CN112010297A - Graphene oxide slurry for interlayer bonding of diamine organic matter, preparation method of graphene oxide slurry, graphene oxide film and preparation method of graphene oxide film - Google Patents
Graphene oxide slurry for interlayer bonding of diamine organic matter, preparation method of graphene oxide slurry, graphene oxide film and preparation method of graphene oxide film Download PDFInfo
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Abstract
The invention provides graphene oxide slurry for an interlayer bonding diamine organic matter and a preparation method thereof, and a graphene oxide film for an interlayer bonding diamine organic matter and a preparation method thereof. The preparation method of the graphene oxide slurry for the interlayer bonding diamine organic matter comprises the following steps: and adding the diamine organic matter aqueous solution into the graphene oxide aqueous dispersion for dispersion. The graphene oxide film prepared from the graphene oxide slurry of the interlayer bonded diamine organic matter can improve the flexibility of the graphene oxide film and reduce the probability of the graphene oxide film of damage, folding, fracture and other defects.
Description
Technical Field
The invention relates to a preparation process for modifying graphene oxide slurry by using diamine substances, belonging to the field of material synthesis and application.
Background
Graphene is a two-dimensional nanomaterial structure of hexagonal honeycomb lattice consisting of only carbon atoms. Since the discovery, it has attracted extensive attention and research due to its excellent mechanical, optical, electrical, and thermal properties. Graphene oxide is an oxide corresponding to graphene, and is obtained by bonding oxygen-containing functional groups such as hydroxyl, carboxyl, carbonyl, and epoxy groups to graphene sheets. Just because the graphene oxide sheet layers contain a large number of functional groups, the graphene oxide sheet layers can be stacked by self-assembly such as hydrogen bonding to form a macroscopic membrane material.
However, in the process of industrially preparing the graphene heat-conducting film, processing treatment needs to be performed on graphene oxide, and in the whole processing process, due to the fact that the graphene oxide film is poor in flexibility, defects such as breakage, folding and fracture are easily caused, the yield of the prepared graphene heat-conducting film is greatly reduced, and the enhancement of the mechanical property of the graphene oxide is an important problem to be solved.
Patent publication No. CN108002373A discloses a method for preparing large-area graphene material by "stitching method", in which nitrogen groups in diamine organic compounds whose two end groups of the molecular structure are primary amines are used to join with carboxyl groups of graphene oxide to form a network structure, so as to form continuous large-area graphene. In the patent technology, graphene oxide is directly dispersed in diamine organic matters, so that good dispersion of graphene is difficult to realize. Meanwhile, under the reaction condition of 100-200 ℃, which is described in the specification, only the effect of 'sewing' can be realized, and the graphene can not be obtained by removing a large amount of oxygen-containing groups of the graphene oxide. Therefore, the patent cannot really obtain graphene film products.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
In view of one or more of the problems of the prior art, the present invention is directed to improving the flexibility of a graphene oxide film and reducing the probability of the graphene oxide film being damaged, folded, broken, or the like.
The invention provides graphene oxide slurry with diamine organic matter bonded between layers, wherein the diamine organic matter is bonded between graphene oxide layers, and the diamine organic matter accounts for 0.08-1.5 wt%, preferably 1 wt% of the mass fraction of the graphene oxide.
According to one aspect of the invention, the bond is a chemical bond.
According to an aspect of the present invention, the content of the graphene oxide in the graphene oxide slurry is 1 to 6 wt%, preferably 4.5%.
According to one aspect of the invention, the diamine organic substance comprises one or a combination of two or more of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine.
Preferably, the diamine organic substance adopts ethylenediamine or p-phenylenediamine.
The invention also provides a preparation method of the graphene oxide slurry for the interlayer bonding diamine organic matter, which comprises the following steps: and adding the diamine organic matter aqueous solution into the graphene oxide aqueous dispersion for dispersion.
According to one aspect of the present invention, the graphene oxide aqueous dispersion has a mass fraction of graphene oxide of 1 to 6 wt%, preferably 4.5 wt%.
According to one aspect of the invention, the diamine organic substance comprises one or a combination of two or more of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine.
Preferably, the diamine organic substance adopts ethylenediamine or p-phenylenediamine.
According to one aspect of the invention, the mass fraction of the diamine organic compound in the diamine organic compound aqueous solution is 0.75 to 3.75 wt%, preferably 1.5 wt%.
