CN108147393A - A kind of high-strength and high ductility high conductivity graphene film and preparation method thereof - Google Patents
A kind of high-strength and high ductility high conductivity graphene film and preparation method thereof Download PDFInfo
- Publication number
- CN108147393A CN108147393A CN201711415510.5A CN201711415510A CN108147393A CN 108147393 A CN108147393 A CN 108147393A CN 201711415510 A CN201711415510 A CN 201711415510A CN 108147393 A CN108147393 A CN 108147393A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- preparation
- graphene film
- macromolecule
- graphene
- 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.)
- Granted
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 technical field of fine, and in particular to a kind of high-strength and high ductility high conductivity graphene film and preparation method thereof.The method of the present invention includes：A small amount of rare earth ion, macromolecule and graphene oxide are hybridly prepared into the uniform hydrosol, cast after air-drying film forming, successively obtains graphene film by reduction, cleaning, drying steps.The present invention three kinds of interactions of structure simultaneously, it is acted on including the π π between the coordinate bond between graphene oxide and rare earth ion, the hydrogen bond between graphene oxide and macromolecule, graphene oxide and macromolecule so that prepared modified graphene film has high intensity, high tenacity and good electric conductivity simultaneously.The method of the present invention raw material is cheap, easy to operate, is suitble to mass production, has good industrialized production basis and wide application prospect.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of high-strength and high ductility conductive graphene membrane and its preparation
Method.
Background technology
Graphene has the excellent properties such as large specific surface area, light weight, intensity height, conductivity height.By graphene nanometer sheet
The graphene film for being assembled into two dimension is successfully realized the application of graphene on a macroscopic scale.Up to the present, researcher
The graphene film of several functions is developed, and Preliminary Applications are in Heat Conduction Material, seperation film, electrode material and electronical display
The fields of grade.
In the exploitation of graphene film, it is an important topic to improve its mechanical performance.Researcher is by introducing high score
Son builds covalently cross-linked graphene nanometer sheet, can significantly improve intensity and modulus (Y. Tian, the Y. W. of graphene film
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).It is but this kind of strong
Covalent bond, which often leads to the thin elongation at break of graphene, to be reduced, and the fracture toughness for eventually leading to material is poor.It should for majority
It is one and its important index with the toughness of, material, therefore prepares the graphene film of rigidity-toughness balanced in practical applications particularly
It is important.Recently, researcher introduces flexible macromolecule chain in graphene film, other than strong covalent bond, macromolecule and graphite
Weaker interface interaction, such as hydrogen bond can also be formed between alkene nanometer sheet, passes through the effect of this weak interface and flexible macromolecule
It adjusts, under the premise of excessively intensity is not sacrificed, toughness (W. Cui, M. the Z. Li, J. of graphene film can be greatly improved
Y. Liu, B. Wang, C. Zhang, L. Jiang and Q. F. Cheng, ACS Nano2014, 8, 9511)；
Even in the case of no covalent bond, only pass through two kinds of weak interface interactions such as hydrogen bond and the synergistic effect of π-π effects, so that it may
With realize the high intensity of graphene film and high tenacity (M. Zhang, L. Huang, J. Chen, C. Li and G. Shi,Adv.Mater.2014, 26, 7588).These research shows that, it is to determine that it is final to adjust the interface interaction in graphene film
The key of mechanical performance.
Coordinate bond is a kind of weaker chemical bond, and strength range is typically in the range of weak hydrogen bond, Van der Waals force and strong is total to
Between valence link.Coordinate bond is also gradually attempted applied in grapheme material, such as cross-linked graphene aeroge and hydrogel, can
To effectively improve the mechanical performance of material.Moreover, the coordinate bond ratio structure covalent bond usually between structure graphene and macromolecule
It is more simple and fast.Therefore, the present invention during graphene film is prepared while builds coordinate bond and other weak bonds, various
Under the synergistic effect of factor, it is prepared into high-intensity and high-tenacity graphene film.
Invention content
The purpose of the present invention is to provide a kind of easy to operate, the side of the highly conductive graphene film of high-intensity and high-tenacity is prepared
Method.
