CN118496667A - Heat-conducting composite film and preparation method thereof, and precursor slurry for manufacturing heat-conducting composite film and preparation method thereof - Google Patents
Heat-conducting composite film and preparation method thereof, and precursor slurry for manufacturing heat-conducting composite film and preparation method thereof Download PDFInfo
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- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 claims description 7
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of polymer composite materials, in particular to a heat-conducting composite film and a preparation method thereof, and precursor slurry for manufacturing the heat-conducting composite film and a preparation method thereof, wherein the preparation method of the precursor slurry comprises the following steps: adding expanded graphite into the poly (paraphenylene terephthalamide) nanofiber solution to form a mixed solution; freezing the mixed solution until the mixed solution is completely frozen, and stirring at a rotating speed of over 1900 rpm to strip the expanded graphite to form a dispersion; adding excessive proton-donating solvent into the dispersion liquid, fully stirring and dispersing, and carrying out suction filtration to obtain precursor slurry. The precursor slurry is prepared by a one-pot method, so that the efficient stripping and dispersion of the heat conducting filler are realized, meanwhile, the efficient assembly of the organic polymer nanofiber and the polymer nanofiber is realized through interface interaction, the organic polymer nanofiber is adhered to the surface of an inorganic heat conducting material, and the low filler-matrix interface thermal resistance of the composite film is endowed by virtue of intermolecular interaction between chemical structures between the organic fiber and the inorganic heat conducting filler.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a heat-conducting composite film and a preparation method thereof, and precursor slurry for manufacturing the heat-conducting composite film and a preparation method thereof.
Background
At present, electronic components are rapidly developed towards miniaturization and integration, and the performance is greatly improved along with accumulation of a large amount of heat generation and heat, so that the service life, stability and reliability of the electronic components are seriously affected, and therefore, efficient removal of waste heat or waste heat becomes a key problem for further development of the electronic components. For this reason, development of a thermal management material excellent in heat conductive property is demanded.
In recent years, a great deal of research has focused on designing and manufacturing polymer-based thermally conductive composite materials with high thermal conductivity, and previous research has found that thermally conductive micro-flake fillers with high crystalline structures (such as graphite, boron nitride, silver, etc.) may be more practical for the thermal conductivity of the composite materials, and such high quality thermally conductive fillers are beneficial to reducing the production cost of thermally conductive composite materials. Meanwhile, the inorganic heat conducting filler with a two-dimensional structure can endow the composite material with excellent in-plane heat conductivity coefficient, and has good application prospect in the field of heat management.
The two-dimensional graphene is used as a common high-heat-conductivity filler, the honeycomb crystal lattice endows the high-heat-conductivity filler with ultrahigh in-plane heat conductivity, but the high-quality graphite heat-conductivity filler prepared at present usually utilizes a liquid phase to assist in stripping, the main principle is that van der Waals force between graphite sheets is overcome by utilizing the action of shearing force to prevent lattice defects, and the prepared filler is smaller in general size, relatively complex in method and higher in cost. Meanwhile, such small-sized micro-platelets are generally used in the preparation of composite materials to ensure dispersibility of the filler in a polymer system, however, such thermally conductive micro-platelets tend to generate more filler-filler and filler-matrix interfaces in a matrix, thereby limiting further improvement of thermal conductivity. In contrast, the preparation of the large-size heat conduction microchip is more beneficial to reducing high interface thermal resistance and radically improving in-plane heat conduction. At present, it is difficult to form high-quality large-size graphite sheets by breaking Van der Waals force between graphite sheet layers, and high cost is required by chemical vapor deposition, so that it is still required to efficiently prepare large-size graphite micro-sheets by a simple and energy-saving method to meet the requirement of reducing interface thermal resistance.
Disclosure of Invention
Based on the technical problems, the invention provides a heat-conducting composite film and a preparation method thereof, and precursor slurry for manufacturing the heat-conducting composite film and a preparation method thereof, so as to solve the problems of high preparation cost, difficult operation, high filler-filler interface thermal resistance and high filler-matrix interface thermal resistance of the conventional small-size heat-conducting micro-plate which is limited by the contribution of the conventional small-size heat-conducting micro-plate to heat conductivity.