According to one aspect of the invention, said dispersing comprises stirring or shaking.
Preferably, the time of dispersion is 1.5 to 2.5h, preferably 2 h.
In the graphene oxide aqueous dispersion, 1-6 wt% of graphene oxide is well dispersed, and the lamella is completely peeled off to form a single lamella structure.
Graphene oxide is immersed into water molecules in the water dispersion liquid, the water molecules open the graphene oxide layers, the negatively charged graphene oxide layers are mutually separated due to electrostatic repulsion, stirring, shaking and other modes are assisted, so that the graphene oxide can be well dispersed in the dispersion liquid, and meanwhile, the insertion of the opened graphene oxide between the layers as diamine organic matters in the next step is better realized. Graphene oxide is an oxide of graphene, and contains oxygen-containing functional groups such as hydroxyl groups, epoxy groups, carbonyl groups, and carboxyl groups. Carboxyl groups are mainly distributed on the edges of graphene oxide, while epoxy groups and hydroxyl groups are mostly distributed on the inner plane of graphene oxide sheets. The carbonyl groups are distributed in both the inner plane and the edges of the graphene oxide sheets.
C ═ O in carbonyl and carboxyl in the graphene oxide sheet layer is a carbon-oxygen double bond, so that the bond energy is relatively low, the activity is relatively high, and the stability is relatively low; and hydroxyl (-OH) and epoxy (-C-O-C-) are carbon-oxygen single bonds, so that the bond energy is relatively large and the activity is relatively weak. Diamine organic matters are easy to generate chemical bonding with carbonyl and carboxyl functional groups containing carbon-oxygen double bonds.
And adding the dispersed diamine organic matter aqueous solution into the graphene oxide aqueous dispersion, fully contacting the diamine organic matter with the completely stripped graphene oxide, entering the graphene oxide layers, and forming full contact with the sheets. The carbonyl group in the graphene oxide sheet layer has stronger chemical activity with the (C ═ O) functional group on the carboxyl group, and the carbonyl group and the (C ═ O) functional group are easy to chemically react with diamine organic molecules, so that the diamine organic molecules are bonded between the graphene oxide sheet layers, and the interaction between the layers can be enhanced.
The invention also provides a graphene oxide film with the diamine organic matter bonded between layers, wherein the graphene oxide film contains the diamine organic matter, and the diamine organic matter is bonded between layers of the graphene oxide film.
According to one aspect of the invention, the bond is a chemical bond.
According to one aspect of the present invention, the diamine organic compound accounts for 0.0008 to 0.09 wt%, preferably 0.045 wt%, of the mass of the graphene oxide.
According to one aspect of the invention, the diamine organic substance comprises one or a combination of two or more of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine.
Preferably, the diamine-based organic substance comprises ethylenediamine or p-phenylenediamine.
According to one aspect of the present invention, the tensile strength of the graphene oxide film in which the diamine-based organic substance is interlaminar bonded is 140-180 MPa. Due to the fact that diamine organic matters are bonded between graphene oxide layers, interaction force between layers is enhanced, and the tensile strength of the graphene oxide film is enhanced in a macroscopic mode.
The invention also provides a preparation method of the graphene oxide film of the interlayer bonding diamine organic matter, which comprises the following steps:
preparing graphene oxide slurry of the interlayer bonding diamine organic matter by adopting a method for preparing graphene oxide slurry of the interlayer bonding diamine organic matter; and
and coating the graphene oxide slurry of the interlayer bonding diamine organic matter, and drying to obtain the graphene oxide film of the interlayer bonding diamine organic matter.
According to one aspect of the invention, the thickness of the coating film is 1 to 3mm, preferably 2 mm.
According to one aspect of the invention, the temperature of the drying is 40-120 ℃, preferably 75 ℃; and/or the drying time is 30min-3h, preferably 1.5 h.
In the process of preparing the graphene oxide film by using the graphene oxide slurry, the graphene oxide lamella is self-assembled by virtue of hydrogen bonds, and diamine organic matters react with carbonyl and carboxyl of the graphene oxide and are linked on the lamella. Compared with a hydrogen bond formed by a graphene oxide sheet layer and water molecules, a chemical bond generated by the reaction of a diamine organic matter and carbonyl, carboxyl and the like in the graphene oxide sheet layer is more stable, as shown in fig. 1 and fig. 2, so that the diamine organic matter is used for enhancing the interaction between the graphene oxide sheet layers, enhancing the self-assembly film forming capability of graphene oxide, simultaneously improving the flexibility of the graphene oxide film and reducing the probability of damage, folding, fracture and the like in the process of preparing the graphene oxide film into the graphene heat conducting film.
