CN115010494B - Preparation method of graphene heat conducting sheet for strengthening longitudinal heat flux transmission - Google Patents
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Abstract
The invention discloses a preparation method of a graphene heat conducting sheet for strengthening longitudinal heat flux transmission, which comprises the following steps: preparing an annular graphene oxide film; (2) a reorganization process of the flat graphene oxide sheets; (3) preparing graphene foam; (4) And preparing the graphene heat conducting sheet for strengthening longitudinal heat flux transmission. According to the invention, graphene oxide slurry electrolyte is guided to the surface of an electrode according to the electrolytic cell principle and is directionally and orderly arranged, a compact layer is formed through electrolytic reduction, graphene oxide recombination is preliminarily realized, macroscopic repair is carried out by means of hydrophilic self-assembly of graphene oxide powder lamellar functional groups, an annular flat band-shaped structure is prepared, the vertical heat conduction performance is enhanced by in-plane thermal diffusion and conduction compensation, the requirement of enhancing large-flux heat dissipation is realized, and the temperature drop is improved by 20-30% compared with that of a graphene sheet without the annular flat structure.
Description
Technical Field
The invention relates to the field of electronic equipment heat dissipation, in particular to a preparation method of a graphene heat conducting sheet for strengthening longitudinal heat flux transmission.
Background
The electronic communication field in the 5G era preferentially enters a high-speed development stage, the total capacity of the market reaches trillions, key materials serve as a core ring of an industrial chain, and the critical capacity of the electronic communication field is expanded by the trillions of industrial space, so that the 5G electronic communication field is improved in multiple aspects such as operation energy efficiency, experience rate and flow density compared with 4G. As the "just-needed" of 5G, the market share of the high thermal conductivity material will account for over 50% of the critical material. In addition to high thermal conductivity, the thermal management material required by the next generation of electronic devices must have high folding performance, but the high thermal conductivity and high flexibility of the existing macroscopic material are the contradictions that a pair of fish and bear paw are difficult to obtain at the same time, and the appearance of the graphene film provides theoretical possibility for solving the contradiction. The graphene film is formed by sp from carbon atoms 2 The honeycomb plane single-layer two-dimensional macromolecules formed by the hybridization mode have a light, simple and strong bonding structure of atomic mass, and the bonding structure endows the honeycomb plane single-layer two-dimensional macromolecules with ultrahigh heat conductivity and better flexibility.
The graphene heat-conducting film can be formed by assembling single-layer graphene at a molecular level through a specific process, inherits the characteristics of high heat conduction (theoretical value of 5300W/mK) and super flexibility of the graphene, and is a choice for breaking through the traditional carbon heat-conducting materials. For the graphene film, the in-plane size of a graphene unit of the graphene film can reach 100-200 mu m and is far larger than the in-plane crystal size of the traditional polyimide graphitized film, which means that the thermal conductivity of the graphene film is far beyond that of a carbonized film in the future, and the development of the graphene film has great subversive significance no matter theoretically or specific heat conduction application indexes.
The heat dispersion in the heat conduction membrane face is emphasized promoting to present graphite alkene heat conduction membrane technology, the heat conduction membrane mainly plays outer heat and air convection heat dissipation's effect, research focus is also in the aspect of solving the orderly pile up that promotes the lamella, the technology maturity progressively reaches a bottleneck, in other words, in the aspect of lamella longitudinal conduction, the more thorough is the crystallization repair in the face, longitudinal conductivity can be difficult to promote more, the longitudinal heat conductivity of graphite alkene membrane that the thermal conductivity is greater than 1200W/mK in the face is usually less than 5W/mK, and what graphite alkene heat conduction membrane looked in the aspect of big flux heat dissipation is the comprehensive ability of heat dissipation and longitudinal conduction in the face, the short slab of longitudinal conduction still has very big restriction nature to big flux heat dissipation demand.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a graphene heat conducting sheet for reinforcing longitudinal heat flux transmission, which comprises the steps of guiding graphene oxide slurry electrolyte to the surface of an electrode through charges according to the principle of an electrolytic cell to be directionally and orderly arranged, forming a compact layer through electrolytic reduction, preliminarily realizing graphene oxide recombination, carrying out macroscopic repair on a graphene oxide powder sheet layer by means of functional group hydrophilicity self-host equipment, preparing the graphene heat conducting sheet with an annular flat band-shaped structure, reinforcing the vertical heat conducting performance by in-plane heat diffusion conduction compensation, realizing the requirement of reinforcing large-flux heat dissipation, and increasing the temperature drop by 20-30% compared with the graphene sheet without the annular flat structure.
