CN113979428B - Preparation method of heat-conducting wave-absorbing composite film and heat-conducting wave-absorbing composite film - Google Patents
Preparation method of heat-conducting wave-absorbing composite film and heat-conducting wave-absorbing composite film Download PDFInfo
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Abstract
The invention discloses a heat-conducting wave-absorbing composite film and a preparation method thereof. The heat-conducting wave-absorbing composite material prepared by the invention has excellent heat-conducting property, the heat-conducting coefficient is up to 2200W/mK, and simultaneously has good electromagnetic shielding property, the highest shielding efficiency can reach 105dB, and the heat-conducting wave-absorbing composite material can be used for heat dissipation design of devices with large heat flux density and electromagnetic shielding.
Description
Technical Field
The application relates to the technical field of electronic functional materials, in particular to a preparation method of a heat-conducting wave-absorbing composite film and the heat-conducting wave-absorbing composite film.
Background
With the advent of the 5G age, electronic chips have been reduced in weight and have been highly integrated. Meanwhile, the working frequency of the electronic chip used by the 5G technology is continuously improved, the power is increased, and the heating value of a unit area is obviously increased, so that the development of the electronic chip used by the 5G technology is restricted by the following two factors:
firstly, the increase of the working frequency of the electronic chip can cause the increase of the electromagnetic interference range and the interference degree between equipment and in the equipment, and the electromagnetic interference and the electromagnetic radiation cause serious harm to the electronic equipment; secondly, the heating value of the unit area of the electronic chip is greatly increased, redundant heat is not timely conducted to the outside, the working state of the electronic component is greatly influenced, equipment failure is even caused in severe cases, and the service life is reduced. Therefore, how to effectively solve the problems of wave absorption and heat conduction of the electronic chip at the same time becomes a development bottleneck of the 5G technology.
Graphene is a novel carbon material with a single-layer two-dimensional honeycomb lattice structure formed by stacking carbon atoms, and the heat conductivity coefficient of a graphene heat conduction film developed by taking graphene as a raw material can reach 2000W/(m.k) at most, but when the graphene is used as a wave absorbing material, the graphene is unfavorable for electromagnetic wave absorption due to overlarge conductivity, and the application of the graphene in the wave absorbing field is limited.
The MXees are novel two-dimensional materials and are composed of a plurality of transition metal carbides, nitrides or carbonitrides with atomic layer thickness, although the MXees show a certain electromagnetic shielding effect in the electromagnetic shielding field, the film prepared from the pure MXees materials has less reflection and scattering loss of electromagnetic waves in the materials due to internal compaction, so that the improvement of the electromagnetic shielding effect is not facilitated, and the electromagnetic shielding performance of the MXees materials has potential for improvement.
Therefore, the applicant has demanded to develop a composite material which combines high heat conductivity and wave absorbing property so as to further develop the field of electronic chips.
Disclosure of Invention
In order to develop high-performance materials in the field of electronic chips and improve heat conduction and wave absorption performance of the materials, the application provides a preparation method of a heat conduction wave absorption composite film and the heat conduction wave absorption composite film.
In a first aspect, the present application provides a method for preparing a heat-conducting wave-absorbing composite film, which adopts the following technical scheme:
the preparation method of the heat-conducting wave-absorbing composite film comprises the following preparation steps:
preparation of MXene nanosheet dispersion: etching the MAX phase material by using an etchant to obtain an organ-shaped MXene phase, and obtaining an MXene nano-sheet dispersion liquid through washing and ultrasonic treatment;
preparing composite slurry: uniformly mixing the dispersion liquid of the nano sheets with the concentration of 0.03-0.15 g/LMXene and the graphene oxide slurry with the concentration of 0.5-2 g/L, controlling the weight ratio of the nano sheets to the graphene oxide to be (1-10) (5-30), and preparing the composite slurry by ultrasonic dispersion;
film preparation: coating and drying the composite slurry to prepare a film;
post-treatment: and (3) graphitizing the film, and calendaring to obtain the heat-conducting wave-absorbing composite film.