The invention has the beneficial effects that:
the invention provides graphene oxide slurry for an interlaminar bonded diamine organic matter, which can enhance the interaction between graphene oxide layers, enables the graphene oxide to be self-assembled more easily to obtain a tightly stacked graphene oxide film, improves the flexibility of the graphene oxide film, and reduces the probability of the graphene oxide film of damage, folding, fracture and other defects.
The tensile strength of the graphene oxide film bonded by ethylenediamine and p-phenylenediamine is 150MPa and 175MPa respectively, while the tensile strength of the graphene oxide film not modified by diamine organic matter is about 90MPa, and the tensile strength is improved by 66.7% and 94.4% respectively. As shown in fig. 3, the tensile properties of the graphene oxide film modified with the diamine organic substance are greatly improved. As shown in FIG. 4, the graphene oxide film modified with ethylenediamine at a wavelength of 1700cm-1The absorbance of (a) was significantly reduced, indicating that ethylenediamine reacted with the C ═ O bonds, resulting in a reduction of the C ═ O bonds in the graphene oxide sheets.
The graphene oxide film with good flexibility is easy to transfer and process, the defects of fracture and the like caused by large film brittleness are reduced, the yield of graphene oxide film preparation is improved, and the industrial manufacturing efficiency of graphene heat-conducting film preparation is improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of ethylenediamine enhanced graphene oxide layer interactions;
FIG. 2 is a schematic representation of p-phenylenediamine enhanced graphene oxide layer interactions;
FIG. 3 is a graph showing the effect of mechanical tensile properties of a graphene oxide film in which a diamine-based organic substance is interlaminar bonded and a graphene oxide film in which a diamine-based organic substance is not interlaminar bonded;
FIG. 4 is a graph comparing infrared data for graphene oxide films to ethylene diamine modified graphene oxide films;
FIG. 5 is a pictorial representation of a graphene oxide film of interlayer bonded ethylene diamine of example 1B;
FIG. 6 is a pictorial representation of a graphene oxide film of interlayer bonded ethylene diamine of example 2B;
FIG. 7 is a pictorial representation of a graphene oxide film of interlayer-bonded p-phenylenediamine of example 3B;
FIG. 8 is a pictorial representation of a graphene oxide film of interlayer-bonded p-phenylenediamine of example 4B;
fig. 9 and 10 are pictorial views of the graphene oxide film of comparative example 5;
1-graphene oxide film modified by p-phenylenediamine, 2-graphene oxide film modified by ethylenediamine, and 3-graphene oxide film without diamine organic matter.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
As a first embodiment of the present invention, there is shown a graphene oxide slurry in which a diamine-based organic substance is chemically bonded between graphene oxide layers, the diamine-based organic substance accounting for 0.08 to 1.5 wt% of the mass fraction of the graphene oxide, for example: 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.11 wt%, 0.12 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.60 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1.0 wt%, 1.05 wt%, 1.1 wt%, 1.15 wt%, 1.2 wt%, 1.25 wt%, 1.3 wt%, 1.35 wt%, 1.4 wt%, 1.45 wt%, 1.46 wt%, 1.47 wt%, 1.48 wt%, 1.49 wt%, 1.5 wt%, etc. In a preferred embodiment, the diamine-based organic substance accounts for 1 wt% of the mass fraction of the graphene oxide. In the graphene oxide slurry, the content of graphene oxide is 1 to 6 wt%, for example: 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8 wt%, 5 wt%, 5.2 wt%, 5.3 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5.8 wt%, 5.9 wt%, 6 wt%, etc. In a preferred embodiment, the content of graphene oxide in the graphene oxide slurry is 4.5 wt%. The diamine organic matter comprises one or the combination of more than two of ethylenediamine, p-phenylenediamine, adipamide or diethylene diamine. In a preferred embodiment, the diamine-based organic compound includes ethylenediamine or p-phenylenediamine.
