CN111057522B - Preparation method and application of nano metal/graphene composite filler - Google Patents
Preparation method and application of nano metal/graphene composite filler Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a nano metal/graphene composite filler, and belongs to the technical field of composite material preparation. According to the invention, metal salt is added into the prepared aminated graphene oxide solution, and a microwave reaction device is adopted to rapidly realize the reduction of metal ions and aminated graphene oxide, so that the nano metal/graphene composite filler is finally obtained. The composite filler prepared by the method has good conductivity, large specific surface area and good dispersibility; the nano metal in the composite filler is uniformly dispersed on the surface of the graphene, so that the problems that the functional filler is easy to agglomerate in a material system and has poor dispersion stability in the prior art are solved; the method has simple process, is green and environment-friendly, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to a preparation method and application of a nano metal/graphene composite filler.
Background
With the wide application of electronic devices in daily life, electromagnetic pollution has become the fourth largest pollution after atmospheric pollution, water pollution and noise pollution, and the development of electromagnetic shielding materials is an effective method for solving the electromagnetic pollution. The metal filler has excellent conductivity and is a traditional electromagnetic shielding functional filler, but the metal filler has the defects of high density, high oxidation tendency, high cost and the like, and further development and application of the metal filler in the electromagnetic shielding material are restricted. Graphene is a novel two-dimensional carbon material which is rapidly developed in recent years, has the advantages of ultrahigh conductivity, low density, high specific surface area, chemical inertness and the like, and has a very wide application prospect in the field of electromagnetic shielding. However, due to van der waals force between graphene sheets, stacking and agglomeration are very easy to occur in a material system, so that the overall performance of the material is affected.
Moreover, the prior patents have the following problems: the addition amount of the metal filler is large, so that the manufacturing cost of the material is increased, and the mechanical property of the material is adversely affected; the metal and the graphene have no binding force on the surfaces and have overlarge density difference, so that the metal and the graphene cannot be uniformly and stably distributed in a material system in the preparation process, and the electromagnetic shielding performance of the material can be influenced; in the preparation process, toxic reducing agents such as sodium borohydride and the like are used, so that the preparation method is harmful to the environment.
Therefore, it is an urgent need to solve the problems of the technical personnel in the field to provide a preparation method of a nano metal/graphene composite filler and an application thereof.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of a nano metal/graphene composite filler, wherein a metal salt is added into a prepared aminated graphene oxide solution, and a microwave reaction device is adopted to rapidly realize reduction of metal ions and aminated graphene oxide, so that the nano metal/graphene composite filler is finally obtained. The nitrogen-containing functional groups on the modified aminated graphene oxide can generate a complexing effect with metal ions, and play a role in anchoring nano metal in the preparation process, and the nano metal is dispersed among graphene sheet layers, so that the spacing effect is achieved, graphene stacking is inhibited, the dispersibility is improved, a vertical conductive path can be formed, the conductivity is improved, and the electromagnetic shielding performance is further improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano metal/graphene composite filler comprises the following specific steps:
(1) Preparing a graphene oxide dispersion liquid: dissolving graphene oxide in deionized water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid; the concentration of the graphene oxide in the dispersion liquid is 1-10 mg/mL;
(2) Preparing aminated graphene oxide: adding ammonia water into the graphene oxide dispersion liquid prepared in the step (1), and adjusting the pH value of the solution to 10-12; heating and refluxing the solution, filtering and washing with deionized water after the reaction is finished and the solution is cooled, and freeze-drying the obtained solid product until the solid product is completely dried to obtain aminated graphene oxide;
(3) Preparing the nano metal/graphene composite filler:
A. adding the aminated graphene oxide prepared in the step (2) into deionized water, and performing ultrasonic dispersion to obtain an aminated graphene oxide dispersion liquid; the concentration of the aminated graphene oxide in the dispersion liquid is 1-10 mg/mL;
B. adding metal salt powder into the aminated graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed liquid; the concentration of the metal salt in the mixed solution is 0.01-0.1 mmol/mL;
C. placing the mixed solution in a microwave reaction device for liquid-phase microwave reduction reaction, and after the reaction is finished, filtering and washing with deionized water after the solution is cooled;
D. and (3) freeze-drying the obtained solid product until the solid product is completely dried to obtain the nano metal/graphene composite filler.
