of the invention are carried out in the case that polymer high-temperature graphitization temperature (more than 3000 DEG C) is lower
Only 1800 DEG C~2600 DEG C, you can to obtain the higher high heat-conductivity conducting extrusion coating paper of degree of graphitization.Subsequently according to product need
Ask and be compacted, compaction pressure 0-50MPa, so as to obtain the high heat-conductivity conducting extrusion coating paper of densification.
The technical concept total as one, the soft graphite alkenyl extrusion coating paper that the present invention also provides a kind of the invention described above exist
Prepare the application in radiating paper, feature radiator (such as transversal radiator).By the soft graphite alkenyl extrusion coating paper of the present invention
Being directly used as transversal radiator has good heat conduction and heat radiation.
The technological principle of the present invention is：High polymer material fiber reinforcement is first prepared, is passed through by macromolecular fibre slurry
The controllable homogeneous high polymer material fiber reinforcement of thickness is prepared in filter shaping；Then by certain density graphene oxide solution
Hydrogel block is formed with macromolecular fibre skeleton through filtering, then graphene oxide/high score is self-assembly of by liquid phase volatilization
Subbundle extrusion coating paper, so that graphene oxide infiltration is mutually through between fiber reinforcement, form uniform three-dimensional structure；Utilize stone
The induction graphitizing of black alkene, the height graphite of macroscopic material system can be realized at lower temperature (1800 DEG C~2600 DEG C)
Change, the compound paper material of the high heat-conductivity conducting has the excellent performances such as high heat conduction radiating concurrently.
Compared with prior art, preparation method of the invention employs vacuum filtration, liquid phase volatilization self-assembly method and low temperature
Graphitization is induced, technique is simple, and raw material are easy to get.In addition using high temperature cabonization reduction and graphitization reduction macromolecular fibre and
When graphene oxide composite material, using the induction graphite effect of graphene, high-graphitized crystallite knot can be formed
Structure, while also retain one dimension fibre and the three-dimensional bridging structure of two-dimensional graphene, so that macromolecule prepared by this method is fine
Dimension embodies more excellent mechanical performance, conductive and heat conduction and heat radiation performance with graphene composite material.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 is polyimides pulp fibers skeleton digital photograph prepared by the embodiment of the present invention 1.
Fig. 2 is polyimides pulp fibers and the flexible displaying of graphene oxide composite material prepared by the embodiment of the present invention 1
Digital photograph.
Fig. 3 is polyimides pulp fibers and the flexible exhibition after the reduction of graphene extrusion coating paper prepared by the embodiment of the present invention 1
Show digital photograph.
Fig. 4 is polyimides pulp fibers and the face region after the reduction of graphene extrusion coating paper prepared by the embodiment of the present invention 1
Stereoscan photograph.
Fig. 5 is that the section after polyimides pulp fibers prepared by the embodiment of the present invention 1 reduce with graphene extrusion coating paper is swept
Retouch electromicroscopic photograph.
Fig. 6 is polyimides pulp fibers and the Raman figure after the reduction of graphene extrusion coating paper prepared by the embodiment of the present invention 1
Spectrum.
Embodiment
For the ease of understanding the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to embodiment in detail below.
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of soft graphite alkenyl extrusion coating paper of the present invention as shown in figures 3 to 6, the soft graphite alkenyl extrusion coating paper include
Macromolecular fibre skeleton and graphene base body, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and in ESEM
Lower graphene base body forms the hasp structure of interpenetrating networks, graphene base body and macromolecular fibre skeleton with macromolecular fibre skeleton
Mass ratio control in about 6 ︰ 1.The thickness control of the soft graphite alkenyl extrusion coating paper is at 50 microns.Macromolecular fibre skeleton is main
It is made up of artificial synthesized polyimides pulp fibers, fibre length 3mm.The soft graphite alkenyl extrusion coating paper is in Raman spectrum
In D peak intensities and G peak intensities ratio ID/IGValue about 0.002.