As a second embodiment of the present invention, a method for preparing a graphene oxide slurry of an interlayer-bonded organic diamine compound is presented, including: and adding the diamine organic matter aqueous solution into the graphene oxide aqueous dispersion for dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide is 1-6 wt%, for example: 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 5.6 wt%, 5.7 wt%, 5.8 wt%, 5.9 wt%, 6 wt%, etc. As a preferred embodiment, the mass fraction of graphene oxide in the slurry is 4.5 wt%. The diamine organic matter comprises one or the combination of more than two of ethylenediamine or p-phenylenediamine, adipamide or diethylene diamine. In a preferred embodiment, the diamine-based organic compound includes ethylenediamine or p-phenylenediamine. The mass fraction of the diamine organic matters in the diamine organic matter aqueous solution is 0.75-3.75 wt%, for example: 0.75 wt%, 0.85 wt%, 0.95 wt%, 1 wt%, 1.01 wt%, 1.02 wt%, 1.03 wt%, 1.04 wt%, 1.05 wt%, 1.08 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.45 wt%, 2.46 wt%, 2.47 wt%, 2.48 wt%, 2.49 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.75 wt%, etc. In a preferred embodiment, the mass fraction of the diamine-based organic substance in the aqueous solution of the diamine-based organic substance is 1.5 wt%. Dispersing includes stirring or shaking. The dispersion time is 1.5-2.5h, for example: 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h and the like. In a preferred embodiment, the time for dispersion is 2 hours.
In the graphene oxide aqueous dispersion, 1-6 wt% of graphene oxide is well dispersed, and the sheets are completely peeled off, the graphene oxide is immersed in water molecules between the graphene oxide layers in the aqueous dispersion, and the water molecules, epoxy groups and hydroxyl groups form hydrogen bonds to open the graphene oxide layers. The negatively charged graphene oxide lamellae are separated from each other by electrostatic repulsion, so that the graphene oxide lamellae are relatively well dispersed in the dispersion.
Graphene oxide is an oxide of graphene, and contains oxygen-containing functional groups such as hydroxyl groups, epoxy groups, carbonyl groups, and carboxyl groups. Carboxyl groups are mainly distributed on the edges of graphene oxide, while epoxy groups and hydroxyl groups are mostly distributed on the inner plane of graphene oxide sheets. The carbonyl groups are distributed in both the inner plane and the edges of the graphene oxide sheets.
C ═ O in carbonyl and carboxyl in the graphene oxide sheet layer is a carbon-oxygen double bond, so that the bond energy is relatively low, the activity is relatively high, and the stability is relatively low; and hydroxyl (-OH) and epoxy (-C-O-C-) are carbon-oxygen single bonds, so that the bond energy is relatively large and the activity is relatively weak. Diamine organic matters are easy to generate chemical bonding with carbonyl and carboxyl functional groups containing carbon-oxygen double bonds.
And adding the dispersed diamine organic matter aqueous solution into the graphene oxide aqueous dispersion, fully contacting the diamine organic matter with the completely stripped graphene oxide, entering the graphene oxide layers, and forming full contact with the sheets. The carbonyl group in the graphene oxide sheet layer has stronger chemical activity with the (C ═ O) functional group on the carboxyl group, and the carbonyl group and the (C ═ O) functional group are easy to chemically react with diamine organic molecules, so that the diamine organic molecules are bonded between the graphene oxide sheet layers, and the interaction between the layers can be enhanced.