The technical scheme of the invention is as follows: a preparation method of a graphene heat conducting sheet for strengthening longitudinal heat flux transmission is characterized by comprising the following steps:
(1) Preparation of annular graphene oxide film
Preparing a graphene oxide dispersion liquid with the concentration of 3-4wt%, introducing the dispersion liquid into an annular hollow stainless steel mold, connecting edges of two rings with a positive and negative direct-current power supply, charging the two ring-shaped molds, rearranging functional groups of graphene oxide lamellar under the guidance of charges, uniformly arranging on the surface of an electrode (as shown in figure 4), freezing by adopting liquid nitrogen in a power-on state until the graphene oxide lamellar functional groups are completely frozen, and locking the arrangement state of the graphene oxide; freeze-drying the mould to obtain graphene oxide powder foam, and then maintaining the graphene oxide powder foam in an annular shape to be stripped from the inner surface of the mould to obtain an annular continuous graphene oxide film;
(2) Recombination treatment of flat graphene oxide sheets
Spraying graphene oxide quantum dots on the inner side surface of the annular graphene oxide film obtained in the step (1) to soak the surface, oppositely attaching the annular film along an intermediate shaft, flatly pressing the annular film, then placing the annular film in a constant humidity box for 12-24 hours, and compacting and forming the annular film by using a flat press to obtain flat graphene oxide sheets (keeping a flat annular structure continuously, and keeping the edge positions of the sheets continuously);
(3) Preparation of graphene heat-conducting foam
Carrying out vacuum drying on the flat graphene oxide sheets in the step (2) under the protection of argon, then carrying out graphitization treatment, and cooling to obtain graphene heat-conducting foam;
(4) Preparation of graphene heat conducting sheet for strengthening longitudinal heat flux transmission
Carrying out flat pressing treatment on the graphene heat-conducting foam in the step (3) by using a flat press to obtain the compact density of 1.85-2.0g/m 3 The graphene heat conducting sheet for strengthening longitudinal heat flux transmission.
The preparation method of the graphene oxide dispersion liquid with the concentration of 3-4wt% in the step (1) comprises the following steps: and adding water into the graphene oxide filter cake to dilute the graphene oxide filter cake to 3-4wt% of aqueous dispersion, carrying out high-pressure homogenization treatment under the pressure of 70MPa, and defoaming to obtain the graphene oxide dispersion.
And (2) putting the graphene oxide dispersion liquid obtained in the step (1) in an annular hollow stainless steel mold, connecting a 24V positive and negative direct-current power supply to the edges of the two rings to electrify the two annular molds, and keeping the electrified state for 10-30min to rearrange the graphene oxide lamellar functional group radicals in order under the guidance of charges.
The step (1) of maintaining the annular shape to be stripped from the inner surface of the mould specifically comprises the following steps: and (3) placing the die into a calendering roller, regulating the pressure of the roller shaft to be 3-5Mpa, rolling for 10-20 circles, and stripping the graphene oxide film from the inner surface of the die.
The step (2) is specifically as follows: spraying graphene oxide quantum dots with the solid content of 0.3-0.8wt% on the inner side surface to soak the surface, attaching the annular membrane along the middle shaft, flatly pressing the graphene oxide sheet by using a flat graphite plate and placing the graphene oxide sheet in a constant humidity box for 12-24h, fully absorbing water from the functional groups on the edge of the graphene oxide sheet in a humid environment, automatically loading the graphene oxide sheet into a macroscopic repair machine for macroscopic repair, then compacting and forming by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 10-20min to obtain the flat graphene oxide sheet.
The vacuum drying in the step (3) comprises the following steps: heating to 95-105 ℃ at a temperature rise curve of 4-6 ℃/min, keeping the temperature for 4-6h, heating to 170-190 ℃ at 1.5-2.5 ℃/min, keeping the temperature for 2-4h, heating to 230-250 ℃ at 1.5-2.5 ℃/min, keeping the temperature for 1.5-2.5h, and naturally cooling to room temperature.