Further, the graphene oxide in the step (1) is prepared by a modified Hummers method.
The method for preparing the graphene oxide by improving the Hummers method comprises the following specific steps: measuring 35mL of concentrated sulfuric acid, cooling to below 2 ℃ under an ice bath condition, adding 1.5g of crystalline flake graphite under an ice bath and stirring state, and slowly adding 4g of potassium permanganate (the temperature of an adding process is controlled to be lower than 20 ℃); raising the temperature of the system to 40 ℃, continuing stirring for 1h, slowly adding 70mL of deionized water, raising the temperature of the system to 95 ℃, and stirring for 1h; 500mL of deionized water was added, 15mL of hydrogen peroxide (30%) was slowly added, and the mixture was washed with 150mL of 10% hydrochloric acid and deionized water; and (3) dispersing the product in 500mL of deionized water again, dialyzing, and performing suction filtration and freeze drying treatment to obtain the graphene oxide.
Further, the ultrasonic dispersion conditions in the step (1) and the step (3) A are as follows: the ultrasonic power is 500-1000W, and the ultrasonic time is 0.5-2 min.
Further, the temperature of the heating reflux reaction in the step (2) is 60-90 ℃, and the time is 3-10 h.
Further, in the step (3) B, the metal salt is one of silver nitrate, copper chloride, copper sulfate, nickel nitrate or nickel sulfate.
Further, the power of the liquid phase microwave reduction reaction in the step (3) C is 300-1100W, and the time is 0.5-5 min.
Further, in the step (2) and the step (3), after the reaction is finished, the solution is cooled to room temperature, filtered, washed by deionized water, and circularly treated for 3 times.
Further, the nano metal/graphene composite filler is applied to preparation of electromagnetic shielding materials.
According to the technical scheme, compared with the prior art, the invention discloses a preparation method and application of a nano metal/graphene composite filler, the graphene is subjected to amination modification, nitrogen-containing functional groups on graphene sheets can generate a complexing effect with metal ions, and the complexing effect plays a role in anchoring nano metal in the preparation process, so that the finally obtained composite filler nano metal has strong binding force with the graphene, and the problem of dispersion stability of the composite filler in a material system due to large density difference is solved; according to the preparation method, the nano metal is adopted to modify the graphene, and the nano metal is dispersed among graphene sheet layers, so that the spacing effect is achieved, the graphene stacking is inhibited, the dispersibility is improved, a vertical conductive path can be formed, the conductivity is improved, and the electromagnetic shielding performance is further improved; the graphene/nano-metal composite filler is rapidly prepared by adopting a liquid-phase microwave reduction method, synchronous reduction of nano-metal and aminated graphene oxide is realized, toxic reducing agents such as hydrazine hydrate, sodium borohydride and the like are not used in the reduction process, and the preparation method is simple in process, green and environment-friendly and suitable for industrial mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is an SEM image of a nano copper/graphene composite filler prepared in example 1 of the present invention;
fig. 2 is a diagram showing the shielding performance of the electromagnetic shielding material prepared from the composite filler according to embodiment 7 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dissolving 0.10g of graphene oxide in 100mL of deionized water by adopting the graphene oxide prepared by an improved Hummers method, and performing ultrasonic dispersion treatment (500W, 2min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (60 ℃,10 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly processing for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (500W, 2min) to obtain an aminated graphene oxide dispersion liquid; adding 1.00g (4 mmol) of copper sulfate pentahydrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device for liquid-phase microwave reduction reaction (300W, 5 min); after the reaction is finished, cooling the solution to room temperature, filtering and washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano copper/graphene composite filler. The nano-copper/graphene composite filler prepared by SEM observation is shown in figure 1; as can be seen from the figure, the graphene sheets are thin, and the nano-copper is uniformly distributed between the graphene sheets.