To achieve the above object, according to an aspect of the present invention, there is provided a method for preparing a precursor slurry for manufacturing a thermally conductive composite film, comprising the steps of:
1) Preparing a poly-p-phenylene terephthamide nanofiber solution, wherein the solvent is dimethyl sulfoxide and deionized water; adding expanded graphite into the poly (paraphenylene terephthalamide) nanofiber solution to form a mixed solution;
2) Freezing the mixed solution obtained in the step 1) until the mixed solution is completely frozen, and mechanically stirring at a rotating speed of over 1900 rpm to strip the expanded graphite to obtain a dispersion liquid;
3) Adding excessive proton-donating solvent into the dispersion liquid in the step 2), fully stirring, dispersing, and carrying out suction filtration to obtain precursor slurry, wherein the proton-donating solvent is one or a mixture of more of ethanol, methanol and deionized water.
The precursor slurry has long-term stability, uniformity and convenient storage, and is mainly prepared from expanded graphite with the surface attached with poly-p-phenylene terephthamide nanofiber (ANF), and is prepared by rapidly stirring a mixed solution of the poly-p-phenylene terephthamide nanofiber (ANF) and the expanded graphite after freezing, stripping and dispersing the expanded graphite, and assembling the expanded graphite with polymer fibers. The precursor slurry is a compound of the high molecular organic nanofiber and the expanded graphite as the heat conducting filler, and the heat conducting filler is used as a main structure, so that the organic high molecular nanofiber is firmly adhered to the surface of the heat conducting filler through intermolecular interaction, the interface thermal resistance of the filler-matrix is greatly reduced, and phonon scattering is reduced.
Optionally, the mass concentration of the poly (paraphenylene terephthalamide) nanofiber solution is 0.1% -5.0%, which can be typical but not limited to mass concentrations of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 4% and the like. If the mass concentration of the poly (paraphenylene terephthamide) nanofiber solution is too high, the preparation is difficult, and the viscosity of the system is too high, which is not beneficial to stirring and dispersing. Preferably, the mass concentration of the poly (paraphenylene terephthamide) nanofiber solution is 0.2%, the manufacturing method is mature, the system viscosity is moderate, and the dispersion of the heat conducting filler is facilitated.
Optionally, the mass ratio of the solid content of the poly (paraphenylene terephthalamide) nanofiber solution to the feeding amount of the expanded graphite is 1:0.01 to 20, may be 1:0.01, 1:0.1, 1: 1. 1: 10. 1:20, etc., typically but not limited to weight percent. Too little addition of the heat conducting material leads to insufficient improvement of the heat conducting performance, and too much addition affects the integral mechanical property of the composite material.
The expanded graphite is an inorganic heat-conducting material with a two-dimensional structure, the interlayer of the expanded graphite is combined by Van der Waals force, the expanded graphite is easily damaged by shearing force, and compared with chemical stripping, the expanded graphite is not easy to damage an intrinsic structure or introduce redundant chemical elements. Meanwhile, the special length-diameter ratio of the two-dimensional multilayer filler is beneficial to preparing the heat conduction composite film with in-plane orientation, so that high in-plane heat transfer efficiency is realized. The expanded graphite has high heat conduction contribution degree of a high-degree crystal structure, stable chemical property and no corrosiveness, and has good development prospect. Meanwhile, the expanded graphite has a loose stacked structure, and the interaction between layers is easily broken through volume expansion, so that the expanded graphite is easily peeled off under the action of shearing force, and the expanded graphite has a transverse large size. Preferably, the average lateral dimension of the graphite platelet obtained after exfoliation is 25-30 μm.
According to the invention, the poly-p-phenylene terephthamide fiber (PPTA) is used as an organic polymer fiber matrix, and the organic polymer fiber material has high intrinsic heat conductivity, high thermal stability and excellent mechanical property, and can be endowed with synchronous improvement of heat conduction performance and mechanical property of the heat conduction composite film through a fiber interconnection network structure.