In a third embodiment of the present invention, a graphene oxide film in which a diamine-based organic substance is bonded between layers is shown, in which the graphene oxide film contains the diamine-based organic substance, and the diamine-based organic substance is bonded between the graphene oxide layers by a chemical bond. The diamine organic matters account for 0.0008-0.09 wt% of the mass of the graphene oxide, such as: 0.0008 wt%, 0.0009 wt%, 0.001 wt%, 0.0011 wt%, 0.0012 wt%, 0.0015 wt%, 0.002 wt%, 0.0025 wt%, 0.003 wt%, 0.0035 wt%, 0.004 wt%, 0.0045 wt%, 0.005 wt%, 0.0055 wt%, 0.0060 wt%, 0.0065 wt%, 0.007 wt%, 0.0075 wt%, 0.008 wt%, 0.0085 wt%, 0.009 wt%, 0.0095 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.085 wt%, 0.086 wt%, 0.087 wt%, 0.088 wt%, 0.089 wt%, 0.0895 wt%, 0.09 wt%, etc. In a preferred embodiment, the diamine-based organic substance accounts for 0.045 wt% of the mass of the graphene oxide. The diamine organic matter comprises one or the combination of more than two of ethylenediamine, p-phenylenediamine, adipamide or diethylene diamine. In a preferred embodiment, ethylenediamine or p-phenylenediamine is used as the diamine-based organic compound. The tensile strength of the graphene oxide film bonded with the diamine organic matter between layers is 140-180MPa, for example: 140MPa, 141MPa, 142MPa, 143MPa, 144MPa, 145MPa, 147MPa, 148MPa, 150MPa, 152MPa, 158MPa, 160MPa, 162MPa, 165MPa, 167MPa, 168MPa, 170MPa, 172MPa, 175MPa, 178MPa, 179MPa, 180MPa, etc., and the like, which is 66.7 to 94.4% higher than a graphene oxide film without an organic diamine bonded between layers, for example: 66.7%, 67%, 68%, 69%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 94.4%, etc.
As a fourth embodiment of the present invention, a method for producing a graphene oxide film in which a diamine-based organic substance is interlaminated is disclosed, the method including: preparing graphene oxide slurry of the interlayer bonding diamine organic matter by adopting a method for preparing graphene oxide slurry of the interlayer bonding diamine organic matter; and coating the graphene oxide slurry of the interlayer bonding diamine organic matter, and drying to obtain the graphene oxide film of the interlayer bonding diamine organic matter. The thickness of the coating film is 1 to 3mm, for example: 1mm, 1.01mm, 1.02mm, 1.03mm, 1.04mm, 1.05mm, 1.08mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 1.95mm, 1.96mm, 1.97mm, 1.98mm, 1.99mm, 2mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, 2.92mm, 2.95mm, 2.96mm, 2.97mm, 2.98mm, 2.99mm, 3mm, etc. In a preferred embodiment, the thickness of the coating film is 2 mm. The temperature of drying is 40-120 ℃, for example: 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, etc., as a preferred embodiment, the drying temperature is 75 ℃; and/or the drying time is 30min-3h, for example: 30min, 40min, 45min 50min, 55min, 60min, 1h15min, 1h30min, 1h45min, 2h15min, 2h30min, 2h45min, 2h50min, 2h55min, 3h, etc., and as a preferred embodiment, the drying time is 1.5 h.
In the process of preparing the graphene oxide film by using the graphene oxide slurry, the graphene oxide lamella is self-assembled by virtue of a hydrogen bond, and diamine organic matters react with carbonyl and carboxyl of the graphene oxide and are linked on the lamella. Compared with a hydrogen bond formed by a graphene oxide sheet layer and water molecules, a chemical bond generated by the reaction of a diamine organic matter and carbonyl, carboxyl and the like in the graphene oxide sheet layer is more stable, as shown in fig. 1 and fig. 2, so that the diamine organic matter is used for enhancing the interaction between the graphene oxide sheet layers, enhancing the self-assembly film forming capability of graphene oxide, simultaneously improving the flexibility of the graphene oxide film and reducing the probability of damage, folding, fracture and the like in the process of preparing the graphene oxide film into the graphene heat conducting film.
The advantages of the invention are further illustrated by the following examples and comparative examples:
example 1A:
this example shows a method for preparing graphene oxide slurry with ethylene diamine interlayer bonding.
1) Preparing a graphene oxide aqueous dispersion:
and mixing the graphene oxide filter cake with deionized water to prepare 898g of graphene oxide slurry, and fully stirring and uniformly shaking the slurry by using a stirrer to obtain the graphene oxide aqueous dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide was 5.77%.
2) Preparing an ethylene diamine aqueous solution:
adding 2ml of ethylenediamine solution with the mass fraction of 99.00% into 100ml of deionized water, and uniformly stirring.
3) Slowly adding the ethylenediamine aqueous solution prepared in the step 2) into the graphene oxide aqueous dispersion prepared in the step 1), and uniformly stirring to obtain the graphene oxide slurry with the ethylenediamine bonded between layers.
Example 1B:
this example illustrates a process for preparing a graphene oxide film of interbonded ethylene diamine using the graphene oxide slurry of interbonded ethylene diamine of example 1A.