Example 2
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.20g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (700W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 12; then heating the solution in water bath (80 ℃,8 h), and after the reaction is finished, cooling the solution to room temperature for filtering and washing with deionized water for 3 times in a circulating manner; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (700W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.85g (5 mmol) of copper chloride dihydrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device for liquid-phase microwave reduction reaction (600W, 3min); after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano copper/graphene composite filler.
Example 3
(1) Dissolving 0.40g of graphene oxide in 100mL of deionized water by adopting the graphene oxide prepared by an improved Hummers method, and performing ultrasonic dispersion treatment (1000W, 0.5 min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (90 ℃,3 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly processing for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 0.5min) to obtain an aminated graphene oxide dispersion liquid; then adding 1.88g (10 mmol) of copper nitrate powder into the amination graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device to perform liquid-phase microwave reduction reaction (1100W, 0.5min); after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano copper/graphene composite filler.
Example 4
(1) Dissolving 1.00g of graphene oxide in 100mL of deionized water by adopting the graphene oxide prepared by an improved Hummers method, and performing ultrasonic dispersion treatment (800W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 11; then heating the solution in water bath (90 ℃,3 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly processing for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (800W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 1.75g (7 mmol) of copper sulfate pentahydrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device for liquid-phase microwave reduction reaction (900W, 3min); after the reaction is finished, cooling the solution to room temperature, filtering and washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano copper/graphene composite filler.
Example 5
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.40g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (1000W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (60 ℃,8 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.17g (1 mmol) of silver nitrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device to perform liquid phase microwave reduction reaction (700W, 1min); after the reaction is finished, cooling the solution to room temperature, filtering and washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano silver/graphene composite filler.
Example 6
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.80g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (1000W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 11; then heating the solution in water bath (70 ℃,8 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly processing for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.51g (3 mmol) of silver nitrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device to perform liquid-phase microwave reduction reaction (1100W, 2min); after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano silver/graphene composite filler.
Example 7
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.40g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (1000W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; and then heating the solution in water bath (80 ℃,8 h), cooling the solution to room temperature after the reaction is finished, filtering, washing with deionized water, and circularly treating for 3 times. Finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.85g (5 mmol) of silver nitrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device to perform liquid-phase microwave reduction reaction (1100W, 3min); after the reaction is finished, cooling the solution to room temperature, filtering and washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano silver/graphene composite filler.
Example 8
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.80g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (1000W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (90 ℃,8 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.34g (2 mmol) of silver nitrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device to perform liquid-phase microwave reduction reaction (1100W, 1min); after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano silver/graphene composite filler.
Example 9
(1) Adopting graphene oxide prepared by an improved Hummers method, dissolving 0.40g of graphene oxide in 100mL of deionized water, and performing ultrasonic dispersion treatment (1000W, 1min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (80 ℃,8 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain an aminated graphene oxide dispersion liquid; then 0.52g (2 mmol) of nickel sulfate hexahydrate powder is added into the amination graphene oxide dispersion liquid and is uniformly stirred to obtain a mixed solution, and then the mixed solution is placed into a microwave reaction device for liquid phase microwave reduction reaction (1100W, 1min); after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano nickel/graphene composite filler.
Example 10
(1) Dissolving 0.60g of graphene oxide in 100mL of deionized water by adopting the graphene oxide prepared by an improved Hummers method, and performing ultrasonic dispersion treatment (600W, 2min) on the mixed solution to obtain a graphene oxide dispersion liquid;
(2) Adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to 10; then heating the solution in water bath (70 ℃,8 h), after the reaction is finished, cooling the solution to room temperature, filtering, washing with deionized water, and circularly processing for 3 times; finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain aminated graphene oxide;
(3) Adding the aminated graphene oxide obtained in the step (2) into 100mL of deionized water for ultrasonic dispersion (600W, 2min) to obtain an aminated graphene oxide dispersion liquid; then adding 0.58g (2 mmol) of nickel nitrate hexahydrate powder into the aminated graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, and then placing the mixed solution into a microwave reaction device for carrying out liquid-phase microwave reduction reaction (600W, 3min); after the reaction is finished, cooling the solution to room temperature, filtering and washing with deionized water, and circularly treating for 3 times; and finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to obtain the nano nickel/graphene composite filler.