By adopting the technical scheme, the MAX phase material is used as a precursor, the Al layer is removed by chemical etching of etchants such as hydrofluoric acid, lithium fluoride and the like, so that an organ-shaped MXene phase is obtained, and the organ-shaped MXene phase is subjected to ultrasonic stripping treatment, so that MXene nanosheet dispersion liquid is obtained;
the surfaces of the MXene nano-sheets and the graphene oxide sheets all contain a large number of polar groups, the MXene nano-sheets and the graphene oxide sheets are two-dimensional materials, the MXene nano-sheets can be assembled together with the graphene oxide, a composite material can be formed through Van der Waals force, hydrogen bond and sub pi-pi conjugated stacking crosslinking, and the composite material is stably suspended in a solvent to form composite slurry; uniformly coating the composite slurry on a substrate, and drying to remove the solvent to form a film;
the temperature of graphitization treatment is generally 2300 ℃ or above, graphene oxide is reduced in the graphitization treatment process of the film, then atoms in the film are partially rearranged, the defect of the film is repaired, the lamellar structure is increased, the hole size distribution is uniform and fine, a stable multi-layer heat conduction network is formed, the number of heat conduction channels of the heat conduction network is increased, and the heat conduction coefficient is improved to 2200W/(m.k); the multi-layer structure and the microporous structure of the heat conduction network can enable electromagnetic waves to be reflected/scattered for multiple times, a better wave absorbing effect is achieved, and the electromagnetic shielding effectiveness reaches 105dB under the thickness;
the composite film which is contracted during graphitization is subjected to calendaring treatment, and the composite film with high heat conducting property and wave absorbing property is obtained by extension.
Optionally, in the post-treatment step, the temperature of the film graphitization treatment is 2500-3000 ℃, and the heat preservation treatment is carried out for 0.5-1 h.
Preferably, in the post-treatment step, the film graphitization treatment is performed under the protection of argon.
By adopting the technical scheme, the formed microporous structure is uniform and fine in the temperature range of graphitization treatment, and the heat conduction performance and the wave absorption performance of the composite film are optimal; and the pore space of the composite membrane is overlarge below the graphitization temperature range, so that the heat conduction performance of the composite membrane is reduced.
Optionally, the specific operation of the MXene nano-sheet dispersion liquid preparation step is as follows:
adding MAX phase material into hydrofluoric acid with concentration of 20-30wt%, wherein the weight ratio of MAX phase material to hydrofluoric acid is 1 (5-10), stirring for 5-10 h when heating to 60-80 ℃ to obtain organ-shaped MXene phase material; washing the organ-shaped MXene phase material in ethanol water solution for at least 3 times, and performing ultrasonic treatment for 1-4 hours at the ultrasonic frequency of 40-60 kHz to obtain the MXene nano-sheet dispersion liquid.
By adopting the technical scheme, the concentration and the etching temperature of the hydrofluoric acid solution are controlled, so that the MAX phase material can sufficiently remove the Al layer and the MXene phase material cannot be over-etched; the size of the MXene nano-sheet is moderate by controlling the ultrasonic frequency and ultrasonic time.
Optionally, the MXene nano-sheets in the MXene nano-sheet dispersion preparation step comprise Ti 3 C 2 T x 、 Ti 2 CT x 、V 2 CT x 、Mo 2 CT x 、Nb 2 CT x 、Nb 4 C 3 T x 、Mo 2 TiC 2 T x And Mo (Mo) 2 Ti 2 C 3 T x At least one of them.
Optionally, in the preparation step of the composite slurry, the weight ratio of the MXene nano-sheets to the graphene oxide is (15-20) (5-6).
By adopting the technical scheme, the weight ratio of the MXene nano-sheet to the graphene oxide is controlled, so that the viscosity of the composite slurry is moderate, and the contact sites of the composite film are increased in the crosslinking forming process, so that the hole rate and the number of heat conduction passages are increased, and the heat conduction effect and the wave absorbing performance of the composite film are further improved.
Optionally, in the step of preparing the composite slurry, the ultrasonic frequency of ultrasonic dispersion is 50-60 kHz, and the ultrasonic time is 1-2 h.
By adopting the technical scheme, the graphene oxide sheets can be fully intercalated between the MXene nano sheets under the ultrasonic frequency and the ultrasonic time.