The graphene oxide slurry of interlayer-bonded ethylenediamine of example 1A was coated into a 2mm film and dried at 75 ℃ for 90min to obtain a graphene oxide film of interlayer-bonded ethylenediamine (as shown in fig. 5).
The tensile strength of the graphene oxide film bonded with ethylenediamine between layers is 150 MPa.
Example 2A:
this example shows a method for preparing graphene oxide slurry with ethylene diamine interlayer bonding.
1) Preparing a graphene oxide aqueous dispersion:
adding deionized water into graphene oxide aqueous slurry with the solid content of 6.00% to prepare 898g of graphene oxide slurry, and fully stirring and uniformly shaking the graphene oxide slurry by a stirrer to obtain the graphene oxide aqueous dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide was 5.77%.
2) Preparing an ethylene diamine aqueous solution:
adding 2ml of ethylenediamine solution with the mass fraction of 99.00% into 100ml of deionized water, and uniformly stirring.
3) Slowly adding the ethylenediamine aqueous solution prepared in the step 2) into the graphene oxide aqueous dispersion prepared in the step 1), and uniformly stirring to obtain the graphene oxide slurry with the ethylenediamine bonded between layers.
Example 2B:
this example illustrates a process for preparing a graphene oxide film of interbonded ethylene diamine using the graphene oxide slurry of interbonded ethylene diamine of example 2A.
The graphene oxide slurry of interlayer-bonded ethylenediamine of example 2A was coated into a 2mm film and dried at 75 ℃ for 90min to obtain a graphene oxide film of interlayer-bonded ethylenediamine (as shown in fig. 6).
The tensile strength of the graphene oxide film with the ethylene diamine bonded between layers is 147 MPa.
Example 3A:
this example shows a method for preparing graphene oxide slurry with interlayer bonded p-phenylenediamine.
1) Preparing a graphene oxide aqueous dispersion:
mixing graphene oxide with deionized water to prepare graphene oxide slurry with the mass of 898g, and fully stirring and uniformly shaking the slurry by a stirrer to obtain the graphene oxide aqueous dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide was 5.77%.
2) Preparation of an aqueous solution of p-phenylenediamine:
adding 2ml of p-phenylenediamine solution with the mass fraction of 99.00 percent into 100ml of deionized water, and uniformly stirring.
3) Slowly adding the p-phenylenediamine aqueous solution prepared in the step 2) into the graphene oxide aqueous dispersion prepared in the step 1), and uniformly stirring to obtain graphene oxide slurry with interlayer bonded p-phenylenediamine.
Example 3B:
this example illustrates a process for preparing a graphene oxide film of interlayer-bonded p-phenylenediamine using the graphene oxide slurry of interlayer-bonded p-phenylenediamine of example 3A.
The graphene oxide slurry of interlayer-bonded p-phenylenediamine of example 3A was coated into a 2mm film and dried at 75 ℃ for 90min to obtain a graphene oxide film of interlayer-bonded p-phenylenediamine (as shown in fig. 7).
The tensile strength of the graphene oxide film bonded with p-phenylenediamine between layers is 175 MPa.
Example 4A:
this example shows a method for preparing graphene oxide slurry with interlayer bonded p-phenylenediamine.
1) Preparing a graphene oxide aqueous dispersion:
adding deionized water into graphene oxide aqueous slurry with the solid content of 5.92% to prepare 898g of graphene oxide slurry, and fully stirring and uniformly shaking the graphene oxide slurry by a stirrer to obtain the graphene oxide aqueous dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide was 5.77%.
2) Preparation of an aqueous solution of p-phenylenediamine:
adding 2ml of p-phenylenediamine solution with the mass fraction of 99.00 percent into 100ml of deionized water, and uniformly stirring.
3) Slowly adding the p-phenylenediamine aqueous solution prepared in the step 2) into the graphene oxide aqueous dispersion prepared in the step 1), and uniformly stirring to obtain graphene oxide slurry with interlayer bonded p-phenylenediamine.
Example 4B:
this example illustrates a process for preparing a graphene oxide film of interlayer-bonded p-phenylenediamine using the graphene oxide slurry of interlayer-bonded p-phenylenediamine of example 4A.
The graphene oxide slurry of interlayer-bonded p-phenylenediamine of example 4A was coated into a 2mm film and dried at 75 ℃ for 90min to obtain a graphene oxide film of interlayer-bonded p-phenylenediamine (as shown in fig. 8).