The preparation method of the highly conductive graphene film of high-strength and high ductility provided by the invention, is as follows：
（1）By a small amount of rare earth ion, water soluble polymer and graphene oxide (GO) mix, obtain uniform suspension or
The hydrosol；Here rare earth ion is introduced and containing the water soluble polymer that coordinating group can be carried out with rare earth, it can be in body
A variety of interactions are built simultaneously in system, are acted on including coordinate bond, hydrogen bond and π-π；
（2）By above-mentioned suspension or hydrosol casting or filtering, then dry, obtain the film of GO bases；
（3）Above-mentioned GO base films obtain high-intensity and high-tenacity high conductivity graphene film by reduction, cleaning, drying.
Above-mentioned steps（1）In, the rare earth ion can be any one or more in rare earth element；The height
Molecule is typically the water soluble polymer containing ligand groups such as carboxyl, hydroxyl, Phens, and such as poly- the third of Phen grafting
The water soluble polymers such as olefin(e) acid (PAAP).
Above-mentioned steps（1）In, the rare earth ion is usually trivalent rare earth ion, can pass through trivalent rare earth compound
Aqueous solution form adds in.
Above-mentioned rare earth compound can be a kind of compound of rare earth element or mixing for a variety of rare earth compounds
Close object.
Above-mentioned steps（1）In, the GO can be Marcano methods, Brodie methods, Staudenmaier methods, Hummers
It is prepared by method and one kind of various methods for being improved on the basis of these methods.
Preferably, the step（1）In, the preservation in liquid form of the GO, without processes such as dry and ultrasounds.
Preferably, the step（1）In, the water soluble polymer and the original mass ratioes that feed intake of GO are 1:99-10:90,
That is in two kinds of materials, water soluble polymer 1-10%, GO 90-99%, the two and for 100%.
Preferably, the step（1）In, the rare earth ion is the 1 ~ 5% of macromolecule and GO gross masses.
Preferably, the step（1）In, the macromolecule and the total total concentrations of GO are 3 ~ 5 mg mL-1。
Preferably, the step（2）In, the material of mold that uses is tetrafluoro plate, glass plate and not when the hydrosol is cast
One kind in rust steel.
Preferably, the step（2）In, the drying temperature is room temperature ~ 80 DEG C.
Preferably, the step（3）In, the reducing agent of reduction is one in hydroiodic acid, hydrazine hydrate, vitamin solution
Kind.
Preferably, the step（3）In, the cleaning agent of cleaning is water and absolute ethyl alcohol.
Preferably, the step（3）In, the drying temperature is room temperature ~ 100 DEG C.
The invention also discloses graphene film made from a kind of above-mentioned preparation method, the thickness of the graphene film is 5 ~ 20
μm。
The method of the present invention constructs three kinds of weak interactions simultaneously in graphene film, including graphene and macromolecule it
Between coordinate bond, the hydrogen bond between graphene and macromolecule, the π-π between graphene and macromolecule act on.Prepared by the present invention
Graphene film has typical fine and close layer structure, " brick-mud " structure of similar natural seashell.In a variety of interface phase interactions
Under synergistic effect, which has high intensity and high tenacity simultaneously.The experimental results showed that the mechanics of the graphene film
Intensity can reach ~ 183 MPa, and fracture toughness can reach ~ 19 MJ m-3.In addition, the graphene film is also with good
Electric conductivity, conductivity reach 36.4 S cm-1。
The method of the present invention, raw material is cheap, and equipment is simple, easy to operate, efficient, can mass produce.Gained graphite
Alkene film-strength is big, good toughness, has excellent rigidity-toughness balanced performance, can be applied to artificial muscle, flexible electrode, inductor etc.
Field.
Specific embodiment
For a further understanding of the present invention, optimization experiment scheme of the present invention is described with reference to embodiments, still
It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses the preparation method of high-intensity and high-tenacity high conductivity graphene film, including following step
Suddenly：
（1）A small amount of rare earth ion, water soluble polymer and GO are mixed to get the uniform hydrosol；
（2）The hydrosol is poured and is cast from mold, is dried to obtain the film of GO bases；
（3）By the film of the GO bases by reducing agent soaking and reducing, cleaning, drying, graphene film is obtained.