Optionally, in the preparation step of the composite slurry, isopropanolamine is added into the graphene oxide solution, and the concentration of the isopropanolamine in the graphene oxide solution is 0.05-0.5 g/L.
Through the technical scheme, the graphene oxide surface is modified by isopropanolamine, and the isopropanolamine is grafted on the graphene oxide surface, so that the polarity of the graphene oxide surface can be increased, the modified graphene oxide and the MXene nano-sheets and the modified graphene oxide sheets are more easily and tightly combined, the number of heat conduction passages and the number of holes in the film are increased, and the heat conduction performance and the wave absorption performance of the composite film are further improved; secondly, isopropanolamine is a good surfactant, so that the film is easy to peel off from the substrate, and the possibility of damage to the film is reduced; finally, the isopropanolamine is carbonized in the graphitization treatment process, carbon particles are formed between the sheets of the composite membrane, a good supporting effect is achieved, the structural stability of the composite membrane is improved, the pore structure inside the composite membrane is increased, and the wave absorbing performance of the composite membrane is improved.
Optionally, in the step of preparing the composite slurry, the size of the sheet diameter of the graphene oxide in the graphene oxide slurry is 0.5-5 μm.
By adopting the technical scheme, the film forming performance of the graphene oxide is better, and the diameter of the graphene oxide sheet is controlled within a proper range, so that the MXene nano sheet can be fully and firmly attached to the graphene oxide sheet layer, and the heat conducting performance and the wave absorbing performance of the composite film are promoted to be optimal.
In a second aspect, the present application provides a heat-conducting wave-absorbing composite film, which adopts the following technical scheme: a heat-conducting wave-absorbing composite film is prepared by the preparation method of the heat-conducting wave-absorbing composite film.
By adopting the technical scheme, the prepared heat-conducting wave-absorbing composite film has better heat-conducting property and wave-absorbing property, active groups on the surface are removed in the graphitization treatment step, and the heat-conducting wave-absorbing composite film has better oxidation resistance, good stability and longer service life.
Preferably, the thickness of the heat-conducting wave-absorbing composite film is 10-700 um.
Through adopting above-mentioned technical scheme, the lightweight development can be accomplished to the heat conduction wave-absorbing complex film, and more specifically, the thickness of heat conduction wave-absorbing complex film can be adjusted in this thickness within range according to actual demand.
In summary, the present application has the following beneficial effects:
1. because graphene oxide and MXene nano sheets are adopted for compounding, the MXene nano sheets are attached to graphene oxide sheets, and the MXene nano sheets form a porous film along with the graphene oxide sheets due to hydrogen bond interaction and pi-pi interaction of sp2 regions, and defects on the film are repaired through graphitization treatment subsequently, so that the pores on the film are uniformly distributed, the pore diameter is reduced, and the porous film has good heat absorption and guide performance.
2. In the application, the film is preferably treated at a high temperature of 2500-3000 ℃ so that the pores in the composite film can be remarkably improved, and the composite film is not easy to ablate in the temperature range.
3. In the method, isopropanolamine is preferentially selected to modify graphene oxide to obtain modified graphene oxide, and the modified graphene oxide enables the internal structure of the film to be compact, so that the development is further towards the light weight direction; meanwhile, carbon particles are formed in the graphitization process, a lamellar structure in the composite film is stably supported, a large number of micropores are formed, and the wave absorbing performance of the composite film is further improved.
Detailed Description
Unless otherwise specified, the raw materials in examples and comparative examples are as follows:
graphene oxide slurries were purchased from Nanjing Xianfeng nanotechnology Co. The cargo numbers and corresponding dimensions are shown in table 1 below.