The preparation method of the above-mentioned soft graphite alkenyl extrusion coating paper of the present embodiment, specifically includes following steps：
(1) length 3mm polyimides pulp fibers are discongested scattered, then (pre-dispersed aramid fiber precipitating is fine with bonding agent
Dimension), deionized water be configured to certain density suspension according to the ︰ 800 of 4 ︰ 1 mass ratio, moderate-speed mixer, obtain homogeneous polyamides
Imines pulp fibers slurry；
(2) graphene oxide is prepared using closed oxidizing process：By raw material and reactor prior to refrigerator cold-storage, 1.8g stones are weighed
Ink and 9g potassium permanganate, are put into kettle courage；The about 90mL concentrated sulfuric acids are measured to pour into kettle, after covering kettle cover, ice bath reacts 2 hours,
75 DEG C are reacted 2 hours.3mg/ml graphene oxide dispersion is configured to after the processes such as scrubbed again, filtering, dialysis, ultrasound；
(3) by the polyimides pulp fibers slurry of gained through vacuum filter, 90 DEG C, that vacuum drying 5min obtains screen cloth shape is more
After hole macromolecular fibre skeleton (referring to Fig. 1), it is transferred on 0.45 μm of cellulose acetate miillpore filter, then adds above-mentioned system
The mass ratio control of the graphene oxide dispersion obtained, graphene oxide and polyimide fiber is 6 ︰ 1, through vacuum filtration, is treated
When free graphene oxide dispersion will disappear above filter cake, vacuum system is turned off；Make graphene oxide with
Foregoing macromolecular fibre skeleton forms the hydrogel block for mutually penetrating intertexture；Hydrogel block through liquid phase volatilize self assembly, i.e.,
Obtain polyimides pulp fibers and graphene oxide composite material (referring to Fig. 2)；
(4) obtained polyimide fiber and graphene oxide composite material are subjected to high temperature reduction, the argon at 2300 DEG C
Gas shielded high-temperature process 2.5h, then be compacted by normal temperature, 5Mpa, 3h, obtain the flexibility of high heat-conductivity conducting as shown in figures 3 to 6
Graphene-based extrusion coating paper.
After testing, the test thickness of soft graphite alkenyl extrusion coating paper made from the present embodiment is 50 μm, and thermal conductivity is
1480W/mK, square resistance are 535m Ω/sq, tensile strength 78.68MPa, D peak intensities and G peak intensities in Raman spectrum
The ratio I of degreeD/IGIt is worth for 0.002.By performing paper folding test method, 135 ° of folding angles, bending number is up to 500
More than secondary.
To investigate radiating effect of the soft graphite alkenyl extrusion coating paper of the present invention in actual use, we devise electronics
Chip test system.By loading power, the hot localised points of simulated power chip can be used for, using temperature measurement system and tied
The real-time monitoring system temperature of high-precision infrared thermometer is closed to answer to compare copper foil, commercially available graphite film and soft graphite alkenyl of the present invention
The heat conduction and heat radiation situation of combined paper.The test system is by paper-like radiator (by conductive paste, copper foil, graphite film, extrusion coating paper group of the present invention
Into), insulating box, analog chip (miniature controlled power electric heater) and its runtime and temperature measurement system (Agilent
34970A data collecting instruments and fluke Ti00 infrared temperature measurement systems) composition.In order to intuitively characterize soft graphite alkenyl extrusion coating paper
Heat-sinking capability, copper foil, graphite film, soft graphite alkenyl extrusion coating paper of the present invention are directly adhered on chip by we with conductive paste
(chip is 1 with heat sink size ratio:10), test system is placed in 25 DEG C of insulating boxs, in the constant work(of 5W, 10W, 15W, 20W
The temperature of statistical simulation chip heating surface under rate.
