CN113881214B - High-conductivity graphene/polymer composite material and preparation method thereof - Google Patents
High-conductivity graphene/polymer composite material and preparation method thereof Download PDFInfo
- Publication number
- CN113881214B CN113881214B CN202111236550.XA CN202111236550A CN113881214B CN 113881214 B CN113881214 B CN 113881214B CN 202111236550 A CN202111236550 A CN 202111236550A CN 113881214 B CN113881214 B CN 113881214B
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- polyurethane
- preparation
- polymer composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention discloses a high-conductivity graphene/polymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps: step 1: fully and uniformly mixing graphene powder and aqueous polyurethane emulsion in a solvent to obtain a graphene dispersion liquid; step 2: brushing the graphene dispersion liquid obtained in the step (1) on the surface of the heated polyurethane thermosol net film, and drying to obtain a graphene/polyurethane net film; and step 3: and (3) folding the graphene/polyurethane mesh film obtained in the step (2) in half in a manner that the graphene coating surfaces are mutually contacted, and carrying out hot pressing to obtain the required composite material. The composite material obtained by the invention has excellent conductive property and mechanical flexibility, the process flow of the invention is simple, the operation is convenient, the requirement on preparation conditions is low, and the problem that the composite material is difficult to process under the condition of high filling amount of functional particles by the traditional melt blending method is solved.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a high-conductivity graphene/polymer composite material and a preparation method thereof.
Background
The polymer material is widely concerned by people due to the advantages of light weight, good flexibility, easy processing and the like, but the inherent insulativity of the polymer material greatly limits the application of the polymer material in the field of power electronic devices requiring a conductive function. The preparation of polymer composite materials by adding conductive functional particles into a polymer matrix is an effective method for enhancing the conductivity of materials widely adopted at present. For the polymer conductive composite material, the key point of the preparation is to form a continuous conductive network in a polymer matrix, and the composite material can have excellent conductive performance only by forming the continuous conductive network.
The traditional polymer-based conductive composite material is mainly prepared by adopting a method of melt mixing and solution mixing, wherein conductive functional particles are randomly distributed in a polymer matrix, the capability of constructing a conductive network is low, and a high-efficiency complete conductive network cannot be formed inside the material. Meanwhile, the conductive particles are wrapped by the polymer, so that the contact resistance and the interface thermal resistance are large, and the inherent good performance of the conductive particles cannot be fully exerted. Although the conductivity of the composite material can be improved by adding the content of the conductive particles, the high addition amount causes problems such as a decrease in mechanical properties of the composite material and a deterioration in processability.
At present, the conductivity of the composite material can be obviously improved by purposefully constructing a conductive path through the microstructure design of the polymer conductive composite material, and common methods comprise the methods of functional particle orientation structure design, hybrid particle compounding, double percolation structure construction, self-assembly 3D network construction and the like. Although the methods can effectively regulate and control the distribution form of the functional particles and realize the construction of the high-efficiency conductive network, the methods are complex in preparation process and high in requirements on instruments and equipment, and large-scale application and production are difficult to realize.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-conductivity graphene/polymer composite material with a high-efficiency conductive network structure and a preparation method thereof, which can be prepared simply, conveniently, efficiently and economically.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-conductivity graphene/polymer composite material,
further, in the step 1, the solid content of the aqueous polyurethane solution is 30%, and the solvent is water.
Further, a vortex oscillator is used for mixing in the step 1.
Further, the temperature for heating the polyurethane hot melt adhesive net film in the step 2 is 70 ℃.
Further, the temperature of hot pressing in the step 3 is 130 ℃, and the pressure is 2 MPa; preheating for 10s during hot pressing, wherein the hot pressing time is 1min, and the cooling time is 3 min.
Further, the mass ratio of the graphene to the aqueous polyurethane emulsion in the step 1 is 9: 1.
Further, the surface density of the polyurethane hot melt adhesive net membrane in the step 2 is 25g/m2。
The graphene/polymer composite material comprises the following components in percentage by mass: 40-60% of graphene and 40-60% of polyurethane.