TABLE 1 graphene oxide dispersion
| Model number | Sheet diameter | Concentration of |
| XF020-100675 | 50-200nm | 0.5mg/mL |
| XF020-100681 | 50-200nm | 2mg/mL |
| XF020-100691 | 50-200nm | 1mg/mL |
| XF020-100056 | 0.5-5μm | 0.5mg/mL |
| XF020-100062 | 0.5-5μm | 2mg/mL |
| XF020-100653 | 0.5-5μm | 1mg/mL |
Examples
Example 1
The heat-conducting wave-absorbing composite film is prepared according to the following steps:
preparation of MXene nanosheet dispersion:
20gMAX phase material Ti 3 AlC 2 Added to 100g of hydrofluoric acid solution (hydrofluoric acid solutionFor commercial products, the mixture is diluted to a concentration of 20wt percent, the temperature is gradually increased to 60 ℃ at a speed of 5 ℃/min, the stirring speed is controlled to be 400rpm, and the mixture is stirred for 10 hours to obtain the organ-shaped MXene phase Ti 3 C 2 T x A material;
organ-like MXene phase Ti 3 C 2 T x Transferring the material into deionized water, and repeatedly washing for 3 times;
0.03g of organ-like MXene phase Ti is taken 3 C 2 T x Putting the material into 1L deionized water, placing the deionized water into ultrasonic dispersion equipment, setting the ultrasonic frequency to be 40kHz, and carrying out ultrasonic treatment for 4 hours to obtain MXene nanosheet dispersion liquid for later use;
preparing composite slurry:
200mL of 0.03g/LMXene nano sheet dispersion liquid is taken, added into 360mL of graphene oxide slurry (the graphene oxide slurry model XF 020-100675), stirred for 1h at 600rpm, placed in ultrasonic dispersion equipment, set to an ultrasonic frequency of 50kHz, and subjected to ultrasonic treatment for 1h to obtain composite slurry;
film preparation:
transferring the composite slurry into a precise coating machine, coating the composite slurry on a substrate, heating to 100 ℃ at a speed of 5 ℃/min, and carrying out heat preservation and drying for 2 hours to obtain a film;
post-treatment:
the film is sent into a graphitizing furnace, the temperature in the graphitizing furnace is raised to 2300 ℃, the heat preservation treatment is carried out for 2 hours, argon is introduced into the graphitizing furnace as a shielding gas in the graphitizing treatment process, and the flexible compressible film is obtained;
the flexible compressible film was put into a three-roll calender and calendered until the thickness of the heat-conducting wave-absorbing composite film was 50 μm.
Examples 2 to 4
The difference between the heat conduction wave-absorbing composite film and the embodiment 1 is that: the process parameters in the post-treatment step are different and the specific process parameters are shown in table 2 below.
TABLE 2 Process parameters in the post-treatment step of the heat-conducting and wave-absorbing composite film
| Examples | Graphitization temperature/. Degree.C | Heat preservation treatment time/h |
| Example 1 | 2300 | 2 |
| Example 2 | 2500 | 1 |
| Example 3 | 2800 | 0.5 |
| Example 4 | 3000 | 0.5 |
Examples 5 to 12
The difference between the heat conduction wave-absorbing composite film and the embodiment 4 is that: the process parameters of the composite slurry preparation step are different, and the specific process parameters are shown in the following table 3.
TABLE 3 Process parameters of preparation steps of the composite slurry of the heat-conducting wave-absorbing composite film
| Examples | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| MXene nanosheet dispersion concentration/(g/L) | 0.03 | 0.03 | 0.03 | 0.03 | 0.1 |
| MXene nanosheet dispersion volume/mL | 200 | 2000 | 1000 | 1200 | 360 |
| MXene nanosheet weight/g | 0.006 | 0.06 | 0.03 | 0.036 | 0.036 |
| Graphene oxide slurry concentration/(g/L) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Graphene oxide slurry volume/mL | 360 | 60 | 240 | 180 | 180 |
| Graphene oxide weight/g | 0.18 | 0.03 | 0.12 | 0.09 | 0.09 |
| Ultrasonic dispersion frequency/kHz | 50 | 50 | 50 | 50 | 50 |
| Ultrasonic dispersion time/h | 2 | 2 | 2 | 2 | 2 |
| Examples | Example 9 | Example 10 | Example 11 | Example 12 | |
| MXene nanosheet dispersion concentration/(g/L) | 0.15 | 0.15 | 0.15 | 0.15 | |
| MXene nanosheet dispersion volume/mL | 240 | 240 | 240 | 240 | |
| MXene nanosheet weight/g | 0.036 | 0.036 | 0.036 | 0.036 | |
| Graphene oxide slurry concentration/(g/L) | 0.5 | 2 | 1 | 1 | |
| Graphene oxide slurry volume/mL | 180 | 45 | 90 | 90 | |
| Graphene oxide weight/g | 0.09 | 0.09 | 0.09 | 0.09 | |
| Ultrasonic dispersion frequency/kHz | 50 | 50 | 50 | 60 | |
| Ultrasonic dispersion time/h | 2 | 2 | 2 | 1 |
Example 13
The difference between the heat conduction wave-absorbing composite film and the embodiment 11 is that: the graphene oxide slurry with the model of XF020-100691 (the sheet diameter is 50-200nm and the concentration is 1 mg/mL) is replaced by the graphene oxide slurry with the model of XF020-100653 (the sheet diameter is 0.5-5 mu m and the concentration is 1 mg/mL) in an equal volume.