The graphitization treatment in the step (3) is as follows: transferring the mixture to a graphitizing furnace for graphitizing treatment, continuously keeping argon protection during the graphitizing treatment, raising the temperature at the speed of 8-12 ℃/min to the graphitizing temperature of 2800-3200 ℃, and keeping the temperature for 3-5h.
And (4) carrying out flat pressing treatment on the flat pressing machine in the step (4), setting the pressure to be 15-20MPa, and maintaining the pressure for 1-3h.
According to the graphene heat conducting sheet obtained by the invention, the edges of two sides are continuous non-broken obtuse ring angles, and the front side and the back side are still the same plane.
Preferably, the method specifically comprises the following steps:
(1) Preparation of annular graphene oxide film
Preparing graphene oxide dispersion liquid with the concentration of 3-4wt%, introducing the dispersion liquid into an annular hollow stainless steel mold, connecting edges of two rings with a 24V positive and negative direct-current power supply, electrifying the two ring-packaged molds, keeping the electrified state for 25-30min, rearranging graphene oxide lamellar functional group free radicals under the guidance of charges, uniformly distributing on the surface of an electrode, then freezing by liquid nitrogen until the graphene oxide lamellar functional group free radicals are completely frozen, and locking the distribution state of the graphene oxide;
cutting off a direct-current power supply, transferring the mold to a vacuum freeze dryer for freeze drying to obtain graphene oxide powder foam, loading the mold into a calendering roller, adjusting the pressure of the roller shaft to be 3-5Mpa, rolling for 10-20 circles, and stripping the graphene oxide film from the inner surface of the mold to obtain an annular continuous graphene oxide film;
(2) Recombination treatment of flat graphene oxide sheets
Spraying graphene oxide quantum dots with solid content of 0.4-0.6wt% on the inner side surface of the annular graphene oxide film in the step (1) to soak the surface, pasting the annular film along an intermediate shaft, flatly pressing a graphene oxide sheet by using a flat graphite plate for 12-24h, compacting and molding by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 10-20min to obtain a flat graphene oxide sheet;
(3) Preparation of graphene heat-conducting foam
Placing the graphene oxide sheet in the step (2) in a vacuum oven, removing air, supplementing argon for protection, heating to 95-105 ℃ at a temperature rise curve of 4-6 ℃/min, keeping the temperature for 4-6h, heating to 170-190 ℃ at a temperature of 1.5-2.5 ℃/min, keeping the temperature for 2-4h, heating to 230-250 ℃ at a temperature of 1.5-2.5 ℃/min, and naturally cooling to room temperature; then transferring the product to a graphitization furnace for graphitization treatment, continuously keeping argon protection during the graphitization treatment, raising the temperature at the speed of 8-12 ℃/min to the graphitization temperature of 2800-3200 ℃, preserving the heat for 3-5h, and naturally cooling to obtain graphene heat-conducting foam;
(4) Preparation of graphene heat conducting sheet for strengthening longitudinal heat flux transmission
Carrying out flat pressing treatment on the graphene heat-conducting foam in the step (3) by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 1-3h to obtain the compact density of 1.85-2.0g/m 3 The graphene heat conducting sheet for strengthening longitudinal heat flux transmission.
The technical principle of the invention is as follows: the graphene oxide dispersion liquid and the annular mold form an electrolytic cell, the graphene oxide dispersion liquid serves as electrolyte to form conductive ion flow, so that the graphene oxide is electrophoresed to the surface of the mold, and a lamellar arrangement is formed in order. And (3) transferring charges on the surface of the mold, electrochemically reducing the charges, and losing functional groups to form a compact film layer. A schematic diagram of an electrochemical assembly of graphene oxide by electromigration is shown in fig. 5. And then carrying out liquid nitrogen quick freezing in a power-on state to protect the sheet recombination from being damaged, and carrying out freeze drying to obtain the graphene oxide powder foam, so as to keep the consistency of the graphene oxide sheet arrangement of the foam. In the recombination treatment process of the flat graphene oxide sheets, the graphene oxide powder sheet layer is subjected to macroscopic repair by means of functional group hydrophilic autonomous assembly, and the prepared graphene heat conducting sheet with the annular flat strip-shaped structure reinforces vertical heat conducting performance by in-plane thermal diffusion conduction compensation, so that the requirement of reinforcing large-flux heat dissipation is met. Compared with the traditional graphene heat conducting sheet (the working principle is shown in figure 9), the graphene heat conducting sheet for longitudinal heat flux transmission is strengthened (the working principle is shown in figure 8), the vertical heat conducting performance is strengthened by in-plane heat diffusion conduction compensation, and the requirement of strengthening large-flux heat dissipation is met.