The invention has the beneficial effects that:
(1) the method has the advantages of simple process flow, convenient operation and low requirement on preparation conditions, and overcomes the difficult problem that the functional particles are difficult to process under high filling amount by the traditional melt blending method;
(2) according to the composite material obtained by the invention, the graphene sheet layers are firstly subjected to hot pressing to form a more compact conductive path, so that the contact resistance between the graphene sheet layers is greatly reduced, a certain amount of high-molecular polymer molecular chains move between the graphene sheet layers on two sides through short-time melting, and the completeness and flexibility of the material structure are ensured; the structure ensures that the material has excellent conductive property and mechanical flexibility.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention.
Fig. 2 is a microscopic morphology of the graphene/polymer composite obtained in example 2.
Detailed Description
The invention is further described with reference to the following figures and specific embodiments.
As shown in fig. 1, a method for preparing a highly conductive graphene/polymer composite material includes the following steps:
step 1: adding graphene powder and a water-based polyurethane solution with the solid content of 30% into distilled water, and uniformly mixing by adopting a vortex oscillator to obtain a graphene dispersion liquid;
step 2: uniformly brushing the graphene dispersion liquid obtained in the step 1 on the surface of a heated polyurethane thermosol net film (with the surface temperature of 70 ℃) by using a brush pen, and drying (after the moisture in the net film is evaporated to dryness) to obtain a graphene/polyurethane net film; the surface density of the polyurethane hot melt adhesive net membrane is 25g/m2。
And step 3: and (3) folding the graphene/polyurethane mesh film obtained in the step (2) in half in a manner that the graphene coating surfaces are in contact with each other, and carrying out hot pressing (hot pressing by adopting a press) to obtain the required composite material. The hot pressing temperature is 130 ℃, and the pressure is 2 MPa; preheating for 10s during hot pressing, wherein the hot pressing time is 1min, and the cooling time is 3 min. The composite material comprises the following components in percentage by mass: 40-60% of graphene and 40-60% of polyurethane.
Example 1
A preparation method of a high-conductivity graphene/polymer composite material comprises the following steps:
step 1: adding graphene and aqueous polyurethane emulsion with the solid content of 30% into distilled water, wherein the mass ratio of the graphene to the aqueous polyurethane emulsion is 9:1, and oscillating and uniformly mixing in a vortex to obtain graphene dispersion liquid.
Step 2: and (3) uniformly brushing the graphene dispersion liquid obtained in the step (1) on the surface of a polyurethane thermosol net film placed on a heating table at 70 ℃ by using a brush pen to obtain the graphene/polyurethane net film.
And step 3: and (3) carrying out hot pressing on the graphene/polyurethane mesh film obtained in the step (2) to obtain the graphene/polymer conductive composite material. The temperature of the hot press is set to be 130 ℃, the pressure is 2MPa, the preheating is carried out for 10s during hot pressing, the hot pressing time is 1min, and the cooling time is 3 min. In the obtained composite material, the mass percentage of graphene is 40% and the mass percentage of polyurethane is 60%.
Example 2
A preparation method of a high-conductivity graphene/polymer composite material comprises the following steps:
step 1: adding graphene and aqueous polyurethane emulsion with the solid content of 30% into distilled water, wherein the mass ratio of the graphene to the aqueous polyurethane emulsion is 9:1, and oscillating and uniformly mixing in a vortex to obtain graphene dispersion liquid.
Step 2: and (3) uniformly brushing the graphene dispersion liquid obtained in the step (1) on the surface of a polyurethane thermosol net film placed on a heating table at 70 ℃ by using a brush pen to obtain the graphene/polyurethane net film.
And step 3: and (3) carrying out hot pressing on the graphene/polyurethane mesh film obtained in the step (2) to obtain the graphene/polymer conductive composite material. The temperature of the hot press is set to be 130 ℃, the pressure is 2MPa, the preheating is carried out for 10s during hot pressing, the hot pressing time is 1min, and the cooling time is 3 min. In the obtained composite material, the mass percentage of graphene is 50% and the mass percentage of polyurethane is 50%.