Examples 14 to 16
The difference between the heat conduction wave-absorbing composite film and the embodiment 13 is that: before the preparation of the composite slurry, the graphene oxide slurry sold in the market is pretreated, and the specific operation is as follows:
adding isopropanolamine into graphene oxide slurry, shaking for 1min, placing in ultrasonic dispersion equipment, setting ultrasonic frequency to be 5kHz, and performing ultrasonic treatment for 10min to obtain modified graphene oxide slurry;
wherein 0.05g isopropanolamine is taken and added into 1L of graphene oxide slurry in the embodiment 14, and the obtained modified graphene oxide slurry is added into MXene nano-sheet dispersion liquid by replacing the graphene oxide slurry with the same volume;
in example 15, 0.2g isopropanolamine was added to 1L of graphene oxide slurry, and the modified graphene oxide slurry obtained was added to the MXene nanoplatelet dispersion in an equal volume instead of the graphene oxide slurry;
in example 16, 0.5g of isopropanolamine was added to 1L of graphene oxide slurry, and the resulting modified graphene oxide slurry was added to the MXene nanoplatelet dispersion in equal volume instead of the graphene oxide slurry.
Example 16
The difference between the heat conductive wave-absorbing composite film and the embodiment 15 is that: the specific process parameters of the preparation steps of the MXene nano-sheet dispersion liquid are different, and the specific process operation is as follows:
20gMAX phase material Ti 3 AlC 2 Adding 333g hydrofluoric acid solution (which is commercially available product and is diluted to 30 wt%) to gradually increase temperature to 80deg.C at a rate of 5deg.C/min, controlling stirring speed to 400rpm, and stirring for 5 hr to obtain organ-like MXene phase Ti 3 C 2 T x A material;
organ-like MXene phase Ti 3 C 2 T x Transfer of material to deionizationRepeatedly washing in the sub water for 3 times;
0.05g of organ-like MXene phase Ti is taken 3 C 2 T x The material is put into 1L deionized water, placed in an ultrasonic dispersing device, set to ultrasonic frequency of 40kHz, and subjected to ultrasonic treatment for 4 hours to obtain MXene nano-sheet dispersion liquid.
Comparative example
Comparative example 1
A pure MXene film is prepared according to the following steps:
preparation of MXene nanosheet dispersion:
adding 20g of MAX phase material Ti3AlC2 into 100g of hydrofluoric acid solution (the hydrofluoric acid solution is a commercial product and diluted to a concentration of 20wt percent), gradually heating to 60 ℃ at a speed of 5 ℃/min, controlling the stirring speed to be 400rpm, and stirring for 10 hours to obtain the organ-shaped MXene phase Ti3C2Tx material;
transferring the organ-shaped MXene phase Ti3C2Tx material into deionized water, and repeatedly washing for 3 times;
0.03g of organ-like MXene phase Ti is taken 3 C 2 T x Putting the material into 1L deionized water, placing the deionized water into ultrasonic dispersion equipment, setting the ultrasonic frequency to be 40kHz, and carrying out ultrasonic treatment for 4 hours to obtain MXene nanosheet dispersion liquid;
transferring the MXene nano-sheet dispersion liquid into a precise coating machine, coating the dispersion liquid on a substrate, heating to 100 ℃ at the speed of 5 ℃/min, and carrying out heat preservation and drying for 2 hours to obtain a film;
the film is sent into a graphitizing furnace, the temperature in the graphitizing furnace is raised to 2300 ℃, the heat preservation treatment is carried out for 2 hours, argon is introduced into the graphitizing furnace as a shielding gas in the graphitizing treatment process, and the flexible compressible film is obtained;
the flexible compressible film was put into a three-roll calender and calendered until the thickness of the heat-conducting wave-absorbing composite film was 50 μm.