The tensile strength of the graphene oxide film bonded with p-phenylenediamine between layers is 167 MPa.
Comparative example 5:
this comparative example shows a process for preparing graphene oxide.
1) Preparing a graphene oxide aqueous dispersion:
and mixing the graphene oxide with deionized water, fully stirring by using a stirrer, and uniformly shaking to obtain the graphene oxide aqueous dispersion. In the graphene oxide aqueous dispersion, the mass fraction of graphene oxide was 5.77%.
2) The graphene oxide slurry was coated into a 2mm film and dried at 75 ℃ for 90min to obtain a graphene oxide film (as shown in fig. 9 and 10).
The graphene oxide film had a tensile strength of 90 MPa.
Examples 1-4 and comparative example 5 were compared by the following table:
the table shows that the diamine organic matter is bonded between the layers of the graphene oxide, so that the bonding force between the layers of the graphene oxide film and the bonding force between graphene oxide sheets are stronger, and the tensile strength of the graphene oxide film is greatly improved.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The graphene oxide slurry bonded with the diamine organic matter between layers is characterized in that the diamine organic matter is bonded between graphene oxide layers, and the diamine organic matter accounts for 0.08-1.5 wt%, preferably 1 wt% of the mass fraction of the graphene oxide slurry.
2. The graphene oxide slurry according to claim 1, wherein the bonding is chemical bonding;
preferably, in the graphene oxide slurry, the mass fraction of graphene oxide is 1-6 wt%, preferably 4.5 wt%;
preferably, the diamine organic substance comprises one or a combination of more than two of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine, preferably ethylenediamine or p-phenylenediamine.
3. The method for preparing graphene oxide slurry for interlayer bonding of diamine-based organic compounds according to claim 1 or 2, comprising: and adding the diamine organic matter aqueous solution into the graphene oxide aqueous dispersion for dispersion.
4. The method for preparing graphene oxide slurry for interlayer bonding of diamine organic compounds according to claim 3, wherein the graphene oxide aqueous dispersion comprises 1-6 wt%, preferably 4.5 wt% of graphene oxide;
preferably, the diamine organic substance comprises one or a combination of more than two of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine, preferably ethylenediamine or p-phenylenediamine;
preferably, the mass fraction of the diamine organic matters in the diamine organic matter aqueous solution is 0.75-3.75 wt%, preferably 1.5 wt%;
preferably, the diamine organic matter accounts for 0.08-1.5 wt%, preferably 1 wt% of the mass fraction of the graphene oxide slurry;
preferably, the dispersing comprises stirring or shaking;
preferably, the time of dispersion is 1.5 to 2.5h, preferably 2 h.
5. A graphene oxide film with diamine organic matter bonded between layers is characterized in that the graphene oxide film contains diamine organic matter, and the diamine organic matter is bonded between graphene oxide layers;
preferably, the bond is a chemical bond;
preferably, the diamine organic matter accounts for 0.0008-0.09 wt% of the mass of the graphene oxide, and preferably 0.045 wt%;
preferably, the diamine organic substance comprises one or a combination of more than two of ethylenediamine, p-phenylenediamine, adipamide or diethylenediamine, preferably ethylenediamine or p-phenylenediamine;
preferably, the tensile strength of the graphene oxide film of the interlayer bonded diamine organic matter is 140-180 MPa.
6. A preparation method of a graphene oxide film of an interlayer bonding diamine organic matter is characterized by comprising the following steps:
preparing graphene oxide slurry of an interlayer bonding diamine organic substance by using the method of claim 3 or 4; and
and coating the graphene oxide slurry of the interlayer bonding diamine organic matter, and drying to obtain the graphene oxide film of the interlayer bonding diamine organic matter.
7. The method for preparing the graphene oxide film in which the diamine organic substance is interlaminated according to claim 4, wherein the thickness of the coating film is 1 to 3mm, preferably 2 mm;
preferably, the temperature of the drying is 40-120 ℃, preferably 75 ℃; and/or the drying time is 30min-3h, preferably 1.5 h.
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| CN202210422084.2A CN114735688A (en) | 2019-05-31 | 2019-05-31 | Graphene oxide slurry for interlayer bonding of diamine organic matter, preparation method of graphene oxide slurry, graphene oxide film and preparation method of graphene oxide film |
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