Comparative example 1
And adding 0.40g of graphene oxide into 100mL of deionized water for ultrasonic dispersion (1000W, 1min) to obtain a graphene oxide dispersion liquid, then placing the dispersion liquid in a microwave reaction device for liquid-phase microwave reduction reaction (1100W, 1min), after the reaction is finished, cooling the solution, filtering and cleaning the solution with deionized water for 3 times in a circulating manner, and freeze-drying the obtained solid product for 24 hours to finally obtain the graphene filler which is not modified by the nano metal.
Comparative example 2
Adding 0.80g of graphene oxide into 100mL of deionized water, performing ultrasonic dispersion (1000W, 1min) to obtain a graphene oxide dispersion liquid, adding 1.00g (4 mmol) of copper sulfate pentahydrate powder into the graphene oxide dispersion liquid, uniformly stirring to obtain a mixed solution, then placing the mixed solution into a microwave reaction device to perform liquid-phase microwave reduction reaction (1100W, 1min), and after the reaction is finished, filtering and cleaning the solution with deionized water for 3 times in a circulating manner. And finally, carrying out freeze drying treatment on the obtained solid product for 24 hours to finally obtain the nano copper/graphene composite filler which is not subjected to amination modification.
The composite filler prepared in the examples 1 to 10 and the comparative examples 1 to 2 is used as the electromagnetic shielding functional filler for preparing the electromagnetic shielding material, preferably, the electromagnetic shielding material is a coating, and the electromagnetic shielding performance of the coating is compared through a test.
The electromagnetic shielding coating comprises the following components in percentage by mass: 30% of resin, 20% of extender filler, 5% of functional filler, 5% of auxiliary agent and 40% of solvent; the preparation process of the electromagnetic shielding coating comprises the following steps: physically blending all components of a coating formula and uniformly dispersing by adopting a mechanical stirrer to prepare the coating; the method for testing the shielding performance of the electromagnetic shielding coating comprises the following steps: the electromagnetic shielding paint is coated on an insulated epoxy resin plate by brush coating according to the regulation of GB/T25471-2010, the dry film thickness of the coating is 100 mu m, and the electromagnetic shielding effectiveness tester is used for testing by adopting a flange coaxial method. The test results are shown in Table 1.
Table 1 shielding effectiveness test results
Note: the blank case is a coating prepared without adding functional filler, and the specific composition comprises 30% of resin, 25% of extender filler, 5% of auxiliary agent and 40% of solvent; the shielding effectiveness reflects the shielding capability of the material on electromagnetic waves, and the larger the value of the shielding effectiveness, the more excellent the electromagnetic shielding performance of the material is.
The results in table 1 show that the blank case is a coating prepared without using a functional filler, the shielding effectiveness to electromagnetic waves is close to 0dB, the composite filler prepared in examples 1 to 10 has better shielding performance when applied to electromagnetic shielding coatings, wherein the shielding effectiveness of the electromagnetic shielding coating prepared from the nano silver/graphene functional filler can reach more than 35dB, and the electromagnetic waves of more than 99.999% can be shielded; by comprehensively comparing examples 1-10 with comparative example 1, the shielding effectiveness of the pure graphene composite coating on electromagnetic waves is 14-16 dB, and the shielding performance of the coating is obviously improved after the nano metal modified graphene is used; by comprehensively comparing examples 1-4 and comparative example 2, the interaction force between the aminated and modified graphene and metal can be better utilized to play a synergistic effect, and the shielding performance of the coating can be further improved.
The shielding performance graph of the electromagnetic shielding material prepared by using the nano silver/graphene composite filler of embodiment 7 is shown in fig. 2, and it can be seen from the graph that the shielding effectiveness of the electromagnetic shielding material is greater than 35dB, and the shielding performance is excellent.