Comparative example 2
Taking 360mL of graphene oxide slurry, transferring the graphene oxide slurry into a precise coating machine, coating the precise coating machine on a substrate, heating to 100 ℃ at a speed of 5 ℃/min, and carrying out heat preservation and drying for 2 hours to obtain a film;
the film is sent into a graphitizing furnace, the temperature in the graphitizing furnace is raised to 2300 ℃, the heat preservation treatment is carried out for 2 hours, argon is introduced into the graphitizing furnace as a shielding gas in the graphitizing treatment process, and the flexible compressible film is obtained;
the flexible compressible film was put into a three-roll calender and calendered until the thickness of the heat-conducting wave-absorbing composite film was 50 μm.
Comparative example 3
A film was distinguished from example 1 in that in the post-treatment step, the film was fed into a graphitization furnace, the temperature was raised to 1000℃in the graphitization furnace, and the heat was preserved for 3 hours.
Performance test
The heat conduction test and the electromagnetic shielding test were conducted on the above examples 1 to 17 and comparative examples 1 to 3 by controlling the thicknesses of the examples 1 to 17 and comparative examples 1 to 3 to be 50.+ -. 0.5. Mu.m.
The thermal conductivity of the films was tested according to ASTM E1461;
testing the shielding effectiveness and shielding wavebands of the films according to ASTM ES-7; the shielding efficiency is more than or equal to 40dB in the shielding wave band.
Detection result
TABLE 4 results of thermal conductivity measurements for examples 1-17 and comparative examples 1-3
TABLE 5 electromagnetic shielding test results for examples 1-17 and comparative examples 1-3
Note that: the larger the maximum electromagnetic shielding efficiency is, the larger the shielding wave band range is, and the better the wave absorbing performance is proved.
It is known from the combination of comparative examples 1 to 3 and example 1 and the combination of tables 4 to 5 that the composite film prepared by combining graphene and MXene nanoplatelets in example 1 through specific graphitization treatment has a synergistic effect in improving the heat conduction performance, and the heat conduction coefficient is higher than that of the pure graphene film (comparative example 2) and the pure MXene film (comparative example 1);
in terms of wave-absorbing performance, the maximum electromagnetic shielding effectiveness of example 1 is smaller than that of a pure MXene film, but the electromagnetic shielding band range is far larger than that of the pure MXene film; the reasons for this may be: the structural defect of the embodiment 1 is repaired in the graphitization treatment process, so that the dielectric property of the composite film is improved, and therefore electromagnetic waves easily enter the composite film, and the wave absorption range of the composite film is enlarged;
the difference between example 1 and comparative example 3 is only that the film treatment temperature is different in the post-treatment, and the thermal conductivity, the electromagnetic shielding maximum efficiency and the electromagnetic shielding band range of comparative example 3 and example 1 are smaller than those of example 1, which shows that graphitizing the film is beneficial to improving the thermal conductivity and the wave absorbing performance of the composite film.
As can be seen from the combination of examples 1-4 and tables 4-5, the graphitization treatment temperatures and times of examples 1-4 are different, and the heat conductivity coefficients, the maximum electromagnetic shielding effectiveness and the detection data of the electromagnetic shielding wave band range of examples 1-4 are all improved significantly, which indicates that the control of the graphitization treatment temperatures and times has a significant effect on the performance of the composite film.
As can be seen from the combination of examples 4 to 12 and tables 4 to 5, the weight ratio of graphene oxide and MXene nanoplatelets only differs in examples 4 to 7, and it can be seen from the detection data that the ratio of example 7 is a preferable ratio, which may be because: in the embodiment 7, the graphene oxide content is moderate, so that MXene nano sheets can be more attached to graphene oxide sheets, and the film forming effect is good when the graphene oxide is used for film forming; in examples 7 to 11, the concentrations of the graphene oxide slurry and the MXene nanoplatelets were changed, and according to the detection data, the optimal concentration of the MXene nanoplatelet dispersion was found to be 0.15g/L, the optimal concentration of the graphene oxide slurry was found to be 1g/L, and the thermal conductivity and the wave absorbing performance of the composite film prepared from the slurry prepared at the optimal concentration were optimal.