Further, a poly-paraphenylene terephthalamide nanofiber (ANF) solution was obtained from the dissociation of poly-paraphenylene terephthalamide fibers. The poly (p-phenylene terephthamide) nanofiber (ANF) has a benzene ring structure and rich surface groups (-OH), and can easily form interactions with the expanded graphite, such as hydrogen bonds, pi-pi interactions and the like, so that the interface heat transmission efficiency is improved. In the invention, poly-p-phenylene terephthalamide nanofiber (ANF) is easy to bond with graphite micro-plates through pi-pi interaction through benzene rings on molecular chain structures.
Preferably, the poly (paraphenylene terephthalamide) nanofiber solution is prepared by the steps of:
adding the poly-p-phenylene terephthalamide fiber and potassium hydroxide into a mixed solvent of dimethyl sulfoxide and deionized water, and dissociating the poly-p-phenylene terephthalamide fiber by stirring to obtain a poly-p-phenylene terephthalamide nanofiber solution.
Optionally, a uniform mixed dispersion containing poly (paraphenylene terephthalamide) nanofibers (ANF) and large-size graphite platelets is prepared, and the rapid stirring (1900 rpm or more) is adjusted to a time of 20 minutes or more, which may be typical but not limiting rapid stirring times of 20 min, 30min, 40 min, 50 min, 60 min, etc. The stirring speed can be 1900 rpm, 2000 rpm, 2300 rpm, 2500 rpm, and the like, which is typical but not limiting. During stirring, the frozen multi-layer expanded graphite is peeled off by using a rapid shearing force, the interlayer Van der Waals force is destroyed, and the intrinsic structure of the heat conduction micro-plate is maintained to the greatest extent in the peeling process. The graphite heat conduction microchip with larger transverse dimension prepared by the invention is beneficial to constructing in-plane orientation and promoting the mutual lap joint between fillers in the composite material, forming an effective heat conduction path and realizing high in-plane heat transfer.
Alternatively, the freezing temperature is below-20 ℃, and may be a typical but non-limiting freezing temperature of-20 ℃, -25 ℃, -30 ℃, and the like, and likewise, the freezing time is above 2h, and may be a typical but non-limiting freezing time of 2h, 3 h, 4 hours, and the like.
Alternatively, in preparing a laterally large-sized graphite thermally conductive micro-sheet solid composite with poly (paraphenylene terephthalamide) nanofibers (ANF) adhered thereto, the fibrous structure may be restored by adding a protonating solvent (i.e., a proton donating solvent) comprising one or a mixture of several of ethanol, methanol, deionized water, preferably deionized water. The poly-p-phenylene terephthamide fiber (PPTA) has chemical inertness and stable structure, can destroy hydrogen bond interaction among fiber molecular chains through strong alkali action to lose proton hydrogen atoms so as to be dissociated to obtain nanofiber solution, and can obtain hydrogen atoms and restore the original molecular chain structure after the protonation solvent is added. The effective adhesion of the fibers to the thermally conductive micro-sheets in the present invention requires the integrated construction of the complete fiber and filler assembly by the protonated solvent.
Alternatively, the preparation of the precursor slurry with complete fiber network requires adjustment of the protonation recovery time, and the mechanical agitation time can be more than 1h, and can be typical but not limiting mechanical agitation times of 1h, 2h, 3h, etc. Considering that the invention requires a complete fiber network to ensure effective improvement of heat conduction performance and mechanical property, excessive protonation solvent and enough protonation time are helpful to ensure that the poly-paraphenylene terephthalamide nanofiber obtains hydrogen atoms and recovers hydrogen bonds at the same time so as to realize recovery of the chemical structure of the original special fiber.
According to another aspect of the invention, the invention further provides a precursor slurry, which is prepared by the method.
According to another aspect of the present invention, the present invention also provides a method for preparing a heat conductive composite film, comprising the steps of:
Dispersing the prepared precursor slurry in a solvent, stirring and dispersing uniformly, then carrying out vacuum filtration, and drying to obtain a heat-conducting composite film; the solvent is one or a mixture of more of ethanol, methanol and deionized water.