The microscopic morphology of the resulting composite material is shown in FIG. 2, and the cross section of the composite material was observed using a field emission scanning electron microscope (aspect-F, FEI, USA). As can be seen from the figure, the composite material has a layered gradient structure, the content of the polymer is gradually reduced from the skin layer to the core layer, the core layer forms a compact graphene conductive path, and a small amount of polymer permeates into the skin layer graphene conductive path.
Example 3
A preparation method of a high-conductivity graphene/polymer composite material comprises the following steps:
step 1: adding graphene powder and aqueous polyurethane emulsion with the solid content of 30% into distilled water, wherein the mass ratio of graphene to aqueous polyurethane emulsion is 9:1, and performing vortex oscillation and uniform mixing to obtain graphene dispersion liquid.
Step 2: and (3) uniformly brushing the graphene dispersion liquid obtained in the step (1) on the surface of a polyurethane thermosol net film placed on a heating table at 70 ℃ by using a brush pen to obtain the graphene/polyurethane net film.
And step 3: and (3) carrying out hot pressing on the graphene/polyurethane mesh film obtained in the step (2) to obtain the graphene/polymer conductive composite material. The temperature of the hot press is set to be 130 ℃, the pressure is 2MPa, the preheating is carried out for 10s during hot pressing, the hot pressing time is 1min, and the cooling time is 3 min. In the obtained composite material, the mass percentage of graphene is 60% and the mass percentage of polyurethane is 40%.
In order to illustrate the effect of the invention, a comparative example was set, in which the composite material was prepared as in example 1, and graphene and aqueous polyurethane were not added.
In order to illustrate the conductivity of the composite material, an RTS-8 four-probe tester was used to test the conductivity of the composite material at different graphene contents, and the test results are shown in table 1.
TABLE 1 conductivity of graphene/Polymer conductive composites
As can be seen from table 1, the graphene/polymer composite material obtained by the present invention exhibits excellent conductive properties. When the graphene content of the composite material is 40%, the conductivity reaches 480.6S/m; when the content of the graphene is increased to 60%, the conductivity of the composite material is as high as 2546.5S/m. The excellent conductive property of the composite material is mainly attributed to the unique layered gradient structure design, the content of the polymer is gradually reduced from the skin layer to the core layer, the core layer forms a compact graphene conductive path, and a small amount of polymer permeates into the skin layer graphene conductive path. According to the invention, a spraying process is adopted, so that graphene conducting layers can be formed on the surface of the hot melt adhesive net film, certain pressure is firstly applied in the hot press molding process to enable graphene sheets to be more compact, the contact resistance between the graphene sheets is effectively reduced, and the melted part of the polyurethane matrix is infiltrated into the graphene conducting layers through heat treatment, so that the structural integrity of the composite material is ensured.
Claims (5)
1. A preparation method of a high-conductivity graphene/polymer composite material is characterized by comprising the following steps:
step 1: fully and uniformly mixing graphene powder and aqueous polyurethane emulsion in a solvent to obtain a graphene dispersion liquid;
step 2: brushing the graphene dispersion liquid obtained in the step (1) on the surface of the heated polyurethane thermosol net film, and drying to obtain a graphene/polyurethane net film; the heating temperature of the polyurethane hot-melt adhesive net film is 70 ℃;
and step 3: folding the graphene/polyurethane mesh film obtained in the step 2 in a manner that the graphene coating surfaces are in contact with each other, and carrying out hot pressing to obtain the required composite material; the hot pressing temperature is 130 ℃, and the pressure is 2 MPa; preheating for 10s during hot pressing, wherein the hot pressing time is 1min, and the cooling time is 3 min; the composite material comprises the following components in percentage by mass: 40-60% of graphene and 40-60% of polyurethane.
2. The preparation method of the highly conductive graphene/polymer composite material according to claim 1, wherein in the step 1, the solid content of the aqueous polyurethane emulsion is 30%, and the solvent is water.
3. The method for preparing the highly conductive graphene/polymer composite material according to claim 1, wherein a vortex oscillator is used for mixing in step 1.
4. The preparation method of the highly conductive graphene/polymer composite material according to claim 1, wherein the mass ratio of the graphene to the aqueous polyurethane emulsion in the step 1 is 9: 1.