In the present invention, the size of the GO is at 2 ~ 50 μm, preferably 5 ~ 10 μm.The preservation in liquid form of the GO,
Without processes such as dry and ultrasounds, GO sizes is avoided further to reduce.A concentration of 3 ~ 5 mg of the macromolecule and GO always
mL-1, preferably 5 mg mL-1.The GO accounts for mass ratio in GO and macromolecule gross weight and is classified as 90 ~ 99%, preferably 95%.
The water soluble polymer need to contain polar functional group, be conducive to form hydrogen bond between graphene；Grafting is adjacent luxuriant and rich with fragrance
The side groups such as sieve quinoline are conducive to form coordinate bond with rare earth metal, and π-π effects are formed between graphene.The macromolecule exists
Shared mass ratio is 1 ~ 10%, preferably 5% in GO and macromolecule gross weight.
The rare earth ion has stronger coordination ability, and coordinate bond is formed with graphene or macromolecule.Rare earth
Type is the rare earth metals such as europium, terbium, and preferably europium chloride is raw material.The rare earth ion is usually excessive, be approximately GO and
The 1 ~ 5% of macromolecule gross weight.
In casting film process, evaporation is to obtain the film of even uniform, preferably room temperature ~ 80 DEG C preferably under temperate condition, more
Preferably room temperature, three days or so time.The mold for pouring film forming, preferably tetrafluoro mold, convenient for the separation of film.
The purpose of reduction process is redox graphene film, obtains graphene film.The preferred hydroiodic acid of reducing agent, reduction temperature
Room temperature, about 24 h of time.The cleaning process is mainly to wash away reducing agent residual and free rare earth ion and the height for reaction
Molecule is preferably first washed and is washed in ethyl alcohol immersion.Preferred room temperature ~ 100 DEG C of drying, 24 h of time.
The high-intensity and high-tenacity graphene film thickness that the present invention is prepared is 5 ~ 20 μm.
In the preparation method of graphene film of the present invention, rare earth ion Eu can be used3+, water soluble polymer neighbour's Féraud
Polyacrylic acid (PAAP), the GO of quinoline grafting, three are uniformly dispersed, mixed sols are made, casting evaporation film forming, using chemistry
It restores, clean, be dried to obtain graphene film.
In the present invention, under the action of rare earth ion, macromolecule, graphene nanometer sheet is stacked into the graphene film
Fine and close layer structure.In the graphene film, interface directly forms the synergistic effect of hydrogen bond, coordinate bond and π-π effects, has
Conducive to the mechanical performance for improving film.The graphene film mechanical strength can reach ~ 183 MPa, and fracture toughness can reach ~
19 MJ m-3.Since electronation has restored the conjugated structure of graphene film well, the graphene film also has good
Electric conductivity, conductivity reach 36.4 S cm-1。
It is specific embodiment below.
Embodiment 1：
118.75 mg GO, 6.25 mg PAAP and 3.75 mg Eu3+Uniformly mixing, is configured to a concentration of 5 mg mL-1It is equal
The even hydrosol.The above-mentioned hydrosol is poured and casts from 60 cm of area2Tetrafluoro mold in, natural evaporation three days, obtain GO at room temperature
Film.Gained GO films are soaked in the hydroiodic acid solution of a concentration of 30wt%, and room temperature reaction is for 24 hours.By deionized water and ethyl alcohol repeatedly
Rinsing, 60 DEG C of vacuum are dried to obtain high intensity, high tenacity, highly conductive graphene film.The graphene film thickness is about 10 μm,
Flexible, foldable, tensile break strength is 183 MPa, and fracture toughness is up to 19 MJ m-3, conductivity is 36.4 S cm-1。
Embodiment 2：
112.5 mg GO, 2.5mg PAAP and 3.75 mg Eu3+Uniformly mixing, is configured to a concentration of 5 mg mL-1Uniform water
Colloidal sol.The above-mentioned hydrosol is poured and casts from 60 cm of area2Tetrafluoro mold in, natural evaporation three days, obtain GO films at room temperature.Institute
It obtains GO films to be soaked in the hydroiodic acid solution of a concentration of 30wt%, room temperature reaction is for 24 hours.It is rinsed repeatedly by deionized water and ethyl alcohol,