The nano metal/graphene composite filler prepared by the preparation method can be used for electromagnetic shielding materials, and can obviously improve the shielding performance of the materials.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a nano metal/graphene composite filler is characterized by comprising the following specific steps:
(1) Preparing a graphene oxide dispersion liquid: dissolving graphene oxide in deionized water, and performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid; the concentration of the graphene oxide in the dispersion liquid is 1-10 mg/mL;
(2) Preparing aminated graphene oxide: adding ammonia water into the graphene oxide dispersion liquid prepared in the step (1), and adjusting the pH value of the solution to 10-12; heating and refluxing the solution, filtering and washing with deionized water after the reaction is finished and the solution is cooled, and freeze-drying the obtained solid product to obtain aminated graphene oxide;
(3) Preparing the nano metal/graphene composite filler:
A. adding the aminated graphene oxide prepared in the step (2) into deionized water, and performing ultrasonic dispersion to obtain an aminated graphene oxide dispersion liquid; the concentration of the aminated graphene oxide in the dispersion liquid is 1-10 mg/mL;
B. adding metal salt powder into the aminated graphene oxide dispersion liquid, and uniformly stirring to obtain a mixed liquid; the concentration of the metal salt in the mixed solution is 0.01-0.1 mmol/mL;
C. carrying out liquid phase microwave reduction reaction on the mixed solution, and after the reaction is finished, filtering and washing the solution by deionized water after the solution is cooled;
D. and (4) freeze-drying the obtained solid product to obtain the nano metal/graphene composite filler.
2. The method for preparing the nano metal/graphene composite filler according to claim 1, wherein the graphene oxide in the step (1) is prepared by a modified Hummers method.
3. The method for preparing the nano metal/graphene composite filler according to claim 1, wherein the ultrasonic dispersion conditions in the step (1) and the step (3) A are as follows: the ultrasonic power is 500-1000W, and the ultrasonic time is 0.5-2 min.
4. The preparation method of the nano metal/graphene composite filler according to claim 1, wherein the temperature of the heating reflux reaction in the step (2) is 60-90 ℃ and the time is 3-10 h.
5. The method for preparing nano metal/graphene composite filler according to claim 1, wherein the metal salt in the step (3) B is one of silver nitrate, copper chloride, copper sulfate, nickel nitrate or nickel sulfate.
6. The method for preparing the nano metal/graphene composite filler according to claim 1, wherein the power of the liquid phase microwave reduction reaction in the step (3) C is 300-1100W, and the time is 0.5-5 min.
7. The preparation method of the nano metal/graphene composite filler according to claim 1, wherein in the step (2) and the step (3) C, after the reaction is finished, the solution is cooled to room temperature, filtered and washed by deionized water, and is circularly treated for 3 times.
8. Use of the nanometal/graphene composite filler according to any one of claims 1 to 7 for the preparation of electromagnetic shielding materials.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555996A (en) * | 2014-07-28 | 2015-04-29 | 南京新月材料科技有限公司 | Preparation method and application of aminated graphene film |
| CN105602194A (en) * | 2015-12-24 | 2016-05-25 | 北京航空航天大学 | Ni nanoparticle modified graphene and preparation method of wave-absorbing material |
| CN107333460A (en) * | 2017-06-30 | 2017-11-07 | 河北大学 | A kind of preparation method of graphene-based metal composite absorbing material |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
| CN109250711A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of preparation method of amination graphene oxide |
| CN109847736A (en) * | 2018-12-24 | 2019-06-07 | 柯良节 | A kind of graphene composite material and the preparation method and application thereof |
-
2019
- 2019-12-30 CN CN201911401733.5A patent/CN111057522B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555996A (en) * | 2014-07-28 | 2015-04-29 | 南京新月材料科技有限公司 | Preparation method and application of aminated graphene film |
| CN105602194A (en) * | 2015-12-24 | 2016-05-25 | 北京航空航天大学 | Ni nanoparticle modified graphene and preparation method of wave-absorbing material |
| CN107333460A (en) * | 2017-06-30 | 2017-11-07 | 河北大学 | A kind of preparation method of graphene-based metal composite absorbing material |
| CN109250710A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of amination graphene oxide |
| CN109250711A (en) * | 2017-07-13 | 2019-01-22 | 山东欧铂新材料有限公司 | A kind of preparation method of amination graphene oxide |
| CN109847736A (en) * | 2018-12-24 | 2019-06-07 | 柯良节 | A kind of graphene composite material and the preparation method and application thereof |
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