The invention has the technical effects that: the graphene oxide slurry electrolyte is guided to the surface of an electrode by the principle of an electrolytic cell to be directionally and orderly arranged, a compact layer is formed by electrolytic reduction, graphene oxide recombination is preliminarily realized, graphene oxide powder sheets are subjected to macroscopic repair by means of functional group hydrophilicity self-assembly, the prepared graphene heat conducting sheets with annular flat band-shaped structures are compensated and reinforced in vertical heat conducting performance by in-plane heat diffusion conduction, the requirement of reinforcing large-flux heat dissipation is realized, and the temperature drop is improved by 20-30% compared with that of graphene sheets without annular flat structures.
Drawings
Fig. 1 is a TEM picture of a graphene oxide dispersion;
FIG. 2 is an SEM image of graphene oxide powder foam;
FIG. 3 is a cross-sectional SEM image of graphene foam;
FIG. 4 is a schematic diagram of graphene oxide lamella self-assembly; wherein, a: an inner mold; b: an outer layer mold; c: a plastic chassis; d: a 24V DC power supply; e: a graphene oxide dispersion;
FIG. 5 is a schematic diagram of an electromigration electrochemical assembly of graphene oxide;
FIG. 6 is a schematic roll press diagram of a ring-shaped graphene oxide film; wherein, a: an inner mold; b: an outer layer mold; c: an annular graphene oxide film; d: rolling the adjustable gap pressing shaft;
FIG. 7 is a schematic illustration of flat graphene oxide sheet preparation;
fig. 8 is a working schematic diagram of a graphene heat conducting sheet for enhancing longitudinal heat flux transmission;
fig. 9 is a working schematic diagram of a conventional graphene heat conducting sheet;
fig. 10 is a graph showing the film attachment (a diagram) and temperature drop test curve (B diagram) of the graphene heat conducting sheet; in the figure B, the ordinate is the temperature, which ranges from 38 to 70 ℃; the abscissa is time; the upper curve is the temperature drop before and after film sticking, the temperature before film sticking is higher, and the temperature after film sticking is reduced; the lower curve is the temperature in the box, and the constant temperature cover is opened when the film is pasted, so that the temperature slightly fluctuates; and after the film is attached, the temperature returns to normal.
Detailed Description
The technical solutions of the present invention are further described below with reference to specific embodiments of the present invention and the accompanying drawings, but the scope of the present invention is not limited to these embodiments. All changes, substitutions and equivalents that do not depart from the spirit and scope of the invention are intended to be included within the scope thereof.
Example 1:
(1) Preparation of annular graphene oxide film
Diluting the graphene oxide filter cake with water to 3wt% of aqueous dispersion, performing high-pressure homogenization treatment under the pressure of 70Mpa, and defoaming to obtain graphene oxide dispersion, wherein a TEM picture of the graphene oxide dispersion is shown in FIG. 1;
as shown in fig. 4, introducing the graphene oxide dispersion liquid into an annular hollow stainless steel metal mold, connecting the edges of two rings with a 24V positive-negative dc power supply, charging the two ring-assembled molds, maintaining the energized state for 30min, rearranging graphene oxide lamellar functional group radicals under the guidance of charges, uniformly arranging on the electrode surface, then freezing liquid nitrogen until the liquid nitrogen is completely frozen, locking the arrangement state of the graphene oxide, cutting off the dc power supply, transferring the mold into a vacuum freeze dryer, and freeze-drying to obtain graphene oxide powder foam, wherein an SEM image of the graphene oxide powder foam is shown in fig. 2;
as shown in fig. 6, the mold is placed into a calendering roll, the roll shaft pressure is adjusted to be 5Mpa, and the graphene oxide film is peeled from the inner surface of the mold by rolling for 20 rings, so as to obtain a ring-shaped continuous graphene oxide film;
(2) Recombination treatment of flat graphene oxide sheets
As shown in fig. 7, the inner side surface of the annular graphene oxide film in step (1) is sprayed with graphene oxide quantum dots with a solid content of 0.5wt%, so as to wet the surface, the annular film is attached to the intermediate shaft, the graphene oxide sheet is flatly pressed in a constant humidity chamber for 24h by using a flat graphite plate, and then is compacted and formed by using a flatting press, the pressure is set at 20MPa, and the pressure is maintained for 20min, so as to obtain the flat graphene oxide sheet.
(3) Preparation of graphene heat-conducting foam
Placing the graphene oxide sheet in the step (2) in a vacuum oven, removing air, supplementing argon for protection, heating to 100 ℃ at a temperature rise curve of 5 ℃/min, keeping the temperature for 5h, heating to 180 ℃ at a temperature rise curve of 2 ℃/min, keeping the temperature for 3h, heating to 240 ℃ at a temperature rise curve of 2 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, transferring to a graphitization furnace for graphitization treatment, continuously keeping argon for protection during the period, heating to a graphitization temperature of 3000 ℃ at a temperature rise speed of 10 ℃/min, keeping the temperature for 4h, and naturally cooling to obtain graphene heat conduction foam, wherein a cross-section SEM image of the graphene heat conduction foam is shown in figure 3;
(4) Preparation of graphene heat conducting sheet for strengthening longitudinal heat flux transmission
Flatly pressing the graphene heat-conducting foam in the step (3) by a flat press, setting the pressure to be 20MPa, and maintaining the pressure for 3 hours to obtain the compact density of 2.0g/m 3 The graphene heat conducting sheet for strengthening longitudinal heat flux transmission.
The edges of two sides of the graphene heat conducting sheet for strengthening the longitudinal heat flux transmission prepared by the method are continuous non-broken obtuse ring angles, and the front side and the back side of the graphene heat conducting sheet are still the same plane.
Comparative example 1: graphene oxide dispersion liquid without electrolytic reduction treatment
(1) Diluting a graphene oxide filter cake to 3wt% of aqueous dispersion liquid by adding water, carrying out high-pressure homogenization treatment under the pressure of 70MPa, and defoaming to obtain graphene oxide dispersion liquid, introducing the dispersion liquid into an annular hollow stainless steel metal mold, standing for 30min, then freezing by using liquid nitrogen until the dispersion liquid is completely frozen, locking the arrangement state of graphene oxide, transferring the mold into a vacuum freeze dryer for freeze drying to obtain graphene oxide powder foam, loading the mold into a calendering roller, adjusting the pressure of the roller shaft to be 5MPa, rolling for 20 circles, and stripping a graphene oxide film from the inner surface of the mold to obtain an annular continuous graphene oxide film;
(2) The process for reorganizing flat graphene oxide sheets was the same as in example 1;
(3) The preparation method of the graphene foam is the same as that of example 1;
(4) The preparation of the graphene heat-conducting sheet for enhancing the longitudinal heat flux transmission is the same as that of example 1.
Comparative example 2: slow freezing after electrolytic reduction to replace liquid nitrogen freezing
(1) Diluting a graphene oxide filter cake to 3wt% of aqueous dispersion liquid by adding water, carrying out high-pressure homogenization treatment under the pressure of 70Mpa, and defoaming to obtain a graphene oxide dispersion liquid, introducing the dispersion liquid into an annular hollow stainless steel metal mold, connecting 24V positive and negative direct-current power supplies to the edges of two rings, electrifying the two rings, keeping the electrified state for 30min, rearranging graphene oxide lamellar functional group radicals under the guidance of charges, uniformly distributing on the surface of an electrode, then transferring to a-30 ℃ refrigeration house for slow freezing, transferring the mold to a vacuum freeze dryer for freeze drying to obtain graphene oxide powder foam, loading the mold into a calendering roller, adjusting the pressure of the roller shaft to 5Mpa, rolling for 20 circles, and stripping the graphene oxide film from the inner surface of the mold to obtain an annular continuous graphene oxide film;
(2) The flat graphene oxide sheets were reconstituted as in example 1;
(3) The preparation method of the graphene foam is the same as that of example 1;
(4) The preparation of the graphene heat-conducting sheet for enhancing the longitudinal heat flux transmission is the same as that of example 1.