60 DEG C of vacuum is dried to obtain high intensity, high tenacity, highly conductive graphene film.The graphene film thickness is about 9 μm, flexible,
Foldable, tensile break strength reaches 75 MPa, and fracture toughness is up to 5.5 MJ m-3, conductivity is 38 S cm-1。
Embodiment 3：
116.25 mg GO, 8.75 mg PAAP and 3.75 mg Eu3+Uniformly mixing, is configured to a concentration of 5 mg mL-1It is equal
The even hydrosol.The above-mentioned hydrosol is poured and casts from 60 cm of area2Tetrafluoro mold in, natural evaporation three days, obtain GO at room temperature
Film.Gained GO films are soaked in the hydroiodic acid solution of a concentration of 30 wt%, and room temperature reaction is for 24 hours.It is anti-by deionized water and ethyl alcohol
Multiple rinsing, 60 DEG C of vacuum are dried to obtain high intensity, high tenacity, highly conductive graphene film.The graphene film thickness is about 12 μ
M, flexible, foldable, tensile break strength reaches 115 MPa, and fracture toughness is up to 5.5 MJ m-3, conductivity is 32 S
cm-1。
Embodiment 4：
112.5 mg GO, 12.5 mg PAAP and 3.75 mg Eu3+Uniformly mixing, is configured to a concentration of 5 mg mL-1It is uniform
The hydrosol.The above-mentioned hydrosol is poured and casts from 60 cm of area2Tetrafluoro mold in, natural evaporation three days, obtain GO films at room temperature.
Gained GO films are soaked in the hydroiodic acid solution of a concentration of 30wt%, and room temperature reaction is for 24 hours.It is floated repeatedly by deionized water and ethyl alcohol
It washes, 60 DEG C of vacuum is dried to obtain high intensity, high tenacity, highly conductive graphene film.The graphene film thickness is about 13.5 μm,
Flexible, foldable, tensile break strength reaches 108 MPa, and fracture toughness is up to 7.5 MJ m-3, conductivity is 29.5 S
cm-1。
Claims (10)
1. a kind of preparation method of the highly conductive graphene film of high-strength and high ductility, which is characterized in that be as follows：
（1）Rare earth ion, water soluble polymer and graphene oxide (GO) are mixed, obtain uniform suspension or water-soluble
Glue；Here introduce rare earth ion and containing can with rare earth carry out coordinating group water soluble polymer, in system simultaneously
A variety of interactions are built, are acted on including coordinate bond, hydrogen bond and π-π；
（2）By above-mentioned suspension or hydrosol casting or filtering, then dry, obtain the film of GO bases；
（3）Above-mentioned GO base films obtain high-intensity and high-tenacity high conductivity graphene film by reduction, cleaning, drying.
2. preparation method according to claim 1, which is characterized in that step（1）Described in rare earth ion be rare earth
Any one or more in element；The macromolecule be selected from containing carboxyl, hydroxyl, phenanthroline ligand group high water solubility
Molecule.
3. preparation method according to claim 2, which is characterized in that step（1）Described in rare earth ion for trivalent it is dilute
Native ion is added in by the aqueous solution form of trivalent rare earth compound；Here, the rare earth compound is a kind of rare earth element
The mixture of compound or a variety of rare earth compounds.
4. according to the preparation method described in one of claim 1-3, which is characterized in that step（1）Described in GO with liquid shape
Formula preserves.
5. preparation method according to claim 4, which is characterized in that step（1）Described in water soluble polymer and GO it is former
Beginning feeds intake mass ratio as 1:99-10:90.
6. preparation method according to claim 5, which is characterized in that step（1）In, the amount of the rare earth ion is
The 1 ~ 5% of macromolecule and GO gross masses.
7. according to the preparation method described in claim 1-3,5, one of 6, which is characterized in that step（1）In, the macromolecule and
A concentration of 3 ~ 5 mg mL total GO-1。
8. preparation method according to claim 7, which is characterized in that step（2）Described in drying temperature be room temperature ~ 80
℃。
9. according to the preparation method described in claim 1-3,5,6, one of 8, which is characterized in that step（3）In, reduction is gone back
Former agent is hydroiodic acid, one kind in hydrazine hydrate, vitamin solution；The cleaning agent of cleaning is water and absolute ethyl alcohol；The drying
Temperature is room temperature ~ 100 DEG C.
10. the graphene film obtained as the preparation method described in one of claim 1-9, thickness is 5 ~ 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 true CN108147393A (en) | 2018-06-12 |
| CN108147393B 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533117A (en) * | 2020-05-13 | 2020-08-14 | 四川大学 | Metal ion crosslinked high-strength stable graphene oxide membrane and preparation method thereof |
| CN112111145A (en) * | 2020-08-21 | 2020-12-22 | 东莞市雄林新材料科技股份有限公司 | Conductive TPU film and preparation method thereof |
| CN116454538A (en) * | 2023-06-16 | 2023-07-18 | 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 |
|---|
| SHIBING YE等: "Graphene-Based Films with Integrated Strength and Toughnessvia a Novel Two-Step Method Combining Gel Casting and SurfaceCrosslinking", 《CHEMNANOMAT》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533117A (en) * | 2020-05-13 | 2020-08-14 | 四川大学 | Metal ion crosslinked high-strength stable graphene oxide membrane and preparation method thereof |
| CN112111145A (en) * | 2020-08-21 | 2020-12-22 | 东莞市雄林新材料科技股份有限公司 | Conductive TPU film and preparation method thereof |
| CN116454538A (en) * | 2023-06-16 | 2023-07-18 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108147393B (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gan et al. | Bioinspired functionalization of MXenes (Ti3C2TX) with amino acids for efficient removal of heavy metal ions | |
| Hosseini et al. | Removal of methylene blue from wastewater using ternary nanocomposite aerogel systems: Carboxymethyl cellulose grafted by polyacrylic acid and decorated with graphene oxide | |
| Zhang et al. | Preparation of amine functionalized carbon nanotubes via a bioinspired strategy and their application in Cu2+ removal | |
| Peyvandi et al. | Surface-modified graphite nanomaterials for improved reinforcement efficiency in cementitious paste | |
| Xie et al. | Mussel inspired functionalization of carbon nanotubes for heavy metal ion removal | |
| CN108147393A (en) | A kind of high-strength and high ductility high conductivity graphene film and preparation method thereof | |
| WO2017219944A1 (en) | Method for preparing graphene-epoxy resin composite material | |
| CN103613755A (en) | Graphene/polyaniline nanometer composite material, preparation method and application | |
| CN109847661B (en) | Preparation method of graphene oxide and silver nanowire assembled ternary elastic hydrogel | |
| CN104032154A (en) | Graphene/metal matrix composite material and preparation method thereof | |
| Nie et al. | Preparation of amphoteric nanocomposite hydrogels based on exfoliation of montmorillonite via in-situ intercalative polymerization of hydrophilic cationic and anionic monomers | |
| CN104530653B (en) | A kind of preparation method of epoxy resin/graphite alkene/Nanometer Copper composite | |
| CN104403275A (en) | Modified grapheme/thermosetting resin composite material and preparation method thereof | |
| Mallakpour et al. | Ultrasonic-assisted biosurface modification of multi-walled carbon nanotubes with Thiamine and its influence on the properties of PVC/Tm-MWCNTs nanocomposite films | |
| CN106881466A (en) | Rare earth modified grapheme strengthens the preparation method of metal-based compound bar | |
| Hou et al. | Nanodiamond decorated graphene oxide and the reinforcement to epoxy | |
| CN111151765B (en) | Preparation method of three-dimensional structure nano carbon material reinforced copper-based composite material | |
| CN102093700A (en) | Method for preparing graphene/waterborne polyurethane conductive composite material | |
| Fu et al. | Biomimic modification of graphene oxide | |
| WO2016086628A1 (en) | Graphene-polyaniline modified carbon nanotube composite and preparation method therefor | |
| WO2010045889A1 (en) | Polymer reinforced composite | |
| CN106653159A (en) | Preparation method and application for composite elastomer containing graphene coated copper nanowire | |
| CN108079952A (en) | The preparation method of the carbon nanotubes of metal ion/LDHs composite materials in a kind of absorption ultra-pure ammonia | |
| Yang et al. | Hydroxylated graphene: A promising reinforcing nanofiller for nanoengineered cement composites | |
| CN109021948A (en) | A kind of preparation method of novel heavy crude thinner |
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 |