5. The method for preparing the highly conductive graphene/polymer composite material according to claim 1, wherein the membrane surface density of the polyurethane hot melt adhesive net in the step 2 is 25g/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111236550.XA CN113881214B (en) | 2021-10-23 | 2021-10-23 | High-conductivity graphene/polymer composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111236550.XA CN113881214B (en) | 2021-10-23 | 2021-10-23 | High-conductivity graphene/polymer composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113881214A CN113881214A (en) | 2022-01-04 |
| CN113881214B true CN113881214B (en) | 2022-04-22 |
Family
ID=79013437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111236550.XA Active CN113881214B (en) | 2021-10-23 | 2021-10-23 | High-conductivity graphene/polymer composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113881214B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201000743D0 (en) * | 2010-01-18 | 2010-03-03 | Univ Manchester | Graphene polymer composite |
| TWI560144B (en) * | 2014-06-24 | 2016-12-01 | Graphene polymer composite material | |
| CN104389111A (en) * | 2014-10-23 | 2015-03-04 | 平湖展鹏热熔胶膜有限公司 | Preparation method for low-melting-point polyurethane hot-melt adhesive net film and crystallization and solidification device |
-
2021
- 2021-10-23 CN CN202111236550.XA patent/CN113881214B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113881214A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103173003B (en) | Carbon nanotube-water-soluble polymer composite flexible electric-heating film as well as preparation method and use thereof | |
| CN101604727B (en) | Electrostrictive composite material and preparation method thereof | |
| CN111073059B (en) | Nano-cellulose electrothermal film and preparation method thereof | |
| KR101623781B1 (en) | Functional molded article and method for producing same | |
| CN101671442A (en) | Preparation method of carbon nano tube array composite material | |
| CN112290040A (en) | Preparation method of composite graphite bipolar plate | |
| CN104552947A (en) | Graphene fused deposition 3D printing method and application thereof | |
| WO2018145372A1 (en) | Method for preparing high-performance polymer based conductive composite material using micro-nano precision assembly method within confinement space | |
| CN108521683B (en) | Nano-cellulose graphene oxide electric heating material and preparation method thereof | |
| CN113861665A (en) | High-thermal-conductivity boron nitride/polyurethane thermal-conductivity composite material and preparation method thereof | |
| CN105885804B (en) | A kind of preparation method of graphene all-carbon composite heat interfacial material | |
| KR20160033856A (en) | Conducting film and method of manufacturing the same | |
| Han et al. | One-step exfoliation and deprotonation of ANF/BNNS suspension for constructing 3D vertically aligned skeleton in epoxy-based thermal management composites | |
| CN113881214B (en) | High-conductivity graphene/polymer composite material and preparation method thereof | |
| CN112662101B (en) | Polyvinyl alcohol-organic phosphonic acid @ graphene-based membrane, multilayer film and preparation method thereof | |
| KR101993883B1 (en) | Method for Manufacturing Non Metallic Silicon Complex Using Nano Hole of CNT and the Silicon Complex | |
| CN110964219B (en) | Nano cellulose membrane with high thermal conductivity and preparation method thereof | |
| Chen et al. | Aramid-based electric heating films by incorporating carbon black | |
| KR102003682B1 (en) | Flow channel plate for fuel cell and method of manufacturing the same | |
| Yao et al. | Biomimetic and flexible high-performance carbon paper prepared by welding three-dimensional carbon fiber network with polyphenylene sulfide spherical sites for fuel cell gas diffusion layer | |
| CN113278218B (en) | Conductive composite material with isolation structure and preparation method thereof | |
| CN111560127B (en) | Method for preparing boron nitride nanosheet by stripping hexagonal boron nitride powder and used for preparing BNNS-cellulose composite material | |
| CN113308800A (en) | Graphene-based high-molecular thermal interface material and preparation method thereof | |
| CN106832522A (en) | A kind of electromagnetic shielding composite material with orientation isolation structure and preparation method thereof | |
| CN113150665A (en) | Medium-high temperature graphene heating slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |