CN108147393B - High-strength high-toughness high-conductivity graphene film and preparation method thereof - Google Patents
High-strength high-toughness high-conductivity graphene film and preparation method thereof Download PDFInfo
- Publication number
- CN108147393B CN108147393B CN201711415510.5A CN201711415510A CN108147393B CN 108147393 B CN108147393 B CN 108147393B CN 201711415510 A CN201711415510 A CN 201711415510A CN 108147393 B CN108147393 B CN 108147393B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- graphene film
- graphene
- toughness
- film
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/26—Mechanical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Landscapes
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a high-strength high-toughness high-conductivity graphene film and a preparation method thereof. The method comprises the following steps: mixing a small amount of rare earth metal ions, a polymer and graphene oxide to prepare uniform hydrosol, casting, air-drying and forming a film, and then carrying out reduction, cleaning and drying steps to obtain the graphene film. According to the invention, three interactions are simultaneously established, including coordination bonds between graphene oxide and rare earth ions, hydrogen bonds between graphene oxide and macromolecules and pi-pi action between graphene oxide and macromolecules, so that the prepared modified graphene film has high strength, high toughness and good electrical conductivity. The method has the advantages of cheap raw materials, simple operation, suitability for mass production, good industrial production basis and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a high-strength high-toughness conductive graphene film and a preparation method thereof.
Background
The graphene has excellent performances of large specific surface area, light weight, high strength, high conductivity and the like. The graphene nanosheets are assembled into the two-dimensional graphene film, so that the application of graphene on a macroscopic scale is successfully realized. To date, researchers have developed graphene films with various functionalities and have been primarily applied to the fields of thermal conductive materials, separation films, electrode materials, and electronic displays.
In the development of graphene films, improving the mechanical properties thereof is an important topic. Researchers can remarkably improve the strength and modulus of the graphene film by introducing macromolecules to construct covalent bond crosslinked graphene nanosheets (Y. Tian, Y.W. Cao, Y. Wang, W.L. Yang and J.C. Feng,Adv.Mater. 2013, 25, 2980; Y. Xu, H. Bai, G. Lu, C. Li and G. Shi, J. Am. Chem. Soc.2008, 130, 5856). However, such strong covalent bonds tend to reduce the elongation at break of the graphene film, eventually resulting in a material with poor fracture toughness. For most applications, the toughness of the material is an important index, so that the preparation of the graphene film with balanced rigidity and toughness is particularly important in practical applications. Recently, researchers introduce a flexible polymer chain into a graphene film, besides a strong covalent bond, a weak interface effect such as a hydrogen bond can be formed between a polymer and a graphene nanosheet, and through the weak interface effect and the adjustment of the flexible polymer, the toughness (W. Cui, M.Z. Li, J.Y. Liu, B. Wang, C. Zha) of the graphene film can be greatly improved on the premise of not sacrificing too much strengthng, L. Jiang and Q. F. Cheng, ACS Nano2014, 8, 9511); even in the absence of covalent bonds, high strength and high toughness of graphene films can be achieved by only two weak interfacial interactions, such as hydrogen bonding and pi-pi interactions (m. Zhang, l. Huang, j. Chen, c. Li and g. Shi,Adv.Mater.2014, 26, 7588). These studies indicate that modulating the interfacial role in graphene films is key to determining their final mechanical properties.
A coordination bond is a relatively weak chemical bond having a strength generally ranging between weak hydrogen bonds, van der waals forces, and strong covalent bonds. Coordination bonds are also gradually tried to be applied to graphene materials, such as cross-linked graphene aerogel, hydrogel and the like, and the mechanical properties of the materials can be effectively improved. Moreover, it is generally simpler and faster to build coordination bonds between graphene and macromolecules than to build covalent bonds. Therefore, in the process of preparing the graphene film, coordination bonds and other weak bonds are simultaneously constructed, and the high-strength and high-toughness graphene film is prepared under the synergistic effect of various factors.
Disclosure of Invention
The invention aims to provide a method for preparing a high-strength, high-toughness and high-conductivity graphene film, which is simple to operate.
The invention provides a preparation method of a high-strength high-toughness high-conductivity graphene film, which comprises the following specific steps:
(1) mixing a small amount of rare earth metal ions, water-soluble polymer and Graphene Oxide (GO) to obtain uniform suspension or hydrosol; the rare earth metal ions and the water-soluble polymer containing the coordination group capable of being coordinated with the rare earth are introduced, so that various interactions including coordination bonds, hydrogen bonds and pi-pi actions can be simultaneously constructed in a system;
(2) casting or filtering the suspension or the hydrosol, and then drying to obtain a GO-based film;
(3) the GO-based thin film is reduced, cleaned and dried to obtain the graphene film with high strength, high toughness and high conductivity.
In the step (1), the rare earth metal ions may be any one or more of rare earth elements; the polymer is usually a water-soluble polymer containing a ligand group such as carboxyl, hydroxyl, or phenanthroline, for example, a water-soluble polymer such as phenanthroline-grafted polyacrylic acid (PAAP).
In the step (1), the rare earth metal ions are usually rare earth ions with a valence of 3, and can be added in the form of an aqueous solution of a rare earth compound with a valence of 3.
The rare earth compound can be a compound of one rare earth element or a mixture of a plurality of rare earth compounds.
In the above step (1), the GO may be prepared by one of a Marcano method, a Brodie method, a Staudenmaier method, a Hummers method, and various methods modified based on these methods.
Preferably, in the step (1), the GO is stored in a liquid form without being subjected to processes such as drying and ultrasonic treatment.
Preferably, in the step (1), the mass ratio of the water-soluble polymer to the original GO feeding materials is 1:99-10:90, namely, in the two materials, the water-soluble polymer accounts for 1-10%, the GO accounts for 90-99%, and the sum of the water-soluble polymer and the GO accounts for 100%.
Preferably, in the step (1), the rare earth metal ions account for 1-5% of the total mass of the polymer and GO.
Preferably, in the step (1), the total concentration of the polymer and GO is 3-5 mg mL-1。
Preferably, in the step (2), the material of the mold used for casting the hydrosol is one of a teflon plate, a glass plate and stainless steel.
Preferably, in the step (2), the drying temperature is room temperature to 80 ℃.
Preferably, in the step (3), the reducing agent for reduction is one of hydroiodic acid, hydrazine hydrate and vitamin solution.
Preferably, in the step (3), the cleaning agent for cleaning is water and absolute ethyl alcohol.
Preferably, in the step (3), the drying temperature is room temperature to 100 ℃.
The invention also discloses a graphene film prepared by the preparation method, and the thickness of the graphene film is 5-20 microns.
According to the method, three weak interactions are simultaneously constructed in the graphene film, including coordination bonds between graphene and macromolecules, hydrogen bonds between graphene and macromolecules, and pi-pi effects between graphene and macromolecules. The graphene film prepared by the invention has a typical compact layered structure, and is similar to a brick-mud structure of a natural shell. Under the synergistic effect of the multiple interface interactions, the graphene film has high strength and high toughness at the same time. Experimental results show that the mechanical strength of the graphene film can reach 183 MPa, and the fracture toughness can reach 19 MJ m-3. In addition, the graphene film has good conductivity, and the conductivity reaches 36.4S cm-1。
The method has the advantages of cheap raw materials, simple equipment, simple and convenient operation, high efficiency and large-scale production. The obtained graphene film has high strength, good toughness and excellent rigidity-toughness balance performance, and can be applied to the fields of artificial muscles, flexible electrodes, inductors and the like.
Detailed Description
For a further understanding of the present invention, the following preferred experimental embodiments are described in conjunction with the examples, but it should be understood that these descriptions are only for the purpose of further illustrating the features and advantages of the present invention, and are not intended to limit the claims of the present invention.
The embodiment of the invention discloses a preparation method of a high-strength, high-toughness and high-conductivity graphene film, which comprises the following steps:
(1) mixing a small amount of rare earth metal ions, water-soluble polymers and GO to obtain uniform hydrosol;
(2) casting the hydrosol in a mold, and drying to obtain a GO-based film;
(3) and soaking and reducing the GO-based film by using a reducing agent, cleaning and drying to obtain the graphene film.
In the invention, the size of GO is 2-50 μm, preferably 5-10 μm. The GO is stored in a liquid form without processes such as drying, ultrasound and the like,avoiding further GO size reduction. The total concentration of the polymer and GO is 3-5 mg mL-1Preferably 5mg mL-1. The GO accounts for 90-99% by mass, preferably 95% by mass of the total weight of GO and the polymer.
The water-soluble polymer needs to contain a polar functional group, so that a hydrogen bond can be formed between the water-soluble polymer and graphene; grafting phenanthroline and other side groups is favorable for forming coordination bonds with rare earth metals and forming pi-pi action with graphene. The weight ratio of the polymer in the total weight of GO and the polymer is 1-10%, preferably 5%.
The rare earth metal ions have strong coordination capacity and form coordination bonds with graphene or macromolecules. The rare earth is europium, terbium and other rare earth metals, preferably europium trichloride. The rare earth metal ions are generally in excess, about 1-5% of the total weight of GO and polymer.
And in the casting film forming process, evaporation is carried out under a preferable mild condition to obtain a flat and uniform film, the temperature is preferably room temperature-80 ℃, more preferably room temperature, and the time is about three days. The preferable PTFE mold of the mold for casting the film is convenient for separating the film.
The reduction process is aimed at reducing the oxidized graphene film to obtain a graphene film. The reducing agent is preferably hydroiodic acid, and the reduction temperature is room temperature and the reduction time is about 24 hours. The cleaning process mainly comprises the steps of washing off reducing agent residues and free rare earth ions and reacting macromolecules, and preferably comprises the steps of firstly washing with water and then soaking and washing with ethanol. The drying is preferably carried out at room temperature to 100 ℃ for 24 hours.
The thickness of the high-strength and high-toughness graphene film prepared by the method is 5-20 mu m.
In the preparation method of the graphene film, rare earth metal ion Eu can be used3+Uniformly dispersing water-soluble high-molecular phenanthroline-grafted polyacrylic acid (PAAP) and GO to prepare mixed sol, casting and evaporating to form a film, and carrying out chemical reduction, cleaning and drying to obtain the graphene film.
According to the invention, under the action of rare earth metal ions and macromolecules, graphene nanosheets are stacked into a compact layered structure. In the graphene film, the interface is in a direct formForming the synergistic effect of hydrogen bond, coordination bond and pi-pi action, and being beneficial to improving the mechanical property of the film. The mechanical strength of the graphene film can reach 183 MPa, and the fracture toughness can reach 19 MJ m-3. The conjugated structure of the graphene film is well restored by chemical reduction, and the graphene film also has good conductivity which reaches 36.4S cm-1。
The following are specific examples.
Example 1:
118.75 mg GO, 6.25 mg PAAP and 3.75 mg Eu3+Mixing well, preparing into 5mg mL-1The homogeneous hydrosol of (a). Casting the hydrosol in an area of 60 cm2And naturally evaporating at room temperature for three days in the tetrafluoro mold to obtain the GO membrane. And soaking the obtained GO membrane in a hydriodic acid solution with the concentration of 30wt% to react for 24 hours at room temperature. And repeatedly rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ in vacuum to obtain the graphene film with high strength, high toughness and high conductivity. The graphene film has the thickness of about 10 mu m, can be bent and folded, has the tensile breaking strength of 183 MPa and the breaking toughness of 19 MJ m-3The conductivity was 36.4S cm-1。
Example 2:
112.5 mg GO, 2.5mg PAAP and 3.75 mg Eu3+Mixing well, preparing into 5mg mL-1The homogeneous hydrosol of (a). Casting the hydrosol in an area of 60 cm2And naturally evaporating at room temperature for three days in the tetrafluoro mold to obtain the GO membrane. And soaking the obtained GO membrane in a hydriodic acid solution with the concentration of 30wt% to react for 24 hours at room temperature. And repeatedly rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ in vacuum to obtain the graphene film with high strength, high toughness and high conductivity. The graphene film has a thickness of about 9 μm, can be bent and folded, has a tensile breaking strength of 75 MPa and a breaking toughness of 5.5 MJ m-3The conductivity is 38S cm-1。
Example 3:
116.25 mg GO, 8.75 mg PAAP and 3.75 mg Eu3+Mixing well, preparing into 5mg mL-1The homogeneous hydrosol of (a). Casting the hydrosol in an area of 60 cm2ToAnd (4) naturally evaporating at room temperature for three days in a fluorine mold to obtain the GO membrane. And soaking the obtained GO membrane in a hydriodic acid solution with the concentration of 30wt% to react for 24 hours at room temperature. And repeatedly rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ in vacuum to obtain the graphene film with high strength, high toughness and high conductivity. The graphene film has the thickness of about 12 mu m, can be bent and folded, the tensile breaking strength reaches 115 MPa, and the breaking toughness can reach 5.5 MJ m-3The conductivity is 32S cm-1。
Example 4:
112.5 mg GO, 12.5 mg PAAP and 3.75 mg Eu3+Mixing well, preparing into 5mg mL-1The homogeneous hydrosol of (a). Casting the hydrosol in an area of 60 cm2And naturally evaporating at room temperature for three days in the tetrafluoro mold to obtain the GO membrane. And soaking the obtained GO membrane in a hydriodic acid solution with the concentration of 30wt% to react for 24 hours at room temperature. And repeatedly rinsing with deionized water and ethanol, and drying at the temperature of 60 ℃ in vacuum to obtain the graphene film with high strength, high toughness and high conductivity. The graphene film has the thickness of about 13.5 mu m, can be bent and folded, the tensile breaking strength reaches 108 MPa, and the fracture toughness reaches 7.5 MJ m-3The conductivity was 29.5S cm-1。
Claims (4)
1. A preparation method of a high-strength high-toughness high-conductivity graphene film is characterized by comprising the following specific steps:
(1) mixing rare earth metal ions, water-soluble polymers and graphene oxide GO to obtain uniform suspension or hydrosol; rare earth metal ions and water-soluble polymers containing coordination groups capable of being coordinated with rare earth are introduced, and various interactions including coordination bonds, hydrogen bonds and pi-pi actions are constructed in a system at the same time;
(2) casting or filtering the suspension or the hydrosol, and then drying to obtain a GO-based film;
(3) the GO-based thin film is subjected to reduction, cleaning and drying to obtain a high-strength high-toughness high-conductivity graphene film;
the polymer in the step (1) is selected from water-soluble polymers containing carboxyl, hydroxyl and phenanthroline ligand groups;
the rare earth metal ions in the step (1) are 3-valent rare earth ions and are added in the form of an aqueous solution of a 3-valent rare earth compound; here, the rare earth compound is a compound of one rare earth element, or a mixture of a plurality of rare earth compounds;
storing the GO in the step (1) in a liquid form;
in the step (1), the mass ratio of the water-soluble polymer to the original GO feeding material is 1:99-10:90, the amount of the rare earth metal ions is 1-5% of the total mass of the polymer and GO, and the total concentration of the polymer and GO is 3-5 mg mL-1。
2. The method according to claim 1, wherein the drying temperature in the step (2) is room temperature to 80 ℃.
3. The method according to claim 1 or 2, wherein in the step (3), the reducing agent for reduction is one of hydriodic acid, hydrazine hydrate, and a vitamin solution; the cleaning agent for cleaning is water and absolute ethyl alcohol; the drying temperature is room temperature-100 ℃.
4. The graphene film obtained by the production method according to any one of claims 1 to 3, wherein the thickness of the graphene film is 5 to 20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711415510.5A CN108147393B (en) | 2017-12-25 | 2017-12-25 | High-strength high-toughness high-conductivity graphene film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711415510.5A CN108147393B (en) | 2017-12-25 | 2017-12-25 | High-strength high-toughness high-conductivity graphene film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108147393A CN108147393A (en) | 2018-06-12 |
| CN108147393B true CN108147393B (en) | 2021-04-30 |
Family
ID=62465410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711415510.5A Active CN108147393B (en) | 2017-12-25 | 2017-12-25 | High-strength high-toughness high-conductivity graphene film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108147393B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533117B (en) * | 2020-05-13 | 2021-08-27 | 四川大学 | Metal ion crosslinked high-strength stable graphene oxide membrane and preparation method thereof |
| CN112111145B (en) * | 2020-08-21 | 2021-12-21 | 苏州市雄林新材料科技有限公司 | Conductive TPU film and preparation method thereof |
| CN116454538B (en) * | 2023-06-16 | 2023-10-10 | 山东华太新能源电池有限公司 | Battery diaphragm material for marine environment and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515560A (en) * | 2011-12-13 | 2012-06-27 | 江苏大学 | Method for preparing graphene/Ag composite conductive film |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
-
2017
- 2017-12-25 CN CN201711415510.5A patent/CN108147393B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515560A (en) * | 2011-12-13 | 2012-06-27 | 江苏大学 | Method for preparing graphene/Ag composite conductive film |
| CN105883781A (en) * | 2016-03-09 | 2016-08-24 | 王祉豫 | Preparation method of large-area reduced graphene oxide membrane |
Non-Patent Citations (1)
| Title |
|---|
| Graphene-Based Films with Integrated Strength and Toughnessvia a Novel Two-Step Method Combining Gel Casting and SurfaceCrosslinking;Shibing Ye等;《ChemNanoMat》;20160905(第2期);第817页左栏第3-18行，第820页左栏第14-16行、右栏试验部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108147393A (en) | 2018-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | A review of etching methods of MXene and applications of MXene conductive hydrogels | |
| Rana et al. | Highly conducting, extremely durable, phosphorylated cellulose-based ionogels for renewable flexible supercapacitors | |
| CN108147393B (en) | High-strength high-toughness high-conductivity graphene film and preparation method thereof | |
| Ai et al. | Highly flexible, self-healable and conductive poly (vinyl alcohol)/Ti3C2Tx MXene film and it’s application in capacitive deionization | |
| Li et al. | Double network hydrogels for energy/environmental applications: challenges and opportunities | |
| Bendi et al. | Metal Organic Framework-Derived Metal Phosphates as Electrode Materials for Supercapacitors. | |
| Guo et al. | A self-healable and easily recyclable supramolecular hydrogel electrolyte for flexible supercapacitors | |
| Wang et al. | Freestanding nanocellulose-composite fibre reinforced 3D polypyrrole electrodes for energy storage applications | |
| Huang et al. | Graphene oxide-based composite hydrogels with self-assembled macroporous structures | |
| Fan et al. | 3D conductive network-based free-standing PANI–RGO–MWNTs hybrid film for high-performance flexible supercapacitor | |
| Li et al. | Preparation and characterization of pH-and temperature-responsive nanocomposite double network hydrogels | |
| Zhu et al. | A facile assembly of 3D robust double network graphene/polyacrylamide architectures via γ-ray irradiation | |
| EP2660199A1 (en) | Composite material of carbon-coated graphene oxide, preparation method and application thereof | |
| CN109575755B (en) | Quaternized lignin dispersed graphene/carbon nanotube-based composite anticorrosive coating and preparation method and application thereof | |
| Zhuang et al. | A physically cross-linked self-healable double-network polymer hydrogel as a framework for nanomaterial | |
| Liu et al. | Robust self-floating covalent organic framework/chitosan aerogels for the efficient removal of sulfamerazine | |
| CN105789569B (en) | A kind of multilevel structure composite material and its preparation and application | |
| CN105968777B (en) | A kind of antistatic composite nano materials film and preparation method thereof | |
| Wang et al. | Hydrogel electrolyte based on sodium polyacrylate/KOH hydrogel reinforced with bacterial cellulose aerogel for flexible supercapacitors | |
| CN110752353B (en) | Flexible self-supporting tin diselenide/carbon nano tube composite film electrode material and preparation method and application thereof | |
| Xia et al. | 2D covalent organic framework-based core-shell structures for high-performance solar-driven steam generation | |
| Ding et al. | Properties of polyacrylamide hydrogel enhanced by kaolinite with expanded layer structure | |
| CN110964219B (en) | Nano cellulose membrane with high thermal conductivity and preparation method thereof | |
| Sun et al. | Sustainable β-cyclodextrin modified polyacrylamide hydrogel for highly efficient solar-driven water purification | |
| Huang et al. | A “two-birds-one-stone” strategy to enhance capacitive deionization performance of flexible Ti 3 C 2 T x MXene film electrodes by surface modification |
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 |