Found after being detected more than, 5, under 10W power, thermal power is smaller, and caloric value is low, passes through hot in paper-like radiator face
Lead hot localised points are uniformly oriented to the natural convection air heat transfer process of surrounding and surface can be quickly by caused by chip
Heat loses, and after persistent fever 40min, chip surface temperature is about：38 DEG C of copper foil, 48 DEG C, 35 DEG C of graphite film, 46 DEG C, this
32 DEG C, 40 DEG C of invention soft graphite alkenyl extrusion coating paper；Under 15W, 20W power after persistent fever 40min, chip surface temperature is about
For：70 DEG C of copper foil, 80 DEG C, 64 DEG C of graphite film, 78 DEG C, 55 DEG C, 60 DEG C of extrusion coating paper of the present invention.By to different firm power conditions
The changing rule observation of the surface temperature of lower electronic chip, it can be seen that soft graphite alkenyl extrusion coating paper of the present invention has fine
Heat conduction and heat radiation ability, can be applied in various radiators (such as transversal radiator) and excellent effect, can also directly be used
Make the radiating paper of mobile phone, computer or other elements, or assembling functional radiator further expands application, also can be in military project state
It is the heat conduction and heat radiation service of device under the extreme condition such as anti-.
Embodiment 2：
A kind of soft graphite alkenyl extrusion coating paper of the invention, the soft graphite alkenyl extrusion coating paper include macromolecular fibre skeleton
And graphene base body, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and under ESEM graphene base body with
Macromolecular fibre skeleton forms the hasp structure of interpenetrating networks, and graphene base body and the mass ratio control of macromolecular fibre skeleton exist
About 8 ︰ 1.The thickness control of the soft graphite alkenyl extrusion coating paper is at 50 microns, and macromolecular fibre skeleton is mainly by artificial synthesized virtue
Synthetic fibre chopped strand (terephthalic acid (TPA) p-phenylenediamine fiber) is formed, and its length is 10mm.The soft graphite alkenyl extrusion coating paper is being drawn
The ratio I of D peak intensities and G peak intensities in graceful spectrumD/IGValue about 0.01.
The preparation method of the above-mentioned soft graphite alkenyl extrusion coating paper of the present embodiment, specifically includes following steps：
(1) length 10mm aramid short fiber is discongested it is scattered, it is then (poly- with bonding agent (polyvinyl alcohol), dispersant
Acrylamide), deionized water be configured to certain density suspension according to the ︰ 1000 of 3 ︰, 5 ︰ 1 mass ratio, wherein polyvinyl alcohol,
Polyacrylamide, deionized water press 3 in advance:1:1000 are made into the aqueous solution, moderate-speed mixer, obtain homogeneous aramid short fiber slurry
Material；
(2) graphene oxide is prepared using closed oxidizing process：By raw material and reactor prior to refrigerator cold-storage, 1.8g stones are weighed
Ink and 9g potassium permanganate, are put into kettle courage；The about 90mL concentrated sulfuric acids are measured to pour into kettle, after covering kettle cover, ice bath reacts 2 hours,
75 DEG C are reacted 2 hours；Graphene oxide point of the graphite oxide by washing, filter, dialyse, being configured to after ultrasonic procedure 6mg/ml
Dispersion liquid；
(3) by the aramid short fiber slurry of gained through vacuum filter, 90 DEG C, vacuum drying 5min obtain the porous height of screen cloth shape
0.22 μm of acetic acid is carefully transferred to after molecular fiber skeleton to mix on fine miillpore filter, then adds graphite oxide obtained above
The mass ratio control of alkene dispersion liquid, graphene oxide and aramid short fiber is 8 ︰ 1, through vacuum filtration, is treated free above filter cake
Graphene oxide dispersion when will disappear, turn off vacuum system；Make graphene oxide fine with foregoing macromolecule
Dimension skeleton forms the hydrogel block for mutually penetrating intertexture；Hydrogel block obtains aramid fiber and is chopped through liquid phase volatilization self assembly
Fiber and graphene oxide composite material；
(4) obtained aramid short fiber and graphene oxide composite material are subjected to high temperature reduction, the argon at 2600 DEG C
Gas shielded high-temperature process 2h, obtain the soft graphite alkenyl extrusion coating paper of high heat-conductivity conducting.
After testing, the test thickness of soft graphite alkenyl extrusion coating paper made from the present embodiment is 50 μm, and thermal conductivity is
1572W/mK, square resistance are 128m Ω/sq, tensile strength 92.8MPa, D peak intensities and G peak intensities in Raman spectrum
Ratio ID/IGIt is worth for 0.01.By performing paper folding test method, 135 ° of folding angles, bending number is up to 600 times
More than.The soft graphite alkenyl extrusion coating paper that the present embodiment is prepared carries out good using rear effect in transversal radiator is prepared
It is good.
Embodiment 3：
A kind of soft graphite alkenyl extrusion coating paper of the invention, the soft graphite alkenyl extrusion coating paper include macromolecular fibre skeleton
And graphene base body, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and under ESEM graphene base body with
Macromolecular fibre skeleton forms the hasp structure of interpenetrating networks, and graphene base body and the mass ratio control of macromolecular fibre skeleton exist
About 8 ︰ 1.The thickness control of the soft graphite alkenyl extrusion coating paper is at 15 microns.Macromolecular fibre skeleton is mainly by artificial synthesized silkworm
Silk is formed, and its length is 10mm or so.D peak intensity and G peak intensity of the soft graphite alkenyl extrusion coating paper in Raman spectrum
Ratio ID/IGValue about 0.01.
The preparation method of the above-mentioned soft graphite alkenyl extrusion coating paper of the present embodiment, specifically includes following steps：
(1) by length 10mm or so silk cocoon fragment, the fibroin of the μ m diameter of diameter about 10~25 is obtained after degumming is dried,
Then certain density suspension is configured to according to the ︰ 800 of 5 ︰ 2 mass ratio with dispersant (polyethylene glycol oxide), deionized water, in
Speed stirring, obtains homogeneous natural silk slurry；
(2) graphene oxide is prepared using electrochemical oxidation process, graphite oxide waited by washing, filtering, dialysis, ultrasound
4mg/ml graphene oxide dispersion is configured to after journey；
(3) it is the natural silk slurry of gained is filtered, it is small after 40 DEG C of dry screen cloth shape porous polymer fiber reinforcements
The heart is transferred on 0.22 μm of nylon micro porous filter membrane, then adds graphene oxide dispersion obtained above, graphene oxide
Mass ratio control with natural silk is 8 ︰ 1, through vacuum filtration, treats that graphene oxide dispersion free above filter cake will disappear
When mistake, vacuum system is turned off；Graphene oxide is formed with foregoing macromolecular fibre skeleton and mutually penetrate intertexture
Hydrogel block；Hydrogel block obtains natural silk and graphene oxide composite material through liquid phase volatilization self assembly；
(4) by obtained natural silk and graphene oxide composite material, argon gas protects high-temperature process 2h at 2600 DEG C,
By 150 DEG C, 5MPa, 5 hours obtain high heat-conductivity conducting soft graphite alkenyl extrusion coating paper after hot compaction.
After testing, the test thickness of soft graphite alkenyl extrusion coating paper made from the present embodiment is 15 μm, and thermal conductivity is
1380W/mK, square resistance are 260m Ω/sq, tensile strength 58.3MPa, D peak intensities and G peak intensities in Raman spectrum
Ratio ID/IGIt is worth for 0.01.By performing paper folding test method, 135 ° of folding angles, bending number is up to 800 times
More than.The soft graphite alkenyl extrusion coating paper that the present embodiment is prepared carries out good using rear effect in transversal radiator is prepared
It is good.
Embodiment 4：
A kind of soft graphite alkenyl extrusion coating paper of the invention, the soft graphite alkenyl extrusion coating paper include macromolecular fibre skeleton
And graphene base body, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and under ESEM graphene base body with
Macromolecular fibre skeleton forms the hasp structure of interpenetrating networks, and graphene base body and the mass ratio control of macromolecular fibre skeleton exist
About 6 ︰ 1.At 100 microns, macromolecular fibre skeleton is mainly chopped fine the thickness control of the soft graphite alkenyl extrusion coating paper by aramid fiber
Dimension is formed, and its length is 10mm.The ratio of D peak intensity and G peak intensity of the soft graphite alkenyl extrusion coating paper in Raman spectrum
ID/IGValue about 0.02.
The preparation method of the above-mentioned soft graphite alkenyl extrusion coating paper of the present embodiment, specifically includes following steps：
(1) length 10mm aramid short fiber is discongested it is scattered, then with bonding agent (pre-dispersed aramid fiber fibrid),
Deionized water is configured to certain density suspension according to the ︰ 800 of 5 ︰ 2 mass ratio, moderate-speed mixer, obtains homogeneous aramid fiber and is chopped
Fibre stuff；
(2) graphene oxide is prepared using improved hummers methods, graphite oxide is by washing, filtering, dialysis, ultrasound
Etc. the graphene oxide dispersion that 5mg/ml is configured to after process；
(3) it is the aramid short fiber slurry of gained is filtered, 40 DEG C of dry screen cloth shape porous polymer fiber reinforcements
Carefully it is transferred on 0.45 μm of nylon micro porous filter membrane afterwards, then adds graphene oxide dispersion obtained above, aoxidizes stone
The mass ratio control of black alkene and aramid short fiber is 6 ︰ 1, through vacuum filtration, treats that graphene oxide free above filter cake disperses
When liquid will disappear, vacuum system is turned off；Graphene oxide is set to form phase IPN with foregoing macromolecular fibre skeleton
The hydrogel block to interweave thoroughly；Hydrogel block obtains aramid short fiber and graphene oxide through liquid phase volatilization self assembly
Composite；
(4) obtained aramid short fiber and graphene oxide composite material are carried out for 2 hours in 1800 DEG C of high-temperature process
Reduction, then after 10MPa, 5 hours, room temperature hot compaction, obtain the soft graphite alkenyl extrusion coating paper of high heat-conductivity conducting.
After testing, the test thickness of soft graphite alkenyl extrusion coating paper made from the present embodiment is 100 μm, and thermal conductivity is
985W/mK, square resistance are 680m Ω/sq, tensile strength 48.6MPa, D peak intensities and G peak intensities in Raman spectrum
Ratio ID/IGIt is worth for 0.02.By performing paper folding test method, 135 ° of folding angles, bending number is up to 200 times
More than.The soft graphite alkenyl extrusion coating paper that the present embodiment is prepared carries out good using rear effect in transversal radiator is prepared
It is good.
Comparative example：
A kind of soft graphite alkenyl extrusion coating paper, the soft graphite alkenyl extrusion coating paper include macromolecular fibre skeleton and graphene
Matrix, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and graphene base body and macromolecule are fine under ESEM
The hasp structure that skeleton forms interpenetrating networks is tieed up, graphene base body and the mass ratio of macromolecular fibre skeleton are controlled in about 10 ︰ 1.
The thickness control of the soft graphite alkenyl extrusion coating paper is at 60 microns, and macromolecular fibre skeleton is mainly by artificial synthesized polyimides
Chopped strand is formed, and its length is 3mm.D peak intensity and G peak intensity of the soft graphite alkenyl extrusion coating paper in Raman spectrum
Ratio ID/IGValue about 0.05.
The preparation method of above-mentioned soft graphite alkenyl extrusion coating paper, specifically includes following steps：
(1) length 3mm polyimides chopped strand is discongested it is scattered, then with bonding agent (polyvinyl alcohol), dispersant
(polyethylene glycol oxide), deionized water are configured to certain density suspension, wherein polyethylene according to the ︰ 1000 of 2 ︰, 4 ︰ 1 mass ratio
Alcohol, polyethylene glycol oxide, deionized water press 3 in advance:1:1000 are made into the aqueous solution, moderate-speed mixer, it is short to obtain homogeneous polyimides
Cut fibre stuff；
(2) graphene oxide is prepared using improved hummers methods, graphite oxide is by washing, filtering, dialysis, ultrasound
Etc. the graphene oxide dispersion that 6mg/ml is configured to after process；
(3) by the polyimides chopped strand slurry of gained through vacuum filter, 90 DEG C, that vacuum drying 5min obtains screen cloth shape is more
After the macromolecular fibre skeleton of hole, carefully it is transferred on 0.45 μm of cellulose acetate miillpore filter, then adds obtained above
The mass ratio control of graphene oxide dispersion, graphene oxide and polyimide fiber is 10 ︰ 1, through vacuum filtration, treats filter cake
When the free graphene oxide dispersion in top will disappear, vacuum system is turned off；Make graphene oxide with it is foregoing
Macromolecular fibre skeleton forms the hydrogel block for mutually penetrating intertexture；Hydrogel block obtains through liquid phase volatilization self assembly
Polyimides chopped strand and graphene oxide composite material；
(4) obtained polyimides chopped strand and graphene oxide composite material are immersed in 55% hydroiodic acid-ice second
Direct electronation is carried out in sour mixed acid, 40 DEG C of reduction temperature, takes out after 24h, is washed by saturated sodium bicarbonate, water, methanol
After washing, soft graphite alkenyl extrusion coating paper is obtained.
After testing, the test thickness of soft graphite alkenyl extrusion coating paper made from this comparative example is 60 μm, thermal conductivity 468W/
MK, square resistance are 1.3k Ω/sq, tensile strength 120.5MPa, the ratio of D peak intensities and G peak intensities in Raman spectrum
Value ID/IGIt is worth for 0.05.By performing paper folding test method, 135 ° of folding angles, bending number is up to more than 100 times.
Embodiment as a comparison, the present embodiment are based on chemical reducing agent direct-reduction process, thermal conductivity factor and electric conductivity prepared by the method
The extrusion coating paper that can be prepared significantly lower than high temperature graphitization method.This aspect is macromolecular fibre sheet as low thermal conductivity material,
Graphene of the heat conductivility of other top layer redox graphene also below high temperature graphitization.
Claims (10)
1. a kind of soft graphite alkenyl extrusion coating paper, it is characterised in that the soft graphite alkenyl extrusion coating paper includes macromolecular fibre
Skeleton and graphene base body, the graphite-structure defect of the soft graphite alkenyl extrusion coating paper is few, and the graphite-structure defect has less
Body is embodied in the ratio I of D peak intensity and G peak intensity of the soft graphite alkenyl extrusion coating paper in Raman spectrumD/IGValue is less than
Or equal to 0.05；And graphene base body forms the hasp structure of interpenetrating networks with macromolecular fibre skeleton.
2. soft graphite alkenyl extrusion coating paper according to claim 1, it is characterised in that the graphene base body and macromolecule
The mass ratio of fiber reinforcement is controlled in 5~11 ︰ 1.
3. soft graphite alkenyl extrusion coating paper according to claim 1, it is characterised in that the soft graphite alkenyl extrusion coating paper
Thermal conductivity in more than 950W/mK, square resistance be 1 Ω/below sq, tensile strength is in more than 28.0MPa；By performing paper
Folding test method is opened, 135 ° of folding angles, bending number is up to more than 100 times.
4. soft graphite alkenyl extrusion coating paper according to claim 1, it is characterised in that selected macromolecular fibre skeleton is main
From at least one of following macromolecular fibre：Polyimide fiber, polyester fiber, poly terephthalic acid p-phenylenediamine are fine
Dimension, vinal, polyacrylonitrile fibre, wool, silk, linen-cotton.
It is 5. a kind of as the preparation method of soft graphite alkenyl extrusion coating paper according to any one of claims 1 to 4, its feature exist
In comprising the following steps：The macromolecular fibre skeleton prepared is taken to be placed on miillpore filter, then the graphite oxide that will have been configured
Alkene dispersion liquid pours into above macromolecular fibre skeleton and carries out decompression suction filtration, then will depressurize filtered hydrogel block through liquid phase
Volatilization self assembly obtains graphene oxide/macromolecular fibre extrusion coating paper, then is reduced, follow-up alternative compacting, high temperature induction
Graphitization obtains product.
6. preparation method according to claim 5, it is characterised in that by the macromolecular fibre slurry of preparation it is filtered, dry
It is dry to obtain the porous macromolecular fibre skeleton of screen cloth shape；
The macromolecular fibre slurry is mainly made up of macromolecular fibre, bonding agent, dispersant and deionized water, wherein macromolecule
Fiber, bonding agent, the mass ratio of dispersant are the ︰ 0~5 of 0.05~10 ︰ 0~15；The macromolecular fibre, bonding agent, dispersant
Summation and deionized water mass ratio control be 0.05~20 ︰ 100~5000.
7. preparation method according to claim 6, it is characterised in that the bonding agent is polyvinyl alcohol, polyethylene glycol, hydroxyl
One or more in methylcellulose, polyvinylpyrrolidone, are either polymer fibrids or are paper pulp wood pulp；
The dispersant is at least one of polyethylene glycol oxide, polyacrylamide.
8. the preparation method according to any one of claim 5~7, it is characterised in that the decompression suction filtration specifically refers to
Graphene oxide dispersion is added on to the miillpore filter for having completed macromolecular fibre skeleton to be filtered by vacuum, and is treated above filter cake
When free graphene oxide dispersion will disappear, vacuum system is turned off；
Graphene oxide in the graphene oxide dispersion is made by wet chemistry method, and the wet chemistry method includes electrochemistry oxygen
Change method, hummers methods, closed oxidizing process, obtained graphene oxide are configured to oxygen after washing and filtering, dialysis, ultrasound
Graphite alkene dispersion liquid, the concentration control of the graphene oxide dispersion is 1-15mg/mL.
9. the preparation method according to any one of claim 5~7, it is characterised in that the reduction is using at high warm
Logos, the graphitization temperature of the high-temperature heat treatment method is 1800 DEG C~2600 DEG C.
10. soft graphite alkenyl a kind of as described in Claims 1 to 4 or that such as any one of claim 5~9 is prepared
Application of the extrusion coating paper in radiating paper, feature radiator is prepared.
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| CN108589268A (en) * | 2018-04-13 | 2018-09-28 | 西安交通大学 | A kind of conductive-nano-fibers material and preparation method |
| CN109956466B (en) * | 2019-04-10 | 2021-09-03 | 湖南大学 | Graphene-based composite film with high thermal conductivity in-plane direction and thickness direction and preparation method thereof |
| CN110184855B (en) * | 2019-05-15 | 2020-11-10 | 西安交通大学 | Breathable and water-washable composite flexible conductive paper and preparation method and application thereof |
| CN110983758A (en) * | 2019-11-05 | 2020-04-10 | 西安科汇电子科技有限公司 | Preparation method of conductive silk fibroin film for flexible mechanical sensor |
| CN113184836A (en) * | 2021-05-11 | 2021-07-30 | 华南理工大学 | High-thermal-conductivity graphene film and preparation method thereof |
| CN113421866B (en) * | 2021-06-11 | 2023-06-30 | 信骅(上海)器材有限公司 | Graphene cooling fin with three-dimensional structure and ultrahigh vertical heat conduction coefficient for semiconductor component and manufacturing method thereof |
| CN113430865B (en) * | 2021-06-11 | 2022-08-16 | 华南理工大学 | High-strength high-conductivity synthetic fiber/graphene composite paper and preparation method thereof |
| CN114853002A (en) * | 2022-05-13 | 2022-08-05 | 武汉理工大学 | Preparation method and application of high-order-degree graphite film |
| CN116515163A (en) * | 2023-05-06 | 2023-08-01 | 四川大学 | Structure/wave absorbing integrated composite material prepared by in-situ foaming filling aramid fiber honeycomb and application thereof |
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