The invention utilizes the negative pressure in the suction filtration process to promote the horizontal arrangement of precursor slurry and design a layered orientation structure, and finally carries out drying and cold pressing treatment, and a layered structure constructed by an inorganic heat conduction microchip material and a poly-p-phenylene terephthamide nanofiber (ANF) matrix material is reserved, so that the heat conduction composite film material is prepared. The precursor slurry is added and uniformly dispersed in deionized water to obtain precursor aqueous dispersion, and the precursor aqueous dispersion is subjected to vacuum suction filtration, drying and cold pressing treatment to obtain the heat-conducting composite film material.
The composite film material containing a small amount of deionized water, which is prepared by vacuum filtration, is placed in a vacuum oven, and the solvent is volatilized at 40-80 ℃ and can be typical but non-limiting volatilization temperatures of 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ so as to completely remove the solvent. The drying time is 8-12 h, which can be 8h, 9 h, 10 h, 11 h, 12 h and other typical but non-limiting drying times, and the longer the drying time, the more the solvent in the composite film can be removed completely.
Preferably, the solvent used to prepare the thermally conductive composite film is the same as the proton donating solvent used to prepare the precursor slurry.
According to another aspect of the invention, the invention also provides a heat-conducting composite film, which is prepared by the method. Preferably, the thickness dimension of the obtained heat-conducting composite film is 30-35 mu m.
Compared with the prior art, the invention has the following beneficial effects:
The heat-conducting composite film material with high heat conductivity and excellent mechanical property has a layered orientation structure, can achieve a better in-plane heat transfer effect, is obtained by vacuum filtration and drying treatment of precursor slurry containing an organic polymer nanofiber matrix (poly-paraphenylene terephthalamide nanofiber) material and an expanded graphite material, and has the advantages of simple preparation method, easily obtained material, low cost, realization under mild conditions and easy realization of industrial production of the heat-conducting composite film material.
The precursor slurry provided by the invention is prepared by a one-pot method, so that the high-efficiency stripping and dispersing of the expanded graphite are realized, and meanwhile, the high-efficiency assembly of the high-molecular nanofiber is realized through interface interaction. The peeled and dispersed graphite micro-plates are used as heat conducting filler, the organic polymer nano-fibers are adhered to the surface of the heat conducting filler, and the low filler-matrix interface thermal resistance of the composite film is endowed by means of intermolecular interaction between chemical structures between the organic fibers and the heat conducting filler. The heat conducting filler is effectively lapped to form an in-plane orientation structure, and the heat conducting path of homogeneous interconnection greatly reduces the interface thermal resistance between the filler and the filler, and heat is rapidly transmitted in a network with inherent high phonon transmission efficiency, so that the heat conducting performance of the composite material is greatly improved, and the interface thermal barrier between the filler and the filler is reduced. The heat-conducting property and the mechanical property of the composite material are synchronously improved, and the heat-conducting material can be applied to realize the heat management of high-efficiency electronic equipment.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a macro morphology of a precursor slurry of example 1 of the present invention;
FIG. 2 is a schematic and schematic diagram of a precursor slurry dispersion according to example 1 of the present invention;
FIG. 3 is a diagram of the microscopic morphology of the two-dimensional structured thermal conductive filler expanded graphite used in the present invention;
FIG. 4 is a graph of the microscopic morphology of large-sized graphite micro-platelets prepared in example 1 of the present invention;
FIG. 5 is a cross-sectional electron microscope of the heat conductive composite film prepared in example 6 of the present invention;
FIG. 6 shows the long-term stability of the thermally conductive composite film prepared from the precursor slurry of example 1 of the present invention, with the number of days of presence being 1, 7 and 14, respectively;
FIG. 7 is a comparison of the thermal conductivity of the thermally conductive composite films prepared in example 2 and comparative example 2 of the present invention;
FIG. 8 is a comparison of mechanical properties of the thermally conductive composite films prepared in example 2 and comparative example 2 of the present invention;
fig. 9 is a comparison of heat conductive properties of the heat conductive composite films prepared in example 2 and comparative example 8 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
Example 1
The preparation method of the precursor slurry for manufacturing the heat-conducting composite film comprises the following steps:
First, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA), 0.45 g potassium hydroxide (KOH) were weighed into a 250 mL round bottom flask, and 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water were added, and the solution was rapidly stirred for 4h at a speed of 1000 rpm to dissociate PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution with a mass percentage concentration of 0.2%.
Weighing 0.7 g of Expanded Graphite (EG), adding into the solution of the poly (p-phenylene terephthamide) nanofiber (ANF), and placing in a refrigerator for freezing treatment to ensure that the solution is completely frozen. And then, in an icing environment, rapidly stirring at a rotating speed of 1900 rpm for 20: 20min to obtain a mixed solution of large-size graphite micro-plates (GMP) and poly (p-phenylene terephthamide) nanofibers (ANF).
The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1 h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water from the stirred precursor solution by suction filtration to obtain precursor slurry.
The appearance of the precursor slurry sample prepared in this embodiment is shown in fig. 1, and slurry particles form a certain network structure due to interaction and steric hindrance, so that the precursor slurry sample is convenient to store and transport.
Fig. 2 is a schematic structural diagram and a schematic diagram of the precursor slurry dispersion provided in example 1, wherein benzene ring groups in the poly (paraphenylene terephthalamide) nanofibers and six-membered rings of large-sized graphite form pi-pi stacking, so that the fibers are tightly adhered to both sides of the heat conductive filler.
FIG. 3 is a microscopic morphology of the expanded graphite of the two-dimensional structure heat conductive filler, and it is evident that the expanded graphite sheets are loosely stacked and are easily peeled off by shearing;
Fig. 4 is a microscopic morphology of the prepared large-size graphite micro-plate, and it can be clearly seen that the graphite has been completely exfoliated from the expanded graphite and has a large independent lamellar structure, which can meet the requirements of the invention.
Example 2
A proper amount of precursor slurry in the example 1 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20 min hours, the moisture is removed by a vacuum filtration method, and the mixture is dried in a vacuum oven at 60 ℃ for 12 hours with a filter membrane, so that the mass ratio of GMP/ANF is 7:3, the thickness of the heat conduction composite film is 30-35 mu m.
The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 75.83 mm 2/s through a flash heat conduction instrument; the mechanical properties of the films were tested by a universal test stretcher, wherein the tensile strength was 14.99 MPa and the elongation at break was 2.61%.
Example 3
Firstly, 0.3g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) are weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water are added, and the solution is rapidly stirred for 4h at a rotating speed of 1000 rpm to dissociate the PPTA to obtain the poly (p-phenylene terephthalamide) nanofiber (ANF) solution, wherein the mass percentage concentration is 0.2%.
Weighing 0.3 g of Expanded Graphite (EG), adding into the poly (p-phenylene terephthamide) nanofiber (ANF) solution, and placing in a refrigerator for freezing treatment to ensure that the solution is completely frozen. And then, in an icing environment, rapidly stirring at a rotating speed of 1900 rpm for 20: 20 min to obtain a mixed solution of large-size graphite micro-plates (GMP) and poly (p-phenylene terephthamide) nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
Example 4
A proper amount of precursor slurry in the example 3 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20 min hours, the moisture is removed by a vacuum filtration method, and the mixture is dried in a vacuum oven at 60 ℃ for 12 hours with a filter membrane, so that the mass ratio of GMP/ANF is 5:5, the thickness of the heat conduction composite film is 30-35 mu m.
The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film was measured by a flash heat conduction meter and was 52.26 mm 2/s, and the mechanical properties of the film were measured by a universal tester, wherein the tensile strength was 47.88: 47.88 MPa and the elongation at break was 4.56%.
Example 5
First, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) were weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water were added, and the solution was rapidly stirred at 1000 rpm to 4h to dissociate PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution at a concentration of 0.2%.
And weighing 0.1285 g Expanded Graphite (EG), adding the EG into the poly (p-phenylene terephthamide) nanofiber (ANF) solution, and placing the solution in a refrigerator for freezing treatment to ensure that the solution is completely frozen. And then, in an icing environment, rapidly stirring at a rotating speed of 1900 rpm for 20: 20 min to obtain a mixed solution of large-size graphite micro-plates (GMP) and poly (p-phenylene terephthamide) nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1 h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
Example 6
A proper amount of precursor slurry in the example 5 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20 min, the moisture is removed by a vacuum filtration method, and the mixture is dried in a vacuum oven at 60 ℃ for 12 hours with a filter membrane, so that the mass ratio of GMP/ANF is 3:7, the thickness of the heat conduction composite film is 30-35 mu m.
The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 38.86 mm 2/s by a flash heat conduction instrument, and the mechanical property of the film is 78.06 MPa by a universal testing machine, wherein the elongation at break is 5.98%. Fig. 5 is a cross-sectional electron microscope image of the heat conducting composite film prepared in this example, and it can be seen that the film forms a dense structure with high in-plane orientation, and meanwhile, large-size graphite micro-plates directly overlap heat conducting paths with high heat transmission in the material, and nanofibers form tight connection on two sides of the filler, so that the thermal resistance between the filler and the matrix is reduced.
Comparative example 1
As a comparative experiment in example 1, the mixed dispersion was not frozen during the preparation of the precursor slurry, and the specific steps were as follows:
Firstly, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) are weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water are added, and the solution is rapidly stirred for 4h at a rotating speed of 1000 rpm to dissociate the PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution with a mass concentration of 0.2%.
0.7 G Expanded Graphite (EG) was weighed into the poly (paraphenylene terephthalamide) nanofiber (ANF) solution described above. Then rapidly stirring at a rotating speed of 1900 rpm and 20: 20min to obtain a mixed solution of large-size Graphite Microplates (GMP) and poly-p-phenylene terephthamide nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
The precursor slurry prepared in comparative example 1 has poor dispersibility, is easily agglomerated, and has poor long-term stability because it is not subjected to freezing treatment. For comparative tests of the long-term stability of the precursor slurries prepared in example 1 and comparative example 1 and their effect on heat conductivity, three groups of samples were taken for each, and the degree of dispersion when stored in 1, 7, 14 was observed for comparison, it can be seen that: the precursor slurry of example 1 exhibited uniformity and redispersibility after 7 days and 14 days of storage, and the thermal conductivity of the film formed after vacuum filtration remained unchanged from that of the film after 1 day of storage (as shown in fig. 6); in contrast, comparative example 1 was severely agglomerated after long-term storage (not more than 7 days), and could not be uniformly dispersed again, and thus a complete film could not be formed by vacuum filtration, and the heat conductive property test could not be performed normally.
Comparative example 2
Taking a proper amount of precursor slurry of comparative example 1 (stored for no more than 1 day), adding deionized water for dispersion, stirring at room temperature for 20 min, removing water by a vacuum filtration method, and placing an attached filter membrane in a vacuum oven at 60 ℃ for drying for 12 hours to obtain a GMP/ANF mass ratio of 7:3, and the thickness of the heat conduction composite film is about 30-35 mu m. The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 45.90 mm 2/s by a flash heat conduction instrument, and the mechanical property of the film is tested by a universal testing machine, wherein the tensile strength is 8.14 MPa, and the elongation at break is 2.13%.
As can be seen from the difference in heat conductive properties between the heat conductive composite thin film materials prepared in example 2 and comparative example 2 of fig. 7, since the large-sized graphite micro-flakes prepared without the freezing treatment were not completely peeled off, and the dispersibility was poor, the heat conductivity was far lower than that of the heat conductive composite thin film obtained by the freezing treatment.
As can be seen from the difference in mechanical properties between the thermally conductive composite film materials prepared in example 2 and comparative example 2 of fig. 8, the large-sized graphite micro-flakes prepared without the freezing treatment have poor dispersibility and excessive interlayer voids, resulting in inferior mechanical strength compared with the thermally conductive composite film obtained by the freezing treatment.