As can be seen from the combination of examples 13 to 16 and tables 4 to 5, the addition of isopropanolamine in examples 14 to 16 can significantly improve the heat conductivity and the wave absorbing performance of the composite membrane, and proves that the addition of isopropanolamine is beneficial to the formation of carbon particles in the composite membrane during graphitization, stably supports the lamellar structure in the composite membrane to form a large number of micropores, and the carbon particles are communicated with adjacent lamellar layers in the composite membrane in the longitudinal direction, so that the heat conductivity coefficient of the composite membrane in all directions is increased, and macroscopic performance is improved.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (8)
1. The preparation method of the heat-conducting wave-absorbing composite film is characterized by comprising the following preparation steps:
preparation of MXene nanosheet dispersion: etching the MAX phase material by using an etchant to obtain an organ-shaped MXene phase, and obtaining an MXene nano-sheet dispersion liquid through washing and ultrasonic treatment;
preparing composite slurry: adding isopropanolamine into the graphene oxide slurry, wherein the concentration of the isopropanolamine in the graphene oxide slurry is 0.05-0.5 g/L, and controlling the size of the sheet diameter of the graphene oxide in the graphene oxide slurry to be 0.5-5 mu m;
uniformly mixing the dispersion liquid of the nano sheets with the concentration of 0.03-0.15 g/LMXene and the graphene oxide slurry with the concentration of 0.5-2 g/L, controlling the weight ratio of the nano sheets to the graphene oxide to be (1-10) (5-30), and preparing the composite slurry by ultrasonic dispersion;
film preparation: coating and drying the composite slurry to prepare a film;
post-treatment: and (3) graphitizing the film, and calendaring to obtain the heat-conducting wave-absorbing composite film.
2. The method for preparing the heat conduction wave-absorbing composite film according to claim 1, wherein the method comprises the following steps: in the post-treatment step, the temperature of the film graphitization treatment is 2500-3000 ℃, and the heat preservation treatment is carried out for 0.5-1 h.
3. The method for preparing the heat conduction wave-absorbing composite film according to claim 1, wherein the method comprises the following steps: the preparation method of the MXene nano-sheet dispersion liquid comprises the following specific operations:
adding MAX phase material into hydrofluoric acid with concentration of 20-30wt%, wherein the weight ratio of MAX phase material to hydrofluoric acid is 1 (5-10), stirring for 5-10 h when heating to 60-80 ℃ to obtain organ-shaped MXene phase material;
washing the organ-shaped MXene phase material, then putting the washed organ-shaped MXene phase material into deionized water, and performing ultrasonic treatment for 1-4 hours at the ultrasonic frequency of 40-60 kHz to obtain the MXene nano-sheet dispersion liquid.
4. The method for preparing the heat conduction wave-absorbing composite film according to claim 1, wherein the method comprises the following steps: the MXene nano-sheet in the preparation step of the MXene nano-sheet dispersion liquid comprises Ti 3 C 2 T x 、Ti 2 CT x 、V 2 CT x 、Mo 2 CT x 、Nb 2 CT x 、Nb 4 C 3 T x 、Mo 2 TiC 2 T x And Mo (Mo) 2 Ti 2 C 3 T x At least one of them.
5. The method for preparing the heat conduction wave-absorbing composite film according to claim 1, wherein the method comprises the following steps: in the preparation step of the composite slurry, the weight ratio of the MXene nano-sheets to the graphene oxide is (5-6) (15-20).
6. The method for preparing the heat conduction wave-absorbing composite film according to claim 1, wherein the method comprises the following steps: in the preparation step of the composite slurry, the ultrasonic frequency of ultrasonic dispersion is 50-60 kHz, and the ultrasonic time is 1-2 h.
7. A heat conductive wave absorbing composite film, characterized in that it is produced by the method for producing a heat conductive wave absorbing composite film according to any one of claims 1 to 6.
8. The heat conducting and wave absorbing composite film according to claim 7, wherein the thickness of the heat conducting and wave absorbing composite film is 10 um-700 um.
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