Comparative example 3: step (2) performing macroscopic repair without performing surface wetting functional group hydrophilic autonomous assembly
(1) The preparation of the ring-shaped graphene oxide film is the same as that of example 1;
(2) Directly attaching graphene oxide powder foam along an annular membrane along a middle shaft, compacting and molding by using a flat press, setting the pressure to be 20MPa, and maintaining the pressure for 20min to obtain flat graphene oxide sheets;
(3) The preparation method of the graphene foam is the same as that of example 1;
(4) The preparation of the graphene heat-conducting sheet for enhancing the longitudinal heat flux transmission is the same as that of example 1.
Comparative example 4: step (4) cutting the flat edge into sections (non-circular flat structure)
(1) Preparation method of annular graphene oxide film is the same as example 1
(2) The process of reorganizing the flat graphene oxide sheets was the same as in example 1.
(3) The graphene foam was prepared in the same manner as in example 1.
(4) Cutting the flat edge of the graphene heat-conducting foam in the step (3) into sections, and passing throughFlat-pressing by a flat press, setting the pressure to be 20MPa, maintaining the pressure for 3 hours to obtain the compacted density of 2.0g/m 3 The laminated graphene thermally conductive sheet of (1).
The plane thermal diffusivity (25 ℃), the longitudinal thermal diffusivity (25 ℃), the plane thermal conductivity (25 ℃), the longitudinal thermal conductivity (25 ℃) and the specific heat capacity (25 ℃) of the graphene heat conducting sheets prepared in example 1 and comparative examples 1-4 are measured by a method for measuring the thermal diffusivity or the thermal conductivity by using a flash method of GB/T22588-2008, and the compaction density is measured by using ISO 12154-2014.
The temperature drop degree measuring method comprises the following steps: setting a constant 40 ℃ environment temperature in the heat dispersion tester instrument, setting constant heating power of a heating core, and after balancing, attaching the diaphragm to a 1W constant-temperature heating element (material red copper, surface area 1cm × 1cm) of the test bed until the temperature is constant; the temperatures before and after the film sticking are read, the temperature difference is the heat dissipation performance of the film, the temperature drop test curve of the graphene heat conducting sheet in the embodiment 1 is shown in fig. 10, and the temperature drop degree is 21 ℃.
The test results are shown in table 1.
Table 1 graphene thermal conductive sheet performance test results
As can be seen from the results of table 1:
1) Compared with the embodiment 1, the graphene oxide dispersion liquid in the comparative example 1 does not adopt electrolytic reduction to form a compact layer, so that the surface thermal diffusion coefficient, the longitudinal thermal diffusion coefficient, the plane thermal conductivity coefficient, the longitudinal thermal conductivity coefficient and the temperature drop degree are all reduced, and particularly, the temperature drop is only 14.5 ℃;
2) Compared with the example 1, the comparative example 2 replaces liquid nitrogen freezing by slow freezing after electrolytic reduction, does not lock the arrangement state of the graphene oxide, reduces the surface heat diffusion coefficient, the longitudinal heat diffusion coefficient, the plane heat conductivity coefficient, the longitudinal heat conductivity coefficient and the temperature reduction degree, particularly has poor longitudinal heat diffusion effect, and has the longitudinal heat diffusion coefficient of only 6mm 2 S, longitudinal thermal conductivity of only 10.2W/(m.K);
3) With fruitCompared with the example 1, the recombination treatment of the flat graphene oxide sheet in the comparative example 3 does not spray graphene oxide quantum dots with the solid content of 0.5wt%, does not have the effect of fully enabling the edge functional groups of the graphene oxide sheet to absorb water and perform self-loading and macroscopic repair in a humid environment, and has the advantages of reduced surface heat diffusion coefficient, longitudinal heat diffusion coefficient, plane heat conductivity coefficient, longitudinal heat conductivity coefficient and temperature drop degree, especially poor plane heat diffusion effect, and only 520mm plane heat diffusion coefficient 2 (ii)/s, in-plane thermal conductivity of only 884W/(m.K);
4) Compared with the example 1, after the flat edge in the step (4) of the comparative example 4 is cut into sections, the surface heat diffusion coefficient, the longitudinal heat diffusion coefficient, the plane heat conductivity coefficient, the longitudinal heat conductivity coefficient and the temperature drop degree of the flat edge are all reduced, especially the longitudinal heat diffusion effect is poor, and the longitudinal heat diffusion coefficient is only 6mm 2 And the longitudinal thermal conductivity is only 10.2W/(m.K). Compared with the graphene sheet with the same thickness and without the annular flat structure in the comparative document 4, the graphene sheet in the embodiment 1 is improved by 26.5% in a 1W constant-temperature heat source temperature drop performance test.
Claims (10)
1. A preparation method of a graphene heat conducting sheet for reinforcing longitudinal heat flux transmission is characterized by comprising the following steps:
(1) Preparation of annular graphene oxide film
Preparing a graphene oxide dispersion liquid with the concentration of 3-4wt%, introducing the dispersion liquid into an annular hollow stainless steel mold, connecting edges of two rings with a positive and negative direct-current power supply, charging the two ring-shaped molds, rearranging functional groups of graphene oxide lamellar under the guidance of charges, uniformly distributing on the surface of an electrode, then freezing by adopting liquid nitrogen in a power-on state until the graphene oxide lamellar functional groups are completely frozen, and locking the distribution state of the graphene oxide; freeze-drying the mould to obtain graphene oxide powder foam, and then maintaining the graphene oxide powder foam in an annular shape to peel off from the inner surface of the mould to obtain an annular continuous graphene oxide film;
(2) Recombination treatment of flat graphene oxide sheets
Spraying graphene oxide quantum dots on the inner edge surface of the annular graphene oxide film in the step (1) to soak the surface, pasting the annular film along an intermediate shaft, flatly pressing, placing in a constant humidity box for 12-24h, and compacting and molding by using a flat press to obtain flat graphene oxide sheets;
(3) Preparation of graphene heat-conducting foam
Carrying out vacuum drying on the flat graphene oxide sheets in the step (2) under the protection of argon, then carrying out graphitization treatment, and cooling to obtain graphene heat-conducting foam;
(4) Preparation of graphene heat conducting sheet for strengthening longitudinal heat flux transmission
Carrying out flat pressing treatment on the graphene heat-conducting foam in the step (3) by using a flat press to obtain the compact density of 1.85-2.0g/m 3 The graphene heat conducting sheet for reinforcing the transmission of longitudinal heat flux.
2. The method for preparing the graphene heat-conducting sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the graphene oxide dispersion liquid with the concentration of 3-4wt% in the step (1) is prepared by: and adding water into the graphene oxide filter cake to dilute the graphene oxide filter cake to 3-4wt% of aqueous dispersion, then carrying out high-pressure homogenization treatment under the pressure of 70MP a, and defoaming to obtain the graphene oxide dispersion.
3. The method for preparing the graphene heat conducting sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the graphene oxide dispersion liquid in the step (1) is placed in an annular hollow stainless steel mold, a 24V positive-negative direct current power supply is connected to the edges of two rings, so that the two-ring mold is charged, the electrified state is kept for 10-30min, and the graphene oxide sheet layer functional group free radicals are rearranged in order under the guidance of charges.
4. The method for preparing the graphene heat-conducting fin for reinforcing longitudinal heat flux transmission according to claim 1, wherein the step (1) of maintaining the annular peeling from the inner surface of the mold comprises the following steps: and (3) placing the die into a calendering roller, adjusting the pressure of the roller shaft to be 3-5MP a, rolling for 10-20 circles, and stripping the graphene oxide film from the inner surface of the die.