In summary, the precursor slurry can be prepared by two processing modes of freezing and non-freezing, so that two composite films with different heat conducting properties and mechanical properties are prepared, and as can be seen from example 1 and comparative example 1, the uniformity and long-term storage property of the precursor slurry prepared by the obtained freezing processing and the precursor slurry prepared by the non-freezing processing are obviously different. The precursor slurry is prepared by jointly assembling the organic polymer nano-fibers and the large-size heat-conducting micro-plates, and the high-efficiency and high-quality preparation of the large-size micro-plates is beneficial to endowing the slurry with uniformity, and meanwhile, the precursor slurry is not easy to aggregate under long-term storage conditions and has repeated dispersibility. The compounding of the organic polymer nano-fibers further promotes the improvement of the mechanical property of the heat conduction composite film; and enhancing the interface interaction between the microchip and the matrix, and further improving the heat conduction performance of the heat conduction composite film.
Comparative example 3
First, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) were weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water were added, and the solution was rapidly stirred at 1000 rpm to 4h to dissociate PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution at a concentration of 0.2%.
0.3 G Expanded Graphite (EG) was weighed into the poly (paraphenylene terephthalamide) nanofiber (ANF) solution described above. Then rapidly stirring at a rotating speed of 1900 rpm and 20: 20min to obtain a mixed solution of large-size Graphite Microplates (GMP) and poly-p-phenylene terephthamide nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
Comparative example 4
A proper amount of precursor slurry in comparative example 3 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20 min ℃, water is removed by a vacuum filtration method, and an attached filter membrane is placed in a vacuum oven at 60 ℃ for drying for 12 hours, so that the mass ratio of GMP/ANF is 5:5, the thickness of the heat conduction composite film is 30-35 mu m. The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 38.11 mm 2/s by a flash heat conduction instrument, and the mechanical property of the film is tested by a universal tester, wherein the tensile strength is 30.47 MPa, and the elongation at break is 3.96%.
Comparative example 5
First, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) were weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water were added, and the solution was rapidly stirred at 1000 rpm to 4h to dissociate PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution at a concentration of 0.2%.
The 0.1285 g Expanded Graphite (EG) was weighed into the poly (paraphenylene terephthalamide) nanofiber (ANF) solution described above. Then rapidly stirring at a rotating speed of 1900 rpm and 20: 20 min to obtain a mixed solution of large-size Graphite Microplates (GMP) and poly-p-phenylene terephthamide nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
Comparative example 6
A proper amount of precursor slurry in comparative example 5 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20 min, water is removed by a vacuum filtration method, and an attached filter membrane is placed in a vacuum oven at 60 ℃ for drying for 12 hours, so that the mass ratio of GMP/ANF is 3:7, the thickness of the heat conduction composite film is 30-35 mu m. The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 15.45 mm 2/s by a flash heat conduction instrument, and the mechanical property of the film is tested by a universal testing machine, wherein the tensile strength is 37.23 MPa, and the elongation at break is 5.25%.
TABLE 1 Performance test results of thermally conductive composite films
Comparative example 7
As a comparative experiment of example 1, the difference from example 1 was only that the rotation speed of stirring peeling was reduced.
First, 0.3 g poly (p-phenylene terephthalamide) fiber (PPTA) and 0.45 g potassium hydroxide (KOH) were weighed into a 250 mL round bottom flask, 150 mL dimethyl sulfoxide (DMSO) and 6 mL deionized water were added, and the solution was rapidly stirred at 1000 rpm to 4h to dissociate PPTA to obtain a poly (p-phenylene terephthalamide) nanofiber (ANF) solution at a concentration of 0.2%.
0.7 G Expanded Graphite (EG) was weighed into the poly (paraphenylene terephthalamide) nanofiber (ANF) solution described above. And then rapidly stirring at a rotating speed of 1600 rpm and 20: 20min to obtain a mixed solution of large-size graphite micro-plates (GMP) and poly-p-phenylene terephthamide nanofibers (ANF). The volume ratio of the added solution to the mixed solution is 1:9 to provide sufficient protons for ANF, stirring 1h at room temperature to uniformly disperse to obtain a precursor solution, and removing a large amount of deionized water by suction filtration to obtain precursor slurry.
Comparative example 8
A proper amount of precursor slurry in comparative example 7 is taken, deionized water is added for dispersion, and the mixture is stirred at room temperature for 20min, the moisture is removed by a vacuum filtration method, and the mixture is dried in a vacuum oven at 60 ℃ for 12 hours with a filter membrane, so that the mass ratio of GMP/ANF is 7:3, the thickness of the heat conduction composite film is 30-35 mu m. The thermal diffusivity in the in-plane direction (consistent with the orientation direction) of the film is 73.60 mm 2/s by a flash heat conduction instrument.
Fig. 9 is a comparison of the difference in heat conductive properties between the heat conductive composite thin film materials prepared in example 2 and comparative example 8, and the thermal diffusivity of the composite thin film was reduced due to the inferior degree of exfoliation of the graphite micro-platelets in comparative example 8 compared to example 2. Further experimental tests showed that the thermal diffusivity of the resulting precursor slurry decreased more significantly as the rotational speed of the stir stripping was further reduced based on comparative example 7.
While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.
Claims (10)
1. A method for preparing a precursor slurry for manufacturing a thermally conductive composite film, comprising the steps of:
1) Preparing a poly-p-phenylene terephthamide nanofiber solution, wherein the solvent is dimethyl sulfoxide and deionized water; adding expanded graphite into the poly (paraphenylene terephthalamide) nanofiber solution to form a mixed solution;
2) Freezing the mixed solution obtained in the step 1) until the mixed solution is completely frozen, and mechanically stirring at a rotating speed of over 1900 rpm so as to strip the expanded graphite to obtain a dispersion liquid;
3) Adding excessive proton-donating solvent into the dispersion liquid in the step 2), fully stirring, dispersing, and carrying out suction filtration to obtain precursor slurry, wherein the proton-donating solvent is at least one of ethanol, methanol and deionized water.
2. The method for preparing a precursor slurry for manufacturing a heat conductive composite film according to claim 1, wherein the mass percentage concentration of the poly (paraphenylene terephthalamide) nanofiber solution is 0.1% -5.0%; and/or the mass ratio of the solid content of the poly (paraphenylene terephthalamide) nanofiber solution to the feeding amount of the expanded graphite is 1: 0.01-20.
3. The method for preparing a precursor slurry for manufacturing a heat conductive composite film according to claim 1, wherein the poly-paraphenylene terephthalamide nanofiber solution is prepared by:
adding the poly-p-phenylene terephthalamide fiber and potassium hydroxide into a mixed solvent of dimethyl sulfoxide and deionized water, and dissociating the poly-p-phenylene terephthalamide fiber by stirring to obtain a poly-p-phenylene terephthalamide nanofiber solution.
4. The method for producing a precursor slurry for use in producing a heat conductive composite film according to claim 1, wherein the temperature at which freezing is performed in step 2) is-20 ℃ or less, and the freezing time is 2h or more; and/or the mechanical stirring time in the step 2) is more than 20 min.
5. The method for preparing a precursor slurry for manufacturing a heat conductive composite film according to claim 1, wherein the average lateral dimension of the graphite micro-plate obtained after the peeling is 25-30 μm.
6. A precursor slurry prepared by the method of any one of claims 1-5.
7. The preparation method of the heat-conducting composite film is characterized by comprising the following steps of:
Dispersing the precursor slurry of claim 6 in a solvent, stirring and dispersing uniformly, vacuum filtering, and drying to obtain a heat-conducting composite film;
The solvent is at least one of ethanol, methanol and deionized water.
8. The method of producing a heat conductive composite film according to claim 7, wherein the thickness dimension of the heat conductive composite film is 30 to 35 μm.
9. The method for preparing a heat conductive composite film according to claim 7, wherein the drying temperature is 40-80 ℃.
10. A thermally conductive composite film prepared by the method of any one of claims 7-9.
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