5. The preparation method of the graphene heat-conducting sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the step (2) is specifically as follows: spraying graphene oxide quantum dots with the solid content of 0.3-0.8wt% on the inner side surface to soak the surface, pasting the annular film along the middle shaft, flatly pressing the graphene oxide sheet by using a flat graphite plate and placing the graphene oxide sheet in a constant humidity box for 12-24h, fully absorbing water from functional groups on the edge of the graphene oxide sheet in a humid environment, carrying out self-assembly and macroscopic repair, then compacting and forming by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 10-20min to obtain the flat graphene oxide sheet.
6. The method for preparing the graphene heat-conducting sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the vacuum drying in the step (3) is: heating to 95-105 ℃ at a temperature rise curve of 4-6 ℃/min, keeping the temperature for 4-6h, heating to 170-190 ℃ at 1.5-2.5 ℃/min, keeping the temperature for 2-4h, heating to 230-250 ℃ at 1.5-2.5 ℃/min, keeping the temperature for 1.5-2.5h, and naturally cooling to room temperature.
7. The method for preparing graphene heat conduction sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the graphitization treatment in the step (3) is: transferring the mixture to a graphitization furnace for graphitization treatment, continuously keeping argon protection during the period, raising the temperature at the speed of 8-12 ℃/min to the graphitization temperature of 2800-3200 ℃, and preserving the heat for 3-5h.
8. The method for preparing the graphene heat-conducting sheet for enhancing longitudinal heat flux transmission according to claim 1, wherein the flat-pressing process of the flat press in the step (4) is performed under a set pressure of 15-20MPa for 1-3h.
9. The method for preparing the graphene heat-conducting sheet for enhancing longitudinal heat flux transmission according to any one of claims 1 to 8,
(1) Preparation of annular graphene oxide film
Preparing a graphene oxide dispersion liquid with the concentration of 3-4wt%, introducing the dispersion liquid into an annular hollow stainless steel mold, connecting the edges of two rings with a 24V positive and negative direct-current power supply, electrifying the two ring-shaped molds, keeping the electrified state for 25-30min, rearranging graphene oxide lamellar functional group free radicals under charge guidance, uniformly distributing on the surface of an electrode, then freezing by liquid nitrogen until the graphene oxide lamellar functional group free radicals are completely frozen, and locking the distribution state of the graphene oxide;
cutting off a direct-current power supply, transferring the mold to a vacuum freeze dryer for freeze drying to obtain graphene oxide powder foam, loading the mold into a calendering roller, adjusting the pressure of the roller shaft to 3-5MP a, rolling for 10-20 circles, and stripping the graphene oxide film from the inner surface of the mold to obtain an annular continuous graphene oxide film;
(2) Recombination treatment of flat graphene oxide sheets
Spraying graphene oxide quantum dots with solid content of 0.4-0.6wt% on the inner side surface of the annular graphene oxide film in the step (1) to soak the surface, pasting the annular film along an intermediate shaft, flatly pressing a graphene oxide sheet by using a flat graphite plate for 12-24h, compacting and molding by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 10-20min to obtain a flat graphene oxide sheet;
(3) Preparation of graphene heat-conducting foam
Placing the graphene oxide sheet in the step (2) in a vacuum oven, removing air, supplementing argon for protection, heating to 95-105 ℃ at a temperature rise curve of 4-6 ℃/min, keeping the temperature for 4-6h, heating to 170-190 ℃ at a temperature of 1.5-2.5 ℃/min, keeping the temperature for 2-4h, heating to 230-250 ℃ at a temperature of 1.5-2.5 ℃/min, and naturally cooling to room temperature; then transferring the product to a graphitization furnace for graphitization treatment, continuously keeping argon protection during the graphitization treatment, raising the temperature at the speed of 8-12 ℃/min to the graphitization temperature of 2800-3200 ℃, preserving the heat for 3-5h, and naturally cooling to obtain graphene heat-conducting foam;
(4) Preparation of graphene heat conducting sheet for strengthening longitudinal heat flux transmission
Carrying out flat pressing treatment on the graphene heat-conducting foam in the step (3) by using a flat press, setting the pressure to be 15-20MPa, and maintaining the pressure for 1-3h to obtain the compact density of 1.85-2.0g/m 3 The graphene heat conducting sheet for reinforcing the transmission of longitudinal heat flux.
10. The graphene thermally conductive sheet for enhancing longitudinal heat flux transfer prepared by the method of any one of claims 1